The pyrolysis of alkyl chlorides on the surface of Pyrex glass

1964 ◽  
Vol 17 (11) ◽  
pp. 1217 ◽  
Author(s):  
JS Shapiro ◽  
ES Swinbourne ◽  
BC Young
Keyword(s):  
Hydrogen Chloride ◽  
Heterogeneous Reaction ◽  
Initial Pressure ◽  
Pyrex Glass ◽  
Kcal Mole ◽  
Arrhenius Activation Energy ◽  
First Order ◽  
Determining Factor ◽  
Chlorine Bond ◽  
Selection Of

A study has been made of the surface-catalysed dehydrochlorination of a selection of gaseous chlorinated hydrocarbons on Pyrex glass. For primary chlorides at 413� the rate sequence: ethyl<n-propyl<isobutyl<neopentyl was observed for 200 mm initial pressure of reagent. Ethyl chloride decomposes at 400-450� according to a first-order law, and the overall Arrhenius activation energy for the heterogeneous reaction is 24.1 kcal/mole; the rate is slightly depressed by the addition of propene and slightly enhanced by hydrogen chloride. Catalysis by hydrogen chloride was observed to be much more marked in the case of isopropyl chloride decomposition at 190-250�, but reproducible behaviour for this reaction was not readily attained. The catalytic action of Pyrex glass is accounted for by the polar surface assisting in the separation of charges within the reacting molecule, emphasis being placed upon the polarization of the carbon-chlorine bond as the important rate-determining factor.

The kinetics of the pyrolysis of Cyclohexyl chloride.

1958 ◽  
Vol 11 (3) ◽  
pp. 314 ◽  
Author(s):  
ES Swinbourne
Keyword(s):  
Gas Phase ◽  
Hydrogen Chloride ◽  
Rate Coefficient ◽  
Initial Pressure ◽  
Order Reaction ◽  
Rate Coefficients ◽  
Homogeneous Reaction ◽  
First Order ◽  
Induction Periods ◽  
Kinetics Of

cycloHexy1 chloride has been shown to decompose in the gas phase at 318-385 �C almost exclusively to cyclohexene and hydrogen chloride. With clean glass-walled reactors the reaction was largely heterogeneous, but after the walls were coated with a carbonaceous film a homogeneous first-order reaction was found to predominate. For initial pressures within the range 4-40 cm mercury the rate coefficients for the homogeneous reaction were expressible as������� k = 5.88 x 1013exp(-50,000 cal/RT) sec-1. There was some evidence for the rate coefficient becoming pressure-dependent below 5-10 mm initial pressure of reactant. The reaction exhibited no induction periods and the velocity was virtually unaffected by the addition of large amounts of propene or cyclohexene and traces of chlorine or bromine. The results were consistent with a unimolecular elimination of hydrogen chloride.

The thermal decomposition of 1-ethoxyethyl chloride and the reverse combination

1967 ◽  
Vol 20 (8) ◽  
pp. 1553 ◽  
Author(s):  
RL Failes ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Transition State ◽  
Hydrogen Chloride ◽  
Ethyl Ether ◽  
Reverse Reaction ◽  
Kcal Mole ◽  
First Order ◽  
Polar Transition

1-Ethoxyethyl chloride decomposes cleanly at 164-221� into vinyl ethyl ether and hydrogen chloride in a first-order manner with k1 = 1010.52exp(-30300/RT) sec-1 (1) The equilibrium of the system at 128-221� approached from either direction at various pressures is well represented by (Kp in atmospheres) 1.987 In Kp = 31.1 � 0.9-(16500�500)/T (2) and this leads to ΔH�f,298(g) = -71.9 kcal mole-1 for 1-ethoxyethyl chloride. Combination of (1) and (2) gives k2 = 108.7exp(-14700/RT) sec-1 ml mole-1 for the reverse reaction and rate measurements verify this. The reactions are molecular, and relative rates indicate a polar transition state.

Nucleophilic decomposition of α-disulfones

1969 ◽  
Vol 47 (6) ◽  
pp. 873-877 ◽  
Author(s):  
Paul Allen Jr. ◽  
Patrick J. Conway
Keyword(s):  
Activation Energy ◽  
Order Reaction ◽  
Second Order ◽  
Hammett Equation ◽  
Second Order Reaction ◽  
Kcal Mole ◽  
Arrhenius Activation Energy ◽  
Hydroxide Ion ◽  
First Order ◽  
Sulfur Bond

The sulfur–sulfur bond of α-disulfones is attacked by hydroxide ion in alcohol to yield sulfinate and sulfonate ion by a second-order reaction, first order in each of the reactants. With aromatic disulfones the ρ value of the Hammett equation is 0.2. The Arrhenius activation energy of the reaction of p-tolyl disulfone is 7.95 kcal/mole.

THE REACTION OF OXYGEN ATOMS WITH NO

1959 ◽  
Vol 37 (10) ◽  
pp. 1690-1695 ◽  
Author(s):  
E. A. Ogryzlo ◽  
H. I. Schiff
Keyword(s):  
Rate Constant ◽  
Negative Temperature Coefficient ◽  
Negative Temperature ◽  
Order Rate Constant ◽  
Third Body ◽  
Kcal Mole ◽  
Arrhenius Activation Energy ◽  
Third Order ◽  
First Order ◽  
Calorimetric Technique

In the reaction between NO and O-atoms, the concentration of NO remains essentially unaltered. The reaction can therefore be considered as a NO-catalyzed recombination of O-atoms. Its rate can be conveniently studied by following the disappearance of O-atoms by an isothermal calorimetric technique. The reaction was found to be third order, first order in the concentrations of O, NO, and M, where M is some third body. The third-order rate constant was found to be 1.85 × 1016 cc2 mole−2 sec−1 when M = O2, A, or He and 2.0 × 1016 cc2 mole−2 sec−1 when M = CO2 The rate constant was found to have a slight negative temperature coefficient which corresponded to a negative Arrhenius activation energy of about 0.2 kcal/mole. A detailed mechanism for the reaction has been proposed.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

A Comparative Study of Numerical Techniques for Nonequilibrium Method of Characteristics

1992 ◽  
Author(s):  
T. Gary Yip ◽  
David M. Crook ◽  
Timothy P. Buell
Keyword(s):  
Method Of Characteristics ◽  
Solution Process ◽  
Initial Pressure ◽  
Single Step ◽  
Supersonic Combustion ◽  
Duct Flow ◽  
Unit Process ◽  
First Order ◽  
Constant Area ◽  
Fifth Order

Abstract Three techniques which employ different approaches for obtaining a method of characteristics solution for chemical non-equilibrium flows are reviewed and compared. Two features of the solution process are evaluated to determine their effect on the accuracy of the solution. The first aspect to be considered is the integration of the stiff conservation equations in a unit process. A new fifth-order accurate, multi-step integration routine is contrasted with a first-order accurate, single-step forward differencing scheme. The second comparison is designed to determine if a solution of the flowfield along continuous streamlines is superior to one along discontinuous segments of the streamlines. Tests are performed, using a chemical model describing the supersonic combustion of H2-air. Calculations of single unit processes are used to validate the techniques and to determine suitable grid sizes. Solutions for constant area duct flow show that the techniques which use the multi-step integration routine are more accurate. Results from the constant area duct test, for an initial pressure of 3.685 atm, show that a method of characteristics technique which utilizes continuous streamlines is able to converge at a grid size two orders of magnitude larger than that needed by a technique which uses discontinuous segments of streamlines.

scholarly journals Penerapan K-Means Clustering Untuk Seleksi Frame Dominan Berbasis NTSC Pada Obyek Bergerak

2020 ◽  
Vol 7 (4) ◽  
pp. 745
Author(s):  
Rizka Indah Armianti ◽  
Achmad Fanany Onnilita Gaffar ◽  
Arief Bramanto Wicaksono Putra
Keyword(s):  
Feature Extraction ◽  
Video Data ◽  
Clustering Method ◽  
Data Frame ◽  
First Order ◽  
Feature Extraction And Selection ◽  
Different Shapes ◽  
Frame Set ◽  
Selection Of

<p class="Abstrak">Obyek dinyatakan bergerak jika terjadi perubahan posisi dimensi disetiap <em>frame</em>. Pergerakan obyek menyebabkan obyek memiliki perbedaan bentuk pola disetiap <em>frame-</em>nya. <em>Frame</em> yang memiliki pola terbaik diantara <em>frame</em> lainnya disebut <em>frame</em> dominan. Penelitian ini bertujuan untuk menyeleksi <em>frame</em> dominan dari rangkaian <em>frame</em> dengan menerapkan metode K-means <em>clustering</em> untuk memperoleh <em>centroid</em> dominan (<em>centroid</em> dengan nilai tertinggi) yang digunakan sebagai dasar seleksi <em>frame</em> dominan. Dalam menyeleksi <em>frame</em> dominan terdapat 4 tahapan utama yaitu akuisisi data, penetapan pola obyek, ekstrasi ciri dan seleksi. Data yang digunakan berupa data video yang kemudian dilakukan proses penetapan pola obyek menggunakan operasi pengolahan citra digital, dengan hasil proses berupa pola obyek RGB yang kemudian dilakukan ekstraksi ciri berbasis NTSC dengan menggunakan metode statistik orde pertama yaitu <em>Mean</em>. Data hasil ekstraksi ciri berjumlah 93 data <em>frame</em> yang selanjutnya dikelompokkan menjadi 3 <em>cluster</em> menggunakan metode K-Means. Dari hasil <em>clustering</em>, <em>centroid</em> dominan terletak pada <em>cluster</em> 3 dengan nilai <em>centroid</em> 0.0177 dan terdiri dari 41 data <em>frame</em>. Selanjutnya diukur jarak kedekatan seluruh data <em>cluster</em> 3 terhadap <em>centroid</em>, data yang memiliki jarak terdekat dengan <em>centroid</em> itulah <em>frame</em> dominan. Hasil seleksi <em>frame</em> dominan ditunjukkan pada jarak antar <em>centroid</em> dengan anggota <em>cluster</em>, dimana dari seluruh 41 data frame tiga jarak terbaik diperoleh adalah 0.0008 dan dua jarak bernilai  0.0010 yang dimiliki oleh <em>frame</em> ke-59, ke-36 dan ke-35.</p><p class="Abstrak"> </p><p class="Abstrak"><em><strong>Abstract</strong></em></p><p class="Abstract"><em>The object is declared moving if there is a change in the position of the dimensions in each frame. The movement of an object causes the object to have different shapes in each frame. The frame that has the best pattern among other frames is called the dominant frame. This study aims to select the dominant frame from the frame set by applying the K-means clustering method to obtain the dominant centroid (the highest value centroid) which is used as the basis for the selection of dominant frames. In selecting dominant frames, there are 4 main stages, namely data acquisition, determination of object patterns, feature extraction and selection. The data used in the form of video data which is then carried out the process of determining the pattern of objects using digital image processing operations, with the results of the process in the form of an RGB object pattern which is then performed NTSC-based feature extraction using the first-order statistical method, Mean. The data from feature extraction are 93 data frames which are then grouped into 3 clusters using the K-Means method. From the results of clustering, the dominant centroid is located in cluster 3 with a centroid value of 0.0177 and consists of 41 data frames. Furthermore, the proximity of all data cluster 3 to the centroid is measured, the data having the closest distance to the centroid is the dominant frame. The results of dominant frame selection are shown in the distance between centroids and cluster members, where from all 41 data frames the three best distances obtained are 0.0008, 0.0010, and 0.0010 owned by 59th, 36th and 35th frames.</em></p><p class="Abstrak"><em><strong><br /></strong></em></p><p> </p>

scholarly journals EFFECT OF DIATOMEAOUS EARTH TREATMENT USING HYDROGEN CHLORIDE AND SULFURIC ACID ON KINETICS OF CADMIUM(II) ADSORPTION

2010 ◽  
Vol 2 (2) ◽  
pp. 107-112
Author(s):  
Nuryono Nuryono ◽  
Narsito Narsito
Keyword(s):  
Aqueous Solution ◽  
Sulfuric Acid ◽  
Hydrogen Chloride ◽  
Rate Constant ◽  
Diatomaceous Earth ◽  
Adsorption Rate ◽  
Physical Interaction ◽  
First Order ◽  
Adsorption Rate Constant ◽  
Kinetics Of

In this research, treatment of diatomaceous earth, Sangiran, Central Java using hydrogen chloride (HCl) and sulfuric acid (H2SO4) on kinetics of Cd(II) adsorption in aqueous solution has been carried out. The work was conducted by mixing an amount of grounded diatomaceous earth (200 mesh in size) with HCl or H2SO4 solution in various concentrations for two hours at temperature range of 100 - 150oC. The mixture was then filtered and washed with water until the filtrate pH is approximately 7 and then the residue was dried for four hours at a temperature of 70oC. The product was used as an adsorbent to adsorb Cd(II) in aqueous solution with various concentrations. The Cd(II) adsorbed was determined by analyzing the rest of Cd(II) in the solution using atomic absorption spectrophotometry. The effect of treatment was evaluated from kinetic parameter of adsorption rate constant calculated based on the simple kinetic model. Results showed  that before equilibrium condition reached, adsorpstion of Cd(II) occurred through two steps, i.e. a step tends to follow a reaction of irreversible first order  (step I) followed by reaction of reversible first order (step II). Treatment with acids, either hydrogen chloride or sulfuric acid, decreased adsorption rate constant for the step I from 15.2/min to a range of 6.4 - 9.4/min.  However, increasing concentration of acid (in a range of concentration investigated) did not give significant and constant change of adsorption rate constant. For step II process,  adsorption involved physical interaction with the sufficient low adsorption energy (in a range of 311.3 - 1001 J/mol).     Keywords: adsorption, cdmium, diatomaceous earth, kinetics.

scholarly journals High Intra-Abdominal Pressure Secondary to Obesity as a Determining Factor for Ventriculoperitoneal Shunt Malfunction

2018 ◽  
Vol 37 (01) ◽  
pp. 50-53
Author(s):  
Barbara Morais ◽  
Vitor Yamaki ◽  
Daniel Cardeal ◽  
Fernanda Andrade ◽  
Wellingson Paiva ◽  
...  
Keyword(s):  
Ventriculoperitoneal Shunt ◽  
Abdominal Ultrasound ◽  
Important Variable ◽  
Abdominal Pressure ◽  
Brain Tomography ◽  
Valve Malfunction ◽  
Determining Factor ◽  
Valve Pressure ◽  
Selection Of

AbstractThe ventriculoperitoneal shunt (VPS) is an established treatment for hydrocephalus. The functioning of the system requires a pressure difference between the cranial and abdominal cavities. The VPS can be particularly problematic in patients with increased intra-abdominal pressure (IAP). We report the case of a 16-year-old girl with VPS since she was 2 months old due to hydrocephalus secondary to myelomeningocele. The patient had been asymptomatic ever since, but she sought the emergency service with intermittent headache and vomiting. A non-enhanced brain tomography, a shunt trajectory X-ray and an abdominal ultrasound revealed no cause of system malfunction. In view of the persistent clinical picture, a revision of the shunt was performed, which revealed adequate intraoperative functioning. She returned with the same symptoms two weeks after surgery. The patient was obese (body mass index [BMI]: 48). We hypothesized intermittent valve malfunction due to increased intra-abdominal pressure. She underwent a ventriculoatrial shunt, without intercurrences. In the postoperative period, the patient presented transient tachycardia and was asymptomatic at the 6-month follow-up. Obesity should be considered an important variable for the inadequate functioning of the VPS due to increased IAP and catheter dystocia to the extraperitoneal cavity. Studies have already correlated the IAP with the BMI, which reaches between 8 mm Hg and 12 mm Hg in obese individuals. Therefore, the BMI can be considered during the selection of valve pressure in systems with non-adjustable valves to prevent insufficient drainage. The recognition of obesity as a cause of VPS malfunction is fundamental to avoid unnecessary surgeries and intermittent malfunction of the system.

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