Kinetics of the liquid-liquid transition of triphenyl phosphite

2006 ◽  
Vol 73 (10) ◽  
Author(s):  
Rei Kurita ◽  
Hajime Tanaka
2005 ◽  
Vol 415 (1-3) ◽  
pp. 146-149 ◽  
Author(s):  
Ryutaro Souda

2013 ◽  
Vol 584 ◽  
pp. 93-97 ◽  
Author(s):  
Y. Terashima ◽  
M. Tsuchie ◽  
K. Takeda ◽  
M. Honda

2020 ◽  
Author(s):  
Finlay Walton ◽  
John Bolling ◽  
Andrew Farrell ◽  
Jamie MacEwen ◽  
Christopher Syme ◽  
...  

Liquid-liquid transitions between two amorphous phases in a single-component liquid (polyamorphism) have defied explanation and courted controversy. All known examples of liquid–liquid transitions have been observed in the supercooled liquid suggesting an intimate connection with vitrification and locally favored structures inhibiting crystallization. However, there is precious little information about the local molecular packing in supercooled liquids meaning that the order parameter of the transition is still unknown. Here, we investigate the liquid–liquid transition in triphenyl phosphite and show that it is caused by the competition between liquid structures that mirror two crystal polymorphs. The liquid–liquid transition is found to be between a geometrically frustrated liquid to a dynamically frustrated glass. These results indicate a general link between polymorphism and polyamorphism and will lead to a much greater understanding of the physical basis of liquid–liquid transitions and allow the discovery of other examples.


Tetrakis(triphenyl phosphite)nickel(0) (NiP 4 ) in solution in methyl methacrylate (MMA) undergoes reversible ligand exchange to form a species NiP 3 (MMA). Kinetic studies based on absorbance measurements are consistent with the view that a rate-controlling dissociation of NiP 4 is followed by rapid and almost complete complexing of NiP 3 with MMA. The enthalpy and entropy of activation for the dissociation have been determined, and also the standard enthalpy and entropy changes for the overall reaction. The initiation of polymerization which occurs in the presence of carbon tetrachloride has been shown to arise from reaction between NiP 3 (MMA) and CCI 4 , and the absolute rate constant of this process has been measured at various temperatures. Each NiP 3 (MMA) yields approximately one free radical, and it is thought that the final product is a Ni II derivative. Part of the oxidation must therefore proceed by a route which does not form radicals. The kinetics of the overall polymerization have been investigated by numerical solution of the appropriate differential equations, using the parameters evaluated, without any stationary state assumptions about the concentration of species involved in initiation. The agreement with experiment is satisfactory over a wide range of conditions.


1966 ◽  
Vol 14 (10) ◽  
pp. 1384-1385 ◽  
Author(s):  
D.A. Rigney ◽  
J.M. Blakely

1972 ◽  
Vol 50 (7) ◽  
pp. 972-976 ◽  
Author(s):  
P. F. Barrett ◽  
W. J. Jacobs

The kinetics of the thermal insertion reaction of SnCl2 with the metal–metal bonded complex (π-C5H5)2Fe2(CO)3P(OC6H5)3 have been studied by following the change in the visible spectrum in THF over the temperature range 40.0 to 55.0 °C. The data are consistent with a two-stage mechanism involving the formation of an intermediate in which the iron–iron bond has been broken but the carbonyl bridges are left intact. From the activation enthalpy of 23.4 ± 0.5 kcal/mol for the formation of the intermediate it is concluded that the triphenyl phosphite has brought about a weakening of the iron–iron bond.


1984 ◽  
Vol 85 (1) ◽  
pp. 105-112 ◽  
Author(s):  
V. G. Chudinov ◽  
V. I. Protasov

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