THE REDUCTION OF NITROBENZENE BY HYDROSULPHIDE ION IN AQUEOUS MEDIA

1962 ◽  
Vol 40 (12) ◽  
pp. 2317-2328 ◽  
Author(s):  
O. J. Cope ◽  
R. K. Brown
Keyword(s):  
Reaction Time ◽  
Rate Constants ◽  
Aqueous Media ◽  
The Other ◽  
First Order ◽  
Order Dependence ◽  
Other Hand ◽  
Nitrobenzene Reduction ◽  
Autocatalytic Effect

The reduction of nitrobenzene by sodium hydrosulphide and sodium hydrodisulphide in aqueous media at 50° has been examined. Goldschmidt's report of first-order dependence upon both nitrobenzene and hydrosulphide is corroborated. The action of hydrosulphide on nitrobenzene produces phenylhydroxylamine, which is reduced by hydrosulphide much more slowly than is nitrobenzene. As reaction progresses, nitrobenzene reduction produces yellow hydrodisulphide, which is responsible for the observed autocatalytic effect. Hydrodisulphide reduces phenylhydroxylamine more rapidly than it does the original nitrobenzene, and hence as reaction time is extended, phenylhydroxylamine disappears more rapidly than does nitrobenzene, yielding only aniline and some unreacted nitrobenzene towards the end of the reaction. Hydrosulphide reduction of phenylhydroxylamine to aniline produces thiosulphate but apparently no hydrodisulphide. Hydrodisulphide reduction of the phenylhydroxylamine leads only to conversion of the yellow hydrodisulphide to a colorless species, apparently thiosulphate. On the other hand hydrosulphide or hydrodisulphide reduction of nitrobenzene is accompanied by thiosulphate formation and some increase in hydrodisulphide. A comparison of the rate constants shows that under the conditions of the reaction, hydrodisulphide ion reduces nitrobenzene about seven times more rapidly than does hydrosulphide ion while phenylhydroxylamine is reduced two to three times more rapidly by hydrodisulphide than is nitrobenzene.

Degradation of chlorpyriphos in water by advanced oxidation processes

2010 ◽  
Vol 10 (1) ◽  
pp. 1-6 ◽  
Author(s):  
R. Murillo ◽  
J. Sarasa ◽  
M. Lanao ◽  
J. L. Ovelleiro
Keyword(s):  
Reaction Time ◽  
Light Source ◽  
Advanced Oxidation Processes ◽  
Advanced Oxidation ◽  
The Other ◽  
Molar Ratio ◽  
Optimum Conditions ◽  
Oxidation Processes ◽  
Other Hand ◽  
Initial Ph

The degradation of chlorpyriphos by different advanced oxidation processes such as photo-Fenton, TiO2, TiO2/H2O2, O3 and O3/H2O2 was investigated. The photo-Fenton and TiO2 processes were optimized using a solar chamber as light source. The optimum dosages of the photo-Fenton treatment were: [H2O2]=0.01 M; [Fe3 + ]=10 mg l−1; initial pH = 3.5. With these optimum conditions total degradation was observed after 15 minutes of reaction time. The application of sunlight was also efficient as total degradation was achieved after 60 minutes. The optimum dosage using only TiO2 as catalyst was 1,000 mg l−1, obtaining the maximum degradation at 20 minutes of reaction time. On the other hand, the addition of 0.02 M of H2O2 to a lower dosage of TiO2 (10 mg l−1) provides the same degradation. The ozonation treatment achieved complete degradation at 30 minutes of reaction time. On the other hand, it was observed that the degradation was faster by adding H2O2 (H2O2/O3 molar ratio = 0.5). In this case, total degradation was observed after 20 minutes.

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

scholarly journals DABCO Catalyzed Synthesis of Xanthene Derivatives in Aqueous Media

2013 ◽  
Vol 2013 ◽  
pp. 1-6 ◽  
Author(s):  
Pradeep Paliwal ◽  
Srinivasa Rao Jetti ◽  
Anjna Bhatewara ◽  
Tanuja Kadre ◽  
Shubha Jain
Keyword(s):  
Reaction Time ◽  
Aqueous Media ◽  
Environmentally Friendly ◽  
The Other ◽  
Short Reaction Time ◽  
Xanthene Derivatives ◽  
Reaction Proceeds ◽  
Conventional Methods

The reaction of 5,5-dimethylcyclohexane-1,3-dione with various heteroarylaldehydes afforded the corresponding heteroaryl substituted xanthene derivatives 1(a–f). The reaction proceeds via the initial Knoevenagel, subsequent Michael, and final heterocyclization reactions using 1,4-diazabicyclo[2.2.2]octane (DABCO) as a catalyst in aqueous media. The synthesized heteroaryl substituted xanthenes 1(a–f) reacted with malononitrile to obtain different alkylidenes 2(a–f). Short reaction time, environmentally friendly procedure, avoiding of cumbersome apparatus, and excellent yields are the main advantages of this procedure which makes it more economic than the other conventional methods.

scholarly journals Deontic Logics as Axiomatic Extensions of First-Order Predicate Logic: An Approach Inspired by Wolniewicz’s Formal Ontology of Situations

Axioms ◽  
2019 ◽  
Vol 8 (4) ◽  
pp. 109 ◽  
Author(s):  
Malec
Keyword(s):  
Deontic Logic ◽  
Predicate Logic ◽  
The Other ◽  
Choice Situation ◽  
Formal Ontology ◽  
Legal Rules ◽  
First Order ◽  
The Third ◽  
Other Hand ◽  
First Order Predicate Logic

The aim of this article is to present a method of creating deontic logics as axiomatic theories built on first-order predicate logic with identity. In the article, these theories are constructed as theories of legal events or as theories of acts. Legal events are understood as sequences (strings) of elementary situations in Wolniewicz′s sense. On the other hand, acts are understood as two-element legal events: the first element of a sequence is a choice situation (a situation that will be changed by an act), and the second element of this sequence is a chosen situation (a situation that arises as a result of that act). In this approach, legal rules (i.e., orders, bans, permits) are treated as sets of legal events. The article presents four deontic systems for legal events: AEP, AEPF, AEPOF, AEPOFI. In the first system, all legal events are permitted; in the second, they are permitted or forbidden; in the third, they are permitted, ordered or forbidden; and in the fourth, they are permitted, ordered, forbidden or irrelevant. Then, we present a deontic logic for acts (AAPOF), in which every act is permitted, ordered or forbidden. The theorems of this logic reflect deontic relations between acts as well as between acts and their parts. The direct inspiration to develop the approach presented in the article was the book Ontology of Situations by Boguslaw Wolniewicz, and indirectly, Wittgenstein’s Tractatus Logico-Philosophicus.

On the reduction of the decision problem. First paper. Ackermann prefix, a single binary predicate

1939 ◽  
Vol 4 (1) ◽  
pp. 1-9 ◽  
Author(s):  
László Kalmár
Keyword(s):  
Decision Problem ◽  
Reduction Process ◽  
The Other ◽  
First Order ◽  
Other Hand ◽  
Special Cases ◽  
Binary Predicate ◽  
Ternary Variables ◽  
Order Predicate Calculus ◽  
Predicate Variable

1. Although the decision problem of the first order predicate calculus has been proved by Church to be unsolvable by any (general) recursive process, perhaps it is not superfluous to investigate the possible reductions of the general problem to simple special cases of it. Indeed, the situation after Church's discovery seems to be analogous to that in algebra after the Ruffini-Abel theorem; and investigations on the reduction of the decision problem might prepare the way for a theory in logic, analogous to that of Galois.It has been proved by Ackermann that any first order formula is equivalent to another having a prefix of the form(1) (Ex1)(x2)(Ex3)(x4)…(xm).On the other hand, I have proved that any first order formula is equivalent to some first order formula containing a single, binary, predicate variable. In the present paper, I shall show that both results can be combined; more explicitly, I shall prove theTheorem. To any given first order formula it is possible to construct an equivalent one with a prefix of the form (1) and a matrix containing no other predicate variable than a single binary one.2. Of course, this theorem cannot be proved by a mere application of the Ackermann reduction method and mine, one after the other. Indeed, Ackermann's method requires the introduction of three auxiliary predicate variables, two of them being ternary variables; on the other hand, my reduction process leads to a more complicated prefix, viz.,(2) (Ex1)…(Exm)(xm+1)(xm+2)(Exm+3)(Exm+4).

scholarly journals A Survey of Conceptualizations of Politeness

2015 ◽  
Vol 5 (6) ◽  
pp. 115
Author(s):  
Lei Qiu
Keyword(s):  
Second Order ◽  
The Other ◽  
Theoretical Construct ◽  
First Order ◽  
Relational Work ◽  
Other Hand ◽  
Uniform Definition

<p>Along with the general trends of research from traditional Gricean approach to postmodern approach, politeness has been conceptualized as facework, social indexing concept, relational work and interactional work. Based on examination of debates over East group-oriented and Western individual-oriented politeness, first-order and second-order politeness, as well as the universality and relativity of conceptualizations, this paper has roughly demonstrated that the tension between universality and relativity of politeness can help to explain the reason for lack of uniform definition and concept in this field. It is essential for researchers to seek a universal second-order culture-general theoretical construct on one hand, and to look at first-order culture-specific constructs on the other hand.</p>

scholarly journals Human perception of shape from touch

2011 ◽  
Vol 366 (1581) ◽  
pp. 3106-3114 ◽  
Author(s):  
Astrid M. L. Kappers
Keyword(s):  
Human Perception ◽  
The Other ◽  
Dominant Factor ◽  
Stimulus Information ◽  
After Effects ◽  
First Order ◽  
Other Hand ◽  
After Effect ◽  
The Difference

In this paper, I focus on the role of active touch in three aspects of shape perception and discrimination studies. First an overview is given of curvature discrimination experiments. The most prominent result is that first-order stimulus information (that is, the difference in attitude or slope over the stimulus) is the dominant factor determining the curvature threshold. Secondly, I compare touch under bimanual and two-finger performance with unimanual and one-finger performance. Consistently, bimanual or two-finger performance turned out to be worse. The most likely explanation for the former finding is that a loss of accuracy during intermanual comparisons is owing to interhemispheric relay. Thirdly, I address the presence of strong after-effects after just briefly touching a shape. These after-effects have been measured and studied in various conditions (such as, static, dynamic, transfer to other hand or finger). Combination of the results of these studies leads to the insight that there are possibly different classes of after-effect: a strong after-effect, caused by immediate contact with the stimulus, that does only partially transfer to the other hand, and one much less strong after-effect, caused by moving over the stimulus for a certain period, which shows a full transfer to other fingers.

Effects of Speed and Accuracy of Exertion of Force on the Relationship between Force Output and Fractionated Reaction Time

1991 ◽  
Vol 73 (1) ◽  
pp. 327-334 ◽  
Author(s):  
Shoko Kawabe-Himeno
Keyword(s):  
Reaction Time ◽  
Isometric Contraction ◽  
Light Signal ◽  
The Other ◽  
Force Output ◽  
Motor Time ◽  
Premotor Time ◽  
Other Hand ◽  
The Relationship ◽  
Speed And Accuracy

The present study was designed to investigate the effect of speed and accuracy of force exertion on the relationship between force output and fractionated reaction time. Subjects exerted their force (10% or 40% of maximum isometric contraction) on “accurate” and “fast” tasks as rapidly as possible at the light signal. On the “fast” task, premotor time for the 40% target was lengthened in comparison with that for the 10% target, and motor time was shortened with an increase of force output. On the “accurate” task, on the other hand, premotor time was independent of magnitude of force, and no relation between motor time and force output was found. These findings show that the relationship between force output and fractionated reaction time may be affected by the effort to exert force accurately.

The Decomposition of Sodium Nitrite Solutions in Aqueous Sulphuric and Perchloric Acids

1963 ◽  
Vol 16 (6) ◽  
pp. 927 ◽  
Author(s):  
NS Bayliss ◽  
DW Watts
Keyword(s):  
Aqueous Solutions ◽  
Acid Composition ◽  
Sodium Nitrite ◽  
Decomposition Rate ◽  
Rate Constants ◽  
First Order ◽  
Order Dependence ◽  
Gaseous Products ◽  
Kinetics Of

The kinetics of the decomposition of aqueous solutions of sulphuric and perchloric acids containing sodium nitrite have been investigated at a number of temperatures. The technique involved flushing the decomposing solutions with dry nitrogen to remove the gaseous products. A first-order dependence of decomposition rate on "analytical nitrite" was found, the rate constants being dependent on the solvent acid composition.

Copolymerization of Ethylene/Diene with Different Metallocene Catalysts

2006 ◽  
Vol 61 (11) ◽  
pp. 1426-1432 ◽  
Author(s):  
Maria de Fátima Vieira Marques ◽  
Fernanda Constantino Rocha ◽  
Narda Juárez Soto
Keyword(s):  
Catalytic Activity ◽  
Thermal Properties ◽  
Reaction Time ◽  
Polymerization Rate ◽  
The Other ◽  
Copolymer Composition ◽  
Metallocene Catalysts ◽  
Ethylene Pressure ◽  
Other Hand ◽  
Catalyst Type

Copolymerizations of ethylene and 1,7-octadiene were carried out employing homogeneous catalysts Cp2ZrCl2, Ph2C(Flu,Cp)ZrCl2 and Et(Ind)2ZrCl2, and methylaluminoxane as cocatalyst. The polymerization characteristics, such as catalytic activity, polymerization rate, copolymer composition, and thermal properties were examined in relation to the catalyst type. Different comonomer concentrations were employed, and the reaction time was varied, ranging from 1 h up to 4 h, at 90°C and at 0.5 bar ethylene pressure. The results showed that the catalyst Cp2ZrCl2 was more efficient than Et(Ind)2ZrCl2 in the preparation of high diene content ethylene/1,7-octadiene copolymers. On the other hand, Et(Ind)2ZrCl2 and Ph2C(Flu,Cp)2ZrCl2 catalysts produced low insaturation content but possibly formed cyclic structures and crosslinking.

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