Substituent effects on the thermodynamic functions of ionization of metasubstituted anilinium ions

1968 ◽  
Vol 21 (4) ◽  
pp. 939 ◽  
Author(s):  
PD Bolton ◽  
FM Hall

Thermodynamic acidity constants of the meta-methoxyanilinium, meta- chloroanilinium, meta-bromoanilinium, and meta-iodoanilinium ions have been measured spectrophotometrically over the temperature range 5-50� and those of the meta-nitroanilinium ion over the temperature range 5-60�. The thermodynamic functions of ionization, ΔG25, ΔH25, ΔS25, and ΔCp,25, have also been calculated for each ion. For a series of seven meta-substituted anilinium ions the acidity constants show close obedience to the Hammett equation over the temperature range 10-50� with the reaction parameter p being a precise linear function of 1/T. The same reaction series also shows a well-defined isoequilibrium relationship of negative slope.


1968 ◽  
Vol 21 (6) ◽  
pp. 1541 ◽  
Author(s):  
PD Bolton ◽  
FM Hall ◽  
J Kudrynski

Thermodynamic ionization constants of 3-ethoxyphenol; 3,5-diethoxyphenol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-diiodophenol, and 3,5-dinitrophenol have been measured spectrophotometrically within the temperature range 5-60�, and the thermodynamic functions of ionization ΔG25, ΔH25, ΔS25, and ΔCp.25 calculated. These results, in conjunction with others measured previously, indicate that, for this reaction series, substituent effects on the free energies of ionization are precisely additive, and on the entropies of ionization closely additive. An assessment of the results in terms of Hepler's internal/external enthalpy theory is made.



1972 ◽  
Vol 50 (7) ◽  
pp. 1030-1035 ◽  
Author(s):  
L. D. Hansen ◽  
L. G. Hepler

Following Swain and Lupton's analysis of substituent effects, we have taken ΔG0 = aete + artr for a typical substituent effect reaction. In this equation ae and ar are substituent constants for electrostatic field and resonance effects while te and tr are corresponding transmission coefficients. Both substituent constants and tr are taken to be independent of solvent and temperature, while te is taken to depend on both solvent and temperature. General conclusions based on analysis of this model are the following. (i) A Hammett ρσ equation with constant σ values that are valid over a range of temperatures for a variety of reactions in several solvents can be obtained only when either the field or the resonance interaction is negligible compared with the other. (ii) A Hammett ρσ equation can be expected to hold for "similar" reaction series in a given solvent at one temperature even when both the field and resonance interactions are important, (iii) An isoequilibrium or isokinetic relationship can be expected only when the field interaction is dominant.The general equations leading to these and other conclusions are presented so that one can later insert appropriate mathematical descriptions of detailed models and thereby obtain information about specific reactions.



1972 ◽  
Vol 25 (1) ◽  
pp. 75 ◽  
Author(s):  
PD Bolton ◽  
FM Hall ◽  
J Kudrynski

Thermodynamic ionization constants of 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 3,5-di-t-butylphenol, and 3,5-dimethoxyphenol have been measured in aqueous solution by an e.m.f./spectrophotometric method within the temperature range 5-60�C and the thermodynamic functions of ionization ΔG25, ΔH25, ΔS25, and ΔCp25 calculated. These results confirm the additivity of substituent effects noted previously for the ionization of 3,5-disubstituted phenols and indicate that this ionization process is relatively insensitive to steric effects.



1960 ◽  
Vol 38 (12) ◽  
pp. 2493-2499 ◽  
Author(s):  
Marvin Charton

The Hammett equation is directly applicable to ortho-substituted benzene reaction series in which reaction site and benzene ring are separated by some group Z, apparently due to the absence of steric effects in these series. The σp values are used in the correlations. Fourteen ortho-substituted benzene reaction series have been correlated. The electrical effect of a substituent in the ortho position is found to be about 0.75 times its effect in the para position. The effect of the side-chain Z in the transmission of substituent effects is OCH2 > SCH2 > CH = CH > SeCH2 > CH2CH2.



2021 ◽  
pp. 1-19
Author(s):  
M. Miri Karbasaki ◽  
M. R. Balooch Shahriari ◽  
O. Sedaghatfar

This article identifies and presents the generalized difference (g-difference) of fuzzy numbers, Fréchet and Gâteaux generalized differentiability (g-differentiability) for fuzzy multi-dimensional mapping which consists of a new concept, fuzzy g-(continuous linear) function; Moreover, the relationship between Fréchet and Gâteaux g-differentiability is studied and shown. The concepts of directional and partial g-differentiability are further framed and the relationship of which will the aforementioned concepts are also explored. Furthermore, characterization is pointed out for Fréchet and Gâteaux g-differentiability; based on level-set and through differentiability of endpoints real-valued functions a characterization is also offered and explored for directional and partial g-differentiability. The sufficient condition for Fréchet and Gâteaux g-differentiability, directional and partial g-differentiability based on level-set and through employing level-wise gH-differentiability (LgH-differentiability) is expressed. Finally, to illustrate the ability and reliability of the aforementioned concepts we have solved some application examples.



1928 ◽  
Vol 11 (6) ◽  
pp. 715-741 ◽  
Author(s):  
Hudson Hoagland

1. The durations of successive periods of induced tonic immobility in the lizard Anolis carolinensis was examined as a function of temperature. An automatic recording method was employed and observations were made of 12,000 to 15,000 immobilizations with six animals over a temperature range of 5° to 35°C. during 5 months. 2. The durations of the immobile periods were found to vary rhythmically in most cases. The reciprocal of the duration of the rhythm, i.e., the rate of change of the process underlying the rhythms, when plotted as a function of temperature according to the Arrhenius equation show distributions of points in two straight line groups. One of these groups or bands of points extends throughout the entire temperature range with a temperature characteristic of approximately µ = 31,000 calories, and the other covers the range of 20° to 35°C. with µ equal to approximately 9,000 calories. 3. The initial stimulus in a series of inductions of immobility appears to set off a mechanism which determines the duration of the state of quiescence. Succeeding forced recoveries seem to have no effect on the normal duration of the rhythm. 4. These results are interpreted by assuming the release, through reflex stimulation, of hormonal substances, one effective between 5° and 35°C. and the other effective between 20° and 35°C. These substances are assumed to act as selective inhibitors of impulses from so called "higher centers," allowing impulses from tonic centers to pass to the muscles. 5. In some experiments a progressive lengthening in successively induced periods of immobility was observed. The logarithm of the frequency of recovery when plotted against time in most of these cases (i.e., except for a few in which irregularities occurred) gave a linear function of negative slope which was substantially unaffected by temperature. In these cases it is assumed that a diffusion process is controlling the amount of available A substance. 6. The results are similar to those obtained by Crozier with Cylisticus convexus. The duration of tonic immobility seems to be maintained in both arthropod and vertebrate by the chemical activity of "hormonal" selective inhibitors. The details of the mechanisms differ, but there is basic similarity. 7. Injections of small amounts of adrenalin above a threshold value are found to prolong the durations of tonic immobility of Anolis, by an amount which is a logarithmic function of the "dose." It is possible that internally secreted adrenalin, above a threshold amount, may be involved in the maintenance of tonic immobility. 8. The production of tonic immobility reflexly is a problem distinct from that of the duration of immobility. It is suggested that the onset may be induced by "shock" to the centers of reflex tonus causing promiscuous discharge of these centers with accompanying inhibition of the higher centers. Such a condition may result when an animal is suddenly lifted from the substratum and overturned, or when, as in the case of Anolis, it struggles with dorsum down. This reaction of the "tonic centers" may at the same time lead to discharge of the adrenal glands by way of their spinal connections thus prolonging the state.



2002 ◽  
Vol 26 (7) ◽  
pp. 861-866 ◽  
Author(s):  
Karel Palát Jr. ◽  
Stanislav Böhm ◽  
Gabriela Braunerová ◽  
Karel Waisser ◽  
Otto Exner




2018 ◽  
Vol 134 (2) ◽  
pp. 1123-1128 ◽  
Author(s):  
N. I. Matskevich ◽  
Th. Wolf ◽  
D. P. Pischur ◽  
S. G. Kozlova ◽  
N. V. Gelfond ◽  
...  


2018 ◽  
Vol 20 (30) ◽  
pp. 20108-20116 ◽  
Author(s):  
V. V. Sereda ◽  
D. S. Tsvetkov ◽  
A. L. Sednev ◽  
A. I. Druzhinina ◽  
D. A. Malyshkin ◽  
...  

Essential thermodynamic functions, obtained for Sr2NiMoO6 and Sr2CoMoO6 in broad temperature range, allowed to evaluate their stability in reducing conditions.



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