scholarly journals Fluorescence Quenching by Reversible Charge Separation Followed by Ions Recombination and Their Separation Suppressed by Coulomb Attraction

2012 ◽  
Vol 2012 ◽  
pp. 1-7
Author(s):  
A. I. Burshtein ◽  
A. B. Doktorov

The Stern-Volmer constant is specified for the luminescence quenched by reversible ionization of excited molecules. The exergonic branch of the Rehm-Weller free energy dependence of this constant is known to be a plateau determined by irreversible ionization being under diffusion control. In the endergonic region the ionization is reversible and competes with the irreversible in-cage recombination of ions and their escape from the cage. At strong Coulomb attraction the latter phenomenon is shown to be negligible compared to the former that determines the shape and location of the descending branch of the Rehm-Weller curve. At weaker Coulomb attraction (at higher solvent polarity), this curve turns down at larger endergonicity. The experimental data obtained in solvents of different polarities are put in order and in full accordance with present theory.

2017 ◽  
Vol 21 (02) ◽  
pp. 152-157 ◽  
Author(s):  
Won-Young Cha ◽  
Juwon Oh ◽  
Masaaki Kitano ◽  
Atsuhiro Osuka ◽  
Dongho Kim

Excited state dynamics of meso-arylethynyl-substituted subporphyrins can be tuned by 4-substituent at the arylethynyl group and solvent polarity. In polar acetonitrile, phenylethynyl subporphyrin 1 exhibited enhanced fluorescence, while (4-dimethylaminophenyl)ethynyl subporphyrin 2 showed red-shifted fluorescence from its charge-separated state and (4-nitrophenyl)ethynyl subporphyrin 3 displayed efficient fluorescence quenching due to charge separation.


Author(s):  
Hellismar W. da Silva ◽  
Renato S. Rodovalho ◽  
Marya F. Velasco ◽  
Camila F. Silva ◽  
Luís S. R. Vale

ABSTRACT The objective of this study was to determine and model the drying kinetics of 'Cabacinha' pepper fruits at different temperatures of the drying air, as well as obtain the thermodynamic properties involved in the drying process of the product. Drying was carried out under controlled conductions of temperature (60, 70, 80, 90 and 100 °C) using three samples of 130 g of fruit, which were weighed periodically until constant mass. The experimental data were adjusted to different mathematical models often used in the representation of fruit drying. Effective diffusion coefficients, calculated from the mathematical model of liquid diffusion, were used to obtain activation energy, enthalpy, entropy and Gibbs free energy. The Midilli model showed the best fit to the experimental data of drying of 'Cabacinha' pepper fruits. The increase in drying temperature promoted an increase in water removal rate, effective diffusion coefficient and Gibbs free energy, besides a reduction in fruit drying time and in the values of entropy and enthalpy. The activation energy for the drying of pepper fruits was 36.09 kJ mol-1.


2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
Emin Karapınar ◽  
Ilkay Hilal Gubbuk ◽  
Bilge Taner ◽  
Pervin Deveci ◽  
Emine Ozcan

Thermal degradation behaviour of the Ni(II) complex of 3,4-methylenedioxaphenylaminoglyoxime was investigated by TG, DTA, and DTG at a heating rate of 10°C min−1under dinitrogen. The acquired experimental data shows that the complex is thermally stable up to 541 K. The pyrolytic decomposition process occurs by melting metal complex and metal oxide remains as final product. The energies of the reactions involved and the mechanism of decomposition at each stage have been examined. The values of kinetic parameters such as activation energy (E), preexponential factor (A) and thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) are also evaluated.


2011 ◽  
Vol 1 (32) ◽  
pp. 15
Author(s):  
Yang-Yih Chen ◽  
Meng-Syue Li ◽  
Hung-Chu Hsu ◽  
Ying-Pin Lin

In this paper, a new third-order Lagrangian asymptotic solution describing nonlinear water wave propagation on the surface of a uniform sloping bottom is presented. The model is formulated in the Lagrangian variables and we use a two-parameter perturbation method to develop a new mathematical derivation. The particle trajectories, wave pressure and Lagrangian velocity potential are obtained as a function of the nonlinear wave steepness  and the bottom slope  perturbed to third order. The analytical solution in Lagrangian form satisfies state of the normal pressure at the free surface. The condition of the conservation of mass flux is examined in detail for the first time. The two important properties in Lagrangian coordinates, Lagrangian wave frequency and Lagrangian mean level, are included in the third-order solution. The solution can also be used to estimate the mean return current for waves progressing over the sloping bottom. The Lagrangian solution untangle the description of the features of wave shoaling in the direction of wave propagation from deep to shallow water, as well as the process of successive deformation of a wave profile and water particle trajectories leading to wave breaking. The proposed model has proved to be capable of a better description of non-linear wave effects than the corresponding approximation of the same order derived by using the Eulerian description. The proposed solution has also been used to determine the wave shoaling process, and the comparisons between the experimental and theoretical results are presented in Fig.1a~1b. In addition, the basic wave-breaking criterion, namely the kinematical Stokes stability condition, has been investigated. The comparisons between the present theory, empirical formula of Goda (2004) and the experiments made by Iwagali et al.(1974), Deo et al.(2003) and Tsai et al.(2005) for the breaking index(Hb/L0) versus the relative water depth(d0/L0) under two different bottom slopes are depicted in Figs 2a~2b. It is found that the theoretical breaking index is well agreement with the experimental results for three bottom slopes. However,for steep slope of 1/3 shown in Fig 2b, the result of Goda‘s empirical formula gives a larger value in comparison with the experimental data and the present theory. Some of empirical formulas presented the breaking wave height in terms of deepwater wave condition, such as in Sunamura (1983) and in Rattanapitikon and Shibayama(2000). Base on the results depicted in Fig. 3a~3b, it showed that the theoretical results are in good agreement with the experimental data (Iwagali et al. 1974, Deo et al.2003 and Tsai et al. 2005) than the empirical formulas. The empirical formula of Sunamura (1983) always predicts an overestimation value.


1995 ◽  
Vol 09 (03n04) ◽  
pp. 237-242 ◽  
Author(s):  
R. MOLDOVAN ◽  
M. TINTARU ◽  
T. BEICA ◽  
S. FRUNZA ◽  
D. N. STOENESCU

The surface tension is calculated as the excess of the free energy per unit area, due to the presence of a surface layer, using Landau–de Gennes expansions, in the hypothesis of a first order transition in the bulk and taking into account the dependence of the surface free energy from the surface tilt angle. The surface order parameter is calculated and surface-ordered phase above the phase transition temperature has been found. A variety of calculated surface tension versus temperature curves with a jump at the phase transition, with positive or negative slope, well describing the experimental data from literature, have been attained.


1998 ◽  
Vol 16 (2) ◽  
pp. 67-75 ◽  
Author(s):  
Wen-Tien Tsai ◽  
Ching-Yuan Chang ◽  
Chih-Yin Ho

Of the major replacements for chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) are now accepted as being prime contributors to stratospheric ozone depletion. As a consequence, the development of adsorbents capable of adsorbing and recovering specific HCFCs has received great attention. This paper describes an investigation of the adsorption equilibrium of 1, 1-dichloro-1-fluoroethane (HCFC-141b) vapour on a commercial hydrophobic zeolite. The corresponding Henry, Freundlich and Dubinin–Radushkevich (D–R) equilibrium isotherms have been determined and found to correlate well with the experimental data. Based on the Henry adsorption isotherms obtained at 283, 303 and 313 K. thermodynamic properties such as the enthalpy, free energy and entropy of adsorption have been computed for the adsorption of HCFC-141b vapour on the adsorbent. The results obtained could be useful in the application of HCFC adsorption on the hydrophobic zeolite studied.


Author(s):  
Burak Erman ◽  
James E. Mark

The classical theories of rubber elasticity presented in chapter 2 are based on a hypothetical chain which may pass freely through its neighbors as well as through itself. In a real chain, however, the volume of a segment is excluded to other segments belonging either to the same chain or to others in the network. Consequently, the uncrossability of chain contours by those occupying the same volume becomes an important factor. This chapter and the following one describe theoretical models treating departures from phantom-like behavior arising from the effect of entanglements, which result from this uncrossability of network chains. The chains in the un-cross-linked bulk polymer are highly entangled. These entanglements are permanently fixed once the chains are joined during formation of the network. The degree of entanglement, or degree of interpenetration, in a network is proportional to the number of chains sharing the volume occupied by a given chain. This is quite important, since the observed differences between experimental results on real networks and predictions of the phantom network theory may frequently be attributed to the effects of entanglements. The decrease in network modulus with increasing tensile strain or swelling is the best-known effect arising from deformation-dependent contributions from entanglements. The constrained-junction model presented in this chapter and the slip-link model presented in chapter 4 are both based on the postulate that, upon stretching, the space available to a chain along the direction of stretch is increased, thus resulting in an increase in the freedom of the chain to fluctuate. Similarly, swelling with a suitable diluent separates the chains from one another, decreasing their correlations with neighboring chains. Experimental data presented in figure 3.1 show that the modulus of a network does indeed decrease with both swelling and elongation, finally becoming independent of deformation, as should be the case for the modulus of a phantom network. Rigorous derivation of the modulus of a network from the elastic free energy for this case will be given in chapter 5. The starting point of the constrained-junction model presented in this chapter is the elastic free energy.


2016 ◽  
Vol 19 (1) ◽  
pp. 9-14 ◽  
Author(s):  
Mohammad Firoz Khan ◽  
Ridwan Bin Rashid ◽  
Md Yeunus Mian ◽  
Mohammad S Rahman ◽  
Mohammad A Rashid

A computational study of medium effect on solvation free energy, dipole moment, polarizability, hyperpolarizability and different molecular properties like chemical hardness & softness, chemical potential, electronegativity and electrophilicity index of metronidazole have been reported in this paper. Becke, 3-parameter, Lee-Yang-Parr (B3LYP) level of theory with 6-31G (d,p) basis set was applied for gas phase and solution. The effect of solvent polarity on solvation free energy, dipole moment, polarizability, hyperpolarizability and molecular properties were calculated by employing Solvation Model on Density (SMD). The solvation free energies and dipole moment of metronidazole were found to be increased in nonpolar to polar solvents. The dipole moment of metronidazole was higher in different solvent than that of the gas phase. Moreover, from non-polar to polar solvents the chemical potential, electronegativity and electrophilicity index were increased. On the other hand, opposite relation was found in the case of chemical hardness and softness. The results obtained in this study may lead to understand the stability and reactivity of metronidazole and the results will be of assistance to use the title molecule as reaction intermediates and pharmaceuticals.Bangladesh Pharmaceutical Journal 19(1): 9-14, 2016


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