A desk computer program for the calculation of rate constants

A desk computer program has been written in BASIC programming language to optimize the values of rate constants determined from kinetic measurements of time and concentration data. The program is capable of the simultaneous refinement of a maximum of 5 rate constants. A FORTRAN version using the Gear method is also available.

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A multistep method with optimal properties for second order differential equations

In the present paper an effective symmetric hybrid six-step method for the approximation of the solution of the Schrödinger equation and related problems is developed. More specifically, we will produced a method with the following properties: (1) is a symmetric hybrid six-step method, (2) is of twelfth algebraic order, (3) has three stages, (4) has eliminated phase-lag, (5) has eliminated the derivatives of the phase-lag up to order three. This numerical pair is obtained for the first time in the literature. We present a detailed analysis for the new obtained numerical scheme. More specifically we present:

• the construction of the new pair
• the computation of the local truncation error of the new numerical pair
• the comparison of the asymptotic form of the local truncation error of the new numerical scheme with the the classical pair of the family (i.e. scheme with constant coefficients), the recently developed scheme of the family with vanished phase-lag and its first derivative and the recently developed algorithm of the family with vanished phase-lag and its first and second derivatives
• the stability and interval of periodicity analysis and
• finally, the accuracy and computational efficiency of the new numerical pair for the solution of the Schrödinger equation.

The theoretical and numerical achievements which are presented in this paper, show the efficiency of the new numerical pair compared with other known or recently developed pairs of the literature.

     

Acuchem: A computer program for modeling complex chemical reaction systems

Acuchem is a program for solving the system of differential equations describing the temporal behavior of spatially homogeneous, isothermal, multicomponent chemical reaction systems. It is designed to provide modelers, data evaluators, and laboratory scientists with an easy to use program for modeling complex chemical reactions, and for presenting the results in tabular or graphical form. The program is described and some examples of its application given. Acuchem is designed to operate on the IBM Personal Computer family and other compatible microcomputers, and is available in a compiled version on a floppy disk.     

A new method for testing polymer gear wear rate and performance

This paper provides details of a new test rig design and methodology intended for, and successfully applied to, measuring the gear wear rate and performance of polymer composite gears under both dry and lubricated conditions. One of its unique contributions is that it continuously measures the gear wear rate, a feature essential for understanding polymer gear behaviour. While sharing some concepts with the traditional back-to-back test configuration used for steel gears, the new method introduces a rotary freedom to the block supporting the polymer gears under test. This block rotates if the gear tooth thickness is reduced, which aids control of the test load. The gear surface wear rate is recorded continuously by using a capacitance transducer to measure the pivot block motion. A second unique contribution of the new test method involves splitting the support block so that controlled misaligned gear engagements (not reported in other designs) can be introduced and subsequent changes to wear behaviour studied. The paper first outlines the test rig concepts and design before discussing in more detail the gear wear rate measuring principles, the methods of centre distance adjustment and the achievement of virtually constant gear loading. Finally, a selection test results are presented in summary to further validate the new test method and illustrate potential applications.     

A combined explicit-implicit method for high accuracy reaction path integration

We present the use of an optimal combined explicit-implicit method for following the reaction path to high accuracy. This is in contrast to most purely implicit reaction path integration algorithms, which are only efficient on stiff ordinary differential equations. The defining equation for the reaction path is considered to be stiff, however, we show here that the reaction path is not uniformly stiff and instead is only stiff near stationary points. The optimal algorithm developed in this work is a combination of explicit and implicit methods with a simple criterion to switch between the two. Using three different chemical reactions, we combine and compare three different integration methods: the implicit trapezoidal method, an explicit stabilized third order algorithm implemented in the code DUMKA3 and the traditional explicit fourth order Runge-Kutta method written in the code RKSUITE. The results for high accuracy show that when the implicit trapezoidal method is combined with either explicit method the number of energy and gradient calculations can potentially be reduced by almost a half compared with integrating either method alone. Finally, to explain the improvements of the combined method we expand on the concepts of stability and stiffness and relate them to the efficiency of integration methods.     

Steepest descent reaction path integration using a first-order predictor-corrector method

The theoretical treatment of chemical reactions inevitably includes the integration of reaction pathways. After reactant, transition structure, and product stationary points on the potential energy surface are located, steepest descent reaction path following provides a means for verifying reaction mechanisms. Accurately integrated paths are also needed when evaluating reaction rates using variational transition state theory or reaction path Hamiltonian models. In this work an Euler-based predictor-corrector integrator is presented and tested using one analytic model surface and five chemical reactions. The use of Hessian updating, as a means for reducing the overall computational cost of the reaction path calculation, is also discussed.     

Self-adapting computer program system for designing organic syntheses

The computer program SCANSYNTH is designed to assist in planning organic syntheses. The system features a new mode of data input/output, and is self-adapting, with simultaneous generation of possible synthesis schemes in the forward and reverse directions. Operational options include modeling of individual reactions, one-step reactions and multi-step reactions.     

A computer program for activation analysis

A computer program for calculating activation analysis results is described. The program comprises two gamma spectrum analysis programs, STOAV and SAMPO and one program for calculating elemental concentrations, KVANT. STOAV is based on a simple summation of channels and SAMPO is based on fitting of mathematical functions. The programs are tested by analyzing the IAEA G-1 test spectra. In the determination of peak location SAMPO is somewhat better than STOAV and in the determination of peak area SAMPO is more than twice as accurate as STOAV. On the other hand, SAMPO is three times as expensive to use with a Cyber 170 computer as STOAV.     

A non-conventional method of polymer PAL spectrum analysis by the LT computer program

A new version of computer program (LT v.10) offers a new concept of polymer spectrum analysis. The theoretical model takes into account a few processes in which positron is involved: the process of slow formation and localization of positronium (Ps), delay formation of positronium from shallow trapped electrons and positron trapping in irradiation-induced centers. The model was applied to two series of spectra for LDPE and HDPE collected at constant temperature (much below the glass temperature) as a function of measurement time. The Ps internal relaxation time and time of localization of Ps in a free-volume center were determined. The results show that the trapping rate of positron is strictly correlated with the amount of the shallow trapped electrons. That suggests a coupling between the positron and electron-trapping centers.     

The computer program LUDI: A new method for the de novo design of enzyme inhibitors

Summary A new computer program is described, which positions small molecules into clefts of protein structures (e.g. an active site of an enzyme) in such a way that hydrogen bonds can be formed with the enzyme and hydrophobic pockets are filled with hydrophobic groups. The program works in three steps. First it calculates interaction sites, which are discrete positions in space suitable to form hydrogen bonds or to fill a hydrophobic pocket. The interaction sites are derived from distributions of nonbonded contacts generated by a search through the Cambridge Structural Database. An alternative route to generate the interaction sites is the use of rules. The second step is the fit of molecular fragments onto the interaction sites. Currently we use a library of 600 fragments for the fitting. The final step in the present program is the connection of some or all of the fitted fragments to a single molecule. This is done by bridge fragments. Applications are presented for the crystal packing of benzoic acid and the enzymes dihydrofolate reductase and trypsin.     

A new computer program for QSAR-analysis: ARTE-QSAR

A new computer program has been designed to build and analyze quantitative-structure activity relationship (QSAR) models through regression analysis. The user is provided with a range of regression and validation techniques. The emphasis of the program lies mainly in the validation of QSAR models in chemical applications. ARTE-QSAR produces an easy interpretable output from which the user can conclude if the obtained model is suitable for prediction and analysis.     

Spectra: A computer program for gamma-ray analysis

A computer program infortran iv is presented for the determination of peak location, peak areas and elemental abundances of γ-ray spectra.     

A Program package using stiff,sparse integration methods for the automatic solution of mass action kinetics equations

A portable program package, MACKSIM, for mass action chemical kinetics simulation, is discussed. As these kinetics are readily expressed in explicit mathematical terms, such a package contains two major and distinct modules, the numerical analysis and the user interface. For the first, MACKSIM uses the latest proven developments incorporating sparse matrix techniques in the backward difference predictor corrector methods originated by Gear for the integration of stiff ordinary differential equations, and thus requires minimal computing time to solve large systems of equations. For the second, the program provides a flexible interface which permits simple specification and variation of reactions, requires no special character input, and has no limit on the number of reactions or species involved other than that imposed by the size of the computer. The technology of these components is discussed briefly, the use of the package for standard reactions is illustrated, and current applications are mentioned.     

A simple computer program for high resolution gamma-ray spectra

A computer program is presented, which locates peaks in high-resolution γ-ray spectra and determines their content. The program has been written in Basic; ‘translations’ have been made into Fortran and Algol. For detailed information the reader is referred to the original TNO Report CL 69/137.     

Constant time interval method for analysis of reaction rate data

In the study of chemical kinetics, many integrated reaction rate equations have the form In [f(A) + a] = bt + c, where a, b, and c are constants and f(A) is some function of the concentration of a reactant (or product) which can be calculated from the data. The left-hand side of this equation cannot be graphed versus time if the constant a is unknown. However, it is shown that f(A2) varies linearly with f(A₁) if A₂ is the concentration of reactant measured at a constant time interval later than A₁. The constants a and b can be determined from the linear graph. A number of specific examples are considered.     

A new spectral collocation method for solving Bratu-type equations using Genocchi polynomials

Journal of Mathematical Chemistry - In this paper, we have introduced a new Genocchi polynomial approximation method for solving Bratu-type equations arising in Engineering. With the help of...     

Spectrophotometric reaction rate method for determination of barbituric acid by inhibition of the hydrochloric acid-bromate reaction

A new kinetic-spectrophotometric method was developed for the determination of barbituric acid. The method is based on its inhibition effect on the reaction between hydrochloric acid and bromate. The decolorization of methyl orange by the reaction products was used to monitor the reaction spectrophotometrically at 510 nm. The variable affecting the rate of the reaction was investigated. The method is simple, rapid, relatively sensitive and precise. The limit of detection is 7.9x10(-7) M and calibration rang is 1x10(-6)-6.0x10(-4) M barbituric acid. The linearity range of the calibration graph is depends on bromate concentration. The relative standard deviation of seven replication determination of 5.6x10(-6) M barbituric acid was 1.8%. The influence of potential interfering substance was studied.     

A generalized computer program for determining the kinetic mechanism of solid-state reactions

A consideration of the various types of reactions controlling kinetic processes in general appears to suggest that it is possible to express all such reactions by a differential equation of the form $\text{dα}\text{d}\text{t}$ = A exp(?E/RT)(1?α)ⁿαⁿ[?1n(1?α1]^pwhere α = fraction of the substance reacted, t = time of reaction, A = pre-exponential factor, E = energy of activation, R = universal gas content, and m, n, p are constants The presence (or absence) of the indices m, n, p, cr any combination of these, in this equation when it is fitted to a set of thermogravimetric data relating to the fraction of the substance decomposed and the absolute temperature can reasonably be expected to throw light on the mechanism of the process.This paper presents the features of a numerical algorithm for studying kinetic data on the above lines and suggests a possible scheme for predicting the most probable kinetic mechanism by a consideration of the differences of the predicted from the experimental values. A computer program was developed on an IBM 360 computer for implementing this scheme and evaluating the kinetic parameters from experimental thermogravimetric data. The values obtained from the program for a pyrolysis reaction which typifies the system and the inferences drawn therefrom regarding the relevant reaction mechanism are included.