The Vulcanization of Elastomers. 20. Sulfur Vulcanization Accelerated with Thiuram Compounds. I

1959 ◽  
Vol 32 (1) ◽  
pp. 139-149 ◽  
Author(s):  
Walter Scheele ◽  
Adolf Franck
Keyword(s):  
Reaction Order ◽  
Accurate Determination ◽  
Sulfur Concentration ◽  
Quantitative Investigation ◽  
Tetramethylthiuram Disulfide ◽  
First Order ◽  
Sulfur Vulcanization ◽  
Complicated Course ◽  
Peak Value

Abstract The present paper deals with the results of an orientating, quantitative investigation of sulfur vulcanization accelerated by thiuram disulfide, with tetramethylthiuram disulfide as the representative example. It was found: In the sulfur cure of natural rubber with tetramethylthiuram disulfide at different TMTD:S ratios, the rates of TMTD decrease and dithiocarbamate formation increase with increasing sulfur concentration, the TMTD content being kept constant. The rates practically do not change any further when the compounds contain 6 gram atoms of sulfur per mole of thiuram disulfide. The peak value of dithiocarbamate formation increases with the increase of sulfur concentration and reaches a constant end value of about 90 mole per cent based on the amount of original thiuram disulfide, when the stocks contain 4 gram atoms of sulfur per mole thiuram disulfide. This end value is identical to the end value of dithiocarbamate formation in the reaction of thiuram disulfide with zinc oxide (in the absence of rubber). The crosslinking, as measured by the change of reciprocal equilibrium swelling per time unit is also a reaction whose rate increases with the sulfur concentration to the point where the compounds contain 6 gram atoms of sulfur per mole of thiuram disulfide. The optimum degrees of crosslinking are roughly proportional to the sulfur concentration; at high sulfur levels the vulcanizates tend to revert. As in the pure TMTD vulcanization, the TMTD decrease as well as the dithiocarbamate formation are always first order reactions. The reversion at higher sulfur levels as well as the complicated course of the increase of combined sulfur during vulcanization render all but impossible an accurate determination of the reaction order for the crosslinking at higher sulfur levels. Nevertheless, in vulcanizations with 1 mole TMTD per 1 or 2 gram atoms of sulfur the crosslinking is a first order reaction.

scholarly journals KINETIC INVESTIGATION OF PROPANE DISAPPEARANCE AND PROPENE FORMATION IN PROPANE OXIDATION ON DILUTED AND LEACHED MoVTeNb CATALYST

2010 ◽  
Vol 10 (2) ◽  
pp. 172-176
Author(s):  
Restu Kartiko Widi
Keyword(s):  
Reaction Kinetics ◽  
Partial Order ◽  
Reaction Order ◽  
Propane Oxidation ◽  
Kinetic Investigation ◽  
Formation Kinetic ◽  
Kinetic Reaction ◽  
First Order ◽  
Langmuir Hinshelwood Mechanism

Reaction kinetics for the oxidation of propane over diluted-leached MoVTeNb is described. This paper is focused on the study of products selectivity profile and determination of the orders of propane disappearance and propene formation. The result shows that selective oxidation of propane to propene over this catalyst follows the Langmuir-Hinshelwood mechanism. The disappearance of propane is first order with respect to hydrocarbon and partial order (0.21) with respect to oxygen. The propene formation is first order with respect to hydrocarbon and not depending on oxygen concentration.   Keywords: propane oxidation, propane disappearance, propene formation, kinetic, reaction order

Vulcanization of Elastomers. 25. Natural Rubber and Synthetic Elastomers with Sulfur and Sulfenamides. I

1960 ◽  
Vol 33 (3) ◽  
pp. 846-856 ◽  
Author(s):  
Walter Scheele ◽  
Horst-Eckart Toussaint ◽  
Yoan-Kun Chai
Keyword(s):  
Reaction Order ◽  
Molar Ratio ◽  
Reactive Intermediate ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Experimental Conditions ◽  
Sulfur Vulcanization ◽  
Different Temperatures ◽  
Kinetics Of ◽  
Time Plot

Abstract The sulfur vulcanization of Perbunan N 2818 (acrylonitrile-butadiene) was investigated in the presence of N-cyclohexyl-2-benzothiazolylsulfenamide (CZ) at different temperatures and various concentrations of reactants. The following were found : 1. The decreasing sulfur concentration vs. time plot followed the 0.8th order under all experimental conditions and an activation energy of 28.2 kcal/mole was calculated. 2. When using the cyclohexylammonium salt of MBT as accelerator, sulfur decrease proceeds at the same rate as with CZ. 3. It was concluded from 1 and 2 that even in the presence of CZ, the ammonium salt was the actual accelerator, which forms during the scorch or induction period through reaction of CZ with the rubber. 4. In view of the discrepancy found in the relation of reaction order with respect to time and concentration of reactants, the formation of a reactive intermediate is postulated; the analogy between the kinetics of sulfenamide accelerated sulfur vulcanization, and those accelerated with MBT as well as DPG is pointed out. 5. In connection with 3 the dependence of starting rate as well as rate constant of 0.8th order of the decreasing sulfur concentration on the molar ratio of CZ/S8 and on the sulfur starting concentration is discussed.

scholarly journals A general expression for coupled enzyme assays of hysteretic enzymes

1984 ◽  
Vol 220 (1) ◽  
pp. 173-178 ◽  
Author(s):  
I E Woodrow ◽  
G A Manson
Keyword(s):  
Relaxation Time ◽  
General Expression ◽  
Accurate Determination ◽  
Relaxation Times ◽  
Rate Equations ◽  
Enzyme Assays ◽  
General Description ◽  
First Order ◽  
Low Concentrations

A general description of a system consisting of a hysteretic enzyme and a series of coupling enzymes is presented. The chloroplast enzyme sedoheptulose-1,7-bisphosphatase and a sequence of three coupling enzymes is used as an example. An analysis using first-order rate equations for the coupling enzymes shows that the observed relaxation time of the system is the sum of the relaxation times of the coupling enzymes and that of the hysteretic enzyme. The behaviour of a system with relatively low concentrations of coupling enzymes, where the first-order assumption is not valid, is analysed by computer stimulation. Several methods for the accurate determination of the relaxation time of the hysteretic enzyme are discussed.

scholarly journals Kinetika Reaksi Hidrolisis Pati Biji Alpukat (Persea americana Mill) dengan Katalis HCl

2020 ◽  
Vol 4 (1) ◽  
pp. 120-131
Author(s):  
Sitti Rahmawati ◽  
Asnila Asnila ◽  
Suherman Suherman ◽  
Paulus Hengky Abram
Keyword(s):  
Reaction Order ◽  
Second Order ◽  
Hydrolysis Reaction ◽  
Starch Hydrolysis ◽  
First Order ◽  
Graph Method ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Avocado Seed

One of the plants that can be used as raw material for making sugar is plants that contain starch content such as avocado seeds. This study aims to determine the reaction order, the reaction rate constant from the hydrolysis of avocado seed starch using HCl. The method of this research is to determine the optimum concentration of HCl hydrolysis reaction from avocado seed starch using various concentrations of HCl (0.5 M; 1 M; 1.5 M; 2 M; 2.5 M) at the optimum temperature and stirring time (90oC for 70 minute). The hydrolysis process was followed by neutralization using 5 M NaOH solution and evaporated to obtain concentrated glucose, glucose was analyzed qualitatively and quantitatively by the Benedict method and the phenol sulfuric acid method. Based on the results of the maximum glucose levels obtained from the hydrolysis of variations in the concentration of HCl avocado seed starch, HCl 1.5 M. Furthermore, determine the kinetics of the starch hydrolysis reaction using time variations (30, 40, 50, 60 and 70) minutes at 90oC and concentrations The HCl 1.5 M. reaction order is determined by the intral method and the graph method. Determination of the first order graph method is done by plotting the value of ln [A] versus time, while the second order by plotting the value of 1 / [A] versus time. The first order with a 93% confidence level was obtained from the value of R2 = 0.9312, while the second order was 85% obtained from the value of R2 = 0.8581. Determination of the order of the integral method k value tends to remain in the first order formula with an average of k = 0.01962 minutes-1. Based on the two methods, it can be determined that the kinetics of the avocado seed starch hydrolysis reaction follows a first-order reaction.

FIRST ORDER PHASE TRANSITIONS IN A SOLID WITH FINITE SIZE

1990 ◽  
Vol 04 (10) ◽  
pp. 1671-1692 ◽  
Author(s):  
G.G. CABRERA
Keyword(s):  
Phase Transitions ◽  
Spontaneous Magnetization ◽  
Accurate Determination ◽  
Finite Size ◽  
Finite Width ◽  
Variable Boundary ◽  
First Order ◽  
Mass Gap ◽  
First Order Phase

First order phase transitions are rounded in solids of finite size. It is shown here that the above rounding is monitored by the correlation length ξL of the finite system, or equivalently by the so-called mass gap for the quantum Hamiltonian version of the model. Scaling with size is studied as a function of variable boundary conditions for the cylinder geometry (infinite strips with finite width), and a striking crossover is found in the mass gap behavior when the coupling g along the boundary becomes anti-periodic. For g>0, the rounding is exponential with size and an accurate determination of the spontaneous magnetization (order parameter) of the infinite system is obtained from numerical extrapolations.

Effects of Coupled Hydrodynamic in the Performance of a DP Barge Operating Close to a FPSO

2011 ◽  
Author(s):  
Daniel P. Vieira ◽  
Edgard B. Malta ◽  
Fabiano P. Rampazzo ◽  
Joa˜o Luis B. Silva ◽  
Eduardo A. Tannuri
Keyword(s):  
Incidence Angle ◽  
Accurate Determination ◽  
Control Surface ◽  
Wave Forces ◽  
Floating Bodies ◽  
First Order ◽  
Code Standard ◽  
Wave Incidence Angle ◽  
Drift Forces

In ocean systems composed by two or more closing floating bodies, coupled hydrodynamics effects must be considered. Dynamic positioned systems (DP), for example, need an accurate determination of environmental forces to guarantee a safe operation. This work presents a numerical methodology, using the WAMIT code, to evaluate both first order motions and mean drift forces of a system composed by a DP Crane Barge operating close to a turret-moored FPSO. The first order wave forces were evaluated using the code standard method. The second order forces (or mean drift forces) were obtained using the alternative control surface method. The work discussions are centered on the effects of FPSO presence on DP Barge hydrodynamics. Two relative positions between vessels were evaluated as well as three FPSO drafts (full, intermediate and ballasted). The effects of wave incidence angle were also discussed.

scholarly journals Fundamental Parameters of the W Serpentis Stars

1989 ◽  
Vol 107 ◽  
pp. 179-189
Author(s):  
J. Andersen ◽  
B. Nordström
Keyword(s):  
Accretion Disks ◽  
Cross Correlation ◽  
Accurate Determination ◽  
Correlation Spectroscopy ◽  
Mass Ratio ◽  
B Stars ◽  
Fundamental Parameters ◽  
First Order ◽  
Synchronous Rotation

AbstractApplication of digital cross-correlation spectroscopy to the spectra of the W Serpentis binaries SX Cas and RX Cas has allowed an accurate determination of the orbits and rotations of the (mass-losing) K-subgiant secondary components. The distortion of the primary radial-velocity curves due to the influence of the prominent accretion disks in these systems has been modelled to first order. This enables us to estimate K1 , and thereby the mass ratio q ≈ 0.30, to within ~±20%. The absolute radii of the secondaries are derived independently from the observed rotations and periods, assuming synchronous rotation. They show that the stars fill their Roche lobes, or at least very nearly so. Rough fits to the available photometry shows both primaries to be unevolved mid-B stars; that in RX Cas appears completely obscured by the disk. Preliminary spectroscopic data for W Ser and W Cru show some promise for similar analyses of these systems.

A quantitative approach to inner shell losses

1978 ◽  
Vol 36 (1) ◽  
pp. 526-527 ◽  
Author(s):  
R.D. Leapman ◽  
P. Rez ◽  
D.F. Mayers
Keyword(s):  
Energy Transfer ◽  
Cross Section ◽  
Cross Sections ◽  
Accurate Determination ◽  
Background Intensity ◽  
Core Excitation ◽  
Quantitative Basis ◽  
Cross Section Differential ◽  
Bound Electrons

Microanalysis by EELS has been developing rapidly and though the general form of the spectrum is now understood there is a need to put the technique on a more quantitative basis (1,2). Certain aspects important for microanalysis include: (i) accurate determination of the partial cross sections, σx(α,ΔE) for core excitation when scattering lies inside collection angle a and energy range ΔE above the edge, (ii) behavior of the background intensity due to excitation of less strongly bound electrons, necessary for extrapolation beneath the signal of interest, (iii) departures from the simple hydrogenic K-edge seen in L and M losses, effecting σx and complicating microanalysis. Such problems might be approached empirically but here we describe how computation can elucidate the spectrum shape.The inelastic cross section differential with respect to energy transfer E and momentum transfer q for electrons of energy E0 and velocity v can be written as

Fast calibration of CBED patterns for quantitative analysis

1993 ◽  
Vol 51 ◽  
pp. 674-675
Author(s):  
M.A. Gribelyuk ◽  
M. Rühle
Keyword(s):  
Reciprocal Lattice ◽  
Accurate Determination ◽  
Incident Beam ◽  
Crystal Thickness ◽  
Structure Model ◽  
Beam Direction ◽  
Transmitted Beam ◽  
Reciprocal Vector ◽  
On Line

A new method is suggested for the accurate determination of the incident beam direction K, crystal thickness t and the coordinates of the basic reciprocal lattice vectors V1 and V2 (Fig. 1) of the ZOLZ plans in pixels of the digitized 2-D CBED pattern. For a given structure model and some estimated values Vest and Kest of some point O in the CBED pattern a set of line scans AkBk is chosen so that all the scans are located within CBED disks.The points on line scans AkBk are conjugate to those on A0B0 since they are shifted by the reciprocal vector gk with respect to each other. As many conjugate scans are considered as CBED disks fall into the energy filtered region of the experimental pattern. Electron intensities of the transmitted beam I0 and diffracted beams Igk for all points on conjugate scans are found as a function of crystal thickness t on the basis of the full dynamical calculation.

Computer-Assisted High-Re Solution TEM

1990 ◽  
Vol 48 (1) ◽  
pp. 162-163
Author(s):  
F.A. Ponce ◽  
H. Hikashi
Keyword(s):  
Signal To Noise Ratio ◽  
Accurate Determination ◽  
Computer Software ◽  
Video Camera ◽  
Image Contrast ◽  
Objective Lens ◽  
Computer Assisted ◽  
Optical Parameters ◽  
Astigmatism Correction

The determination of the atomic positions from HRTEM micrographs is only possible if the optical parameters are known to a certain accuracy, and reliable through-focus series are available to match the experimental images with calculated images of possible atomic models. The main limitation in interpreting images at the atomic level is the knowledge of the optical parameters such as beam alignment, astigmatism correction and defocus value. Under ordinary conditions, the uncertainty in these values is sufficiently large to prevent the accurate determination of the atomic positions. Therefore, in order to achieve the resolution power of the microscope (under 0.2nm) it is necessary to take extraordinary measures. The use of on line computers has been proposed [e.g.: 2-5] and used with certain amount of success.We have built a system that can perform operations in the range of one frame stored and analyzed per second. A schematic diagram of the system is shown in figure 1. A JEOL 4000EX microscope equipped with an external computer interface is directly linked to a SUN-3 computer. All electrical parameters in the microscope can be changed via this interface by the use of a set of commands. The image is received from a video camera. A commercial image processor improves the signal-to-noise ratio by recursively averaging with a time constant, usually set at 0.25 sec. The computer software is based on a multi-window system and is entirely mouse-driven. All operations can be performed by clicking the mouse on the appropiate windows and buttons. This capability leads to extreme friendliness, ease of operation, and high operator speeds. Image analysis can be done in various ways. Here, we have measured the image contrast and used it to optimize certain parameters. The system is designed to have instant access to: (a) x- and y- alignment coils, (b) x- and y- astigmatism correction coils, and (c) objective lens current. The algorithm is shown in figure 2. Figure 3 shows an example taken from a thin CdTe crystal. The image contrast is displayed for changing objective lens current (defocus value). The display is calibrated in angstroms. Images are stored on the disk and are accessible by clicking the data points in the graph. Some of the frame-store images are displayed in Fig. 4.

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