Unterscheidung von Stickstoff- und Phosphor-Inversion, Rotation um die N-P-Bindung und Ligandenaustausch am Phosphor

1968 ◽  
Vol 23 (6) ◽  
pp. 759-766 ◽  
Author(s):  
D. Imbery ◽  
H. Friebolin

A large number of aminophosphines were prepared to study the kinetic processes. It could be shown that at room temperature there is rapid nitrogen-inversion but slow phosphorous-inversion. At higher temperatures ( + 80 °C), a rapid chlorine-exchange takes place with inversion of configuration at phosphorous. At low temperatures ( — 80 °C), rotation around the N-P-bond was slow. A dependence of the barrier of rotation on the size of the substituents could be recognized. It is possible that pπ-dπ-bonding is partially responsible for the relatively high barrier of rotation compared with derivatives of ethane and hydrazine.

Author(s):  
Chandrakant Sarode ◽  
Sachin Yeole ◽  
Ganesh Chaudhari ◽  
Govinda Waghulde ◽  
Gaurav Gupta

Aims: To develop an efficient protocol, which involves an elegant exploration of the catalytic potential of both the room temperature and surfactant ionic liquids towards the synthesis of biologically important derivatives of 2-aminothiazole. Objective: Specific heat capacity data as a function of temperature for the synthesized 2- aminothiazole derivatives has been advanced by exploring their thermal profiles. Method: The thermal gravimetry analysis and differential scanning calorimetry techniques are used systematically. Results: The present strategy could prove to be a useful general strategy for researchers working in the field of surfactants and surfactant based ionic liquids towards their exploration in organic synthesis. In addition to that, effect of electronic parameters on the melting temperature of the corresponding 2-aminothiazole has been demonstrated with the help of thermal analysis. Specific heat capacity data as a function of temperature for the synthesized 2-aminothiazole derivatives has also been reported. Conclusion: Melting behavior of the synthesized 2-aminothiazole derivatives is to be described on the basis of electronic effects with the help of thermal analysis. Additionally, the specific heat capacity data can be helpful to the chemists, those are engaged in chemical modelling as well as docking studies. Furthermore, the data also helps to determine valuable thermodynamic parameters such as entropy and enthalpy.


2021 ◽  
Vol 26 (2) ◽  
pp. 47
Author(s):  
Julien Eustache ◽  
Antony Plait ◽  
Frédéric Dubas ◽  
Raynal Glises

Compared to conventional vapor-compression refrigeration systems, magnetic refrigeration is a promising and potential alternative technology. The magnetocaloric effect (MCE) is used to produce heat and cold sources through a magnetocaloric material (MCM). The material is submitted to a magnetic field with active magnetic regenerative refrigeration (AMRR) cycles. Initially, this effect was widely used for cryogenic applications to achieve very low temperatures. However, this technology must be improved to replace vapor-compression devices operating around room temperature. Therefore, over the last 30 years, a lot of studies have been done to obtain more efficient devices. Thus, the modeling is a crucial step to perform a preliminary study and optimization. In this paper, after a large introduction on MCE research, a state-of-the-art of multi-physics modeling on the AMRR cycle modeling is made. To end this paper, a suggestion of innovative and advanced modeling solutions to study magnetocaloric regenerator is described.


Introduction .—In nearly all the previous determinations of the ratio of the specific heats of gases, from measurements of the pressures and temperature before and after an adiabatic expansion, large expansion chambers of fror 50 to 130 litres capacity have been used. Professor Callendar first suggests the use of smaller vessels, and in 1914, Mercer (‘Proc. Phys. Soc.,’ vol. 26 p. 155) made some measurements with several gases, but at room temperature only, using volumes of about 300 and 2000 c. c. respectively. He obtained values which indicated that small vessels could be used, and that, with proper corrections, a considerable degree of accuracy might be obtained. The one other experimenter who has used a small expansion chamber, capacity about 1 litre, is M. C. Shields (‘Phys. Rev.,’ 1917), who measured this ratio for air and for hydrogen at room temperature, about 18° C., and its value for hydroger at — 190° C. The chief advantage gained by the use of large expansion chambers is that no correction, or at the most, a very small one, has to be made for any systematic error due to the size of the containing vessels, but it is clear that, in the determinations of the ratio of the specific heats of gases at low temperatures, the use of small vessels becomes a practical necessity in order that uniform and steady temperature conditions may be obtained. Owing, however, to the presence of a systematic error depending upon the dimensions of the expansion chamber, the magnitude of which had not been definitely settled by experiment, the following work was undertaken with the object of investigating the method more fully, especially with regard to it? applicability to the determination of this ratio at low temperatures.


Visual purple is soluble and stable in a mixture of glycerol and water (3:1). At room temperature the spectrum of such a solution is identical with that of the aqueous solution. At — 73° C the peak of the absorption curve is higher and narrower than at room temperature, and it is shifted towards longer waves. The product of photodecomposition at — 73° C has a spectrum in ­ dependent of pH and is at low temperatures thermostable and photostable, but at room temperature it decomposes therm ally to indicator yellow. The primary product appears to be identical with transient orange. The quantum yields of the photoreaction at low and at room temperature are of the same order.


1995 ◽  
Vol 403 ◽  
Author(s):  
D. V. Dimitrov ◽  
A. S. Murthy ◽  
G. C. Hadjipanayis ◽  
C. P. SWANN

AbstractFe-O and Co-O films were prepared by DC magnetron sputtering in a mixture of Ar and O2 gases. By varying the oxygen to argon ratio, oxide films with stoichiometry FeO, Fe3O4, α-Fe2O3, CoO and Co3O4 were produced. TEM studies showed that the Fe – oxide films were polycrystalline consisting of small almost spherical grains, about 10 nm in size. Co-O films had different microstructure with grain size and shape dependent on the amount of oxygen. X-ray diffraction studies showed that the grains in Fe-O films were randomly oriented in contrast to Co-O films in which a <111> texture was observed. Pure FeO and α-Fe2O3 films were found to be superparamagnetic at room temperature but strongly ferromagnetic at low temperatures in contrast to the antiferromagnetic nature of bulk samples. A very large shift in the hysteresis loop, about 3800 Oe, was observed in field cooled Co-CoO films indicating the presence of a large unidirectional exchange anisotropy.


2000 ◽  
Vol 29 (3) ◽  
pp. 489-496 ◽  
Author(s):  
Alfredo O. R. Carvalho ◽  
Luiz G. E. Vieira

High quality DNA for molecular studies can be easily extracted from fresh specimens. However, live samples are difficult to keep for long periods thus making their preservation a serious problem, specially when they are collected and transported from remote locations. In order to establish an efficient method to preserve Atta spp. (leaf-cutting ants) for RAPD analysis, six different storage methods were examined: 1) -70°C; 2) 95% ethanol at -20°C; 3) 95% ethanol at 4°C; 4) 95% ethanol at room temperature; 5) silica gel at room temperature; and 6) buffer (0.25 M EDTA, 2.5% SDS, 0.5 M Tris-HCl, pH 9.2) at room temperature. DNA was extracted (Cheung et al., 1993 - modified) and examined after 90, 210 and 360 days of storage. Freshly killed specimens were used as control. DNA yield was measured with a minifluorometer. DNA quality was determined by scanning photographs with a densitometer and the integral of the scan was calculated for DNA of size > 9.4 kb. Data were analyzed using a completely randomized split-plot design with four replicates. All methods were efficient to preserve Atta spp. DNA up to 210 days. At 360 days, DNA was degraded only in 95% ethanol at room temperature, which resulted in RAPD profiles with missing bands. Although preservation at low temperatures is recommended for long periods, methods using silica gel and buffer can be considered satisfactory alternatives when refrigeration and transportation are limiting factors.


The magnetic and other related properties of neodymium sulphate have been the subject of numerous investigations in recent years, but there is still a remarkable conflict of evidence on all the essential points. The two available determinations of the susceptibility of the powdered salt at low temperatures, those of Gorter and de Haas (1931) from 290 to 14° K and of Selwood (1933) from 343 to 83° K both fit the expression X ( T + 45) = constant over the range of temperature common to both, but the constants are not the same and the susceptibilities at room temperature differ by 11%. The fact that the two sets of results can be converted the one into the other by multiplying throughout by a constant factor suggested that the difference in the observed susceptibilities was due to some error of calibration. It could, however, also be due to the different purity of the samples examined though the explanation of the occurrence of the constant factor is then by no means obvious. From their analysis of the absorption spectrum of crystals of neodymium sulphate octahydrate Spedding and others (1937) conclude that the crystalline field around the Nd+++ ion is predominantly cubic in character since they find three energy levels at 0, 77 and 260 cm. -1 .* Calculations of the susceptibility from these levels reproduce Selwood’s value at room temperature but give no agreement with the observations-at other temperatures. On the other hand, Penney and Schlapp (1932) have shown that Gorter and de Haas’s results fit well on the curve calculated for a crystalline field of cubic symmetry and such a strength that the resultant three levels lie at 0, 238 and 834 cm. -1 , an overall spacing almost three times as great as Spedding’s.


2016 ◽  
Vol 27 (4) ◽  
pp. 1265-1278 ◽  
Author(s):  
Mateusz Kuprianowicz ◽  
Marcin Kaźmierczak ◽  
Hanna Wójtowicz-Rajchel

The photochemical decomposition of hydrogen sulphide has been investigated at pressures between 8 and 550 mm of mercury and at temperatures between 27 and 650° C, using the narrow cadmium line ( λ 2288) and the broad mercury band (about λ 2550). At room temperature the quantum yield increases with pressure from 1.09 at 30 mm to 1.26 at 200 mm. Above 200 mm pressure there was no further increase in the quantum yield. Temperature had little effect on the quantum yield at λ 2550, but there was a marked increase in the rate of hydrogen production between 500 and 650° C with 2288 Å radiation. This may have been caused by the decomposition of excited hydrosulphide radicals. The results are consistent with a mechanism involving hydrogen atoms and hydrosulphide radicals. The mercury-photosensitized reaction is less efficient than the photochemical decomposition, the quantum yield being only about 0.45. The efficiency increased with temperature and approached unity at high temperatures and pressures. This agrees with the suggestion that a large fraction of the quenching collisions lead to the formation of Hg ( 3 P 0 ) atoms. The thermal decomposition is heterogeneous at low temperatures and becomes homogeneous and of the second order at 650° C. The experimental evidence suggests the bimolecular mechanism 2H 2 S → 2H 2 + S 2 . The activation energies are 25 kcal/mole (heterogeneous) and 50 kcal/mole (homogeneous).


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