At a Glance Highlights of Thermokinetics 3 Purpose Kinetic analysis Predictions Optimization Thermokinetics is the software for studying chemical kinetics (reactional kinetics). It investigates the reaction rates of chemical processes depending on time and temperature. Thermokinetics software features a unique model-based method that allows for analysis of multi-step processes, determination of a kinetic model and predictions as well as optimizations based on this model. Professional version only: The software determines kinetics model including Number of reaction steps Step contribution to the total effect Based on the created kinetic model, the software simulates the reaction rate and conversion for user-defined temperature programs. This allows for prediction of sample properties for temperature conditions, which differ from the conditions originally used during the measurement(s). The Thermokinetics software can optimize the temperature program in order to achieve the desired system behavior such as constant conversion rate or given rate of production of the final product. System Requirements, General Data of the Software Operating system Application language Integrated help system Microsoft Windows 7, Windows 8, Windows 8.1, Windows 10 32 bit or 64 bit English Context-sensitive, browser-style HTML help interface Desktop PC, laptop or Tablet PC; Intel Core i3 processor, 4 GB RAM, hard disk space 20 GB, Minimal hardware requirements display 1440 x 1050 Software delivery Online updates Internet download. CD is available as paid option Search for free software updates online Microsoft and Window s are registered trademarks of Microsoft Corporation in the United 1 5
Data for Analysis (Basic and Professional) Data type for kinetic analysis Number of measurement data Import Baseline types DSC Correction TGA DTA DSC DIL EGA Rheology DMA-E Pressure Temperature increase Up to 16 measurements per analysis Data import can be done using ASCII format. Data should contain either three columns (time, temperature, signal) or, alternatively, two columns (time and signal or temperature and signal) and the value of the heating rate. Linear Horizontal area proportional Tangential area proportional Horizontal left starting Horizontal right starting Zero Bezier Correction of DSC data regarding thermal resistance and time constant. Model-Free Methods (Basic and Professional) Definition Conversion-dependent Results for conversiondependent Methods based on a single conversion Results for single conversion Model-free analysis allows to find the activation energy of the reaction without assumption of a kinetic model. Friedman Ozawa-Flynn Wall (OFW) Kissinger-Akhira-Sunose (KAS) Graph (log (heating rate) or log dx/dt versus 1000/T) Energy plot Table of activation energies and pre-exponential factors ASTM E698 ASTM E2890 ASTM E1641 Graph (log (heating rate) versus 1000/T) One value of the activation energy and one value of the pre-exponential factor 2 5
Model-Based Methods for Single-Step Reactions (Linear Regression Basic and Professional) Automatic determination Kinetic models s Models with diffusion control Calculation settings Kinetic results Statistical results Automatic determination of the best reaction type and statistical comparison of all reaction types tested. Single-step: 1 model Reaction of 1 st order Reaction of n-th order Two-dimensional phase boundary Three-dimensional phase boundary One-dimensional diffusion Two-dimensional diffusion Three-dimensional diffusion Lander s type Three-dimensional diffusion Ginstling-Brounsthein type Prout-Tompkins equation Expanded Prout-Tompkins equation (na) Reaction of 1 st order with autocatalysis by X Reaction of n-th order with autocatalysis by X Two-dimensional nucleation Three-dimensional nucleation n-dimensional nucleation according to Avrami-Erofeev 1-dimensional diffusion accordong to Fick s law 3-dimensional diffusion according to Fick s law Reaction with inhibitor m-th order reaction with positive equilibrium temperature m-th order reaction with negative equilibrium temperature Power law of n-th order Modelling of reactions with diffusion control, containing variation of the glass transition during a curing reaction. Fit of the dependence of T g versus conversion by both the exponential model and the model according to di Benedetto. Calculation of TTT diagram Possibility to select one of 8 weighing functions in order to get the best fit for the data-containing curve (e.g., higher weighing of the data at the lower or upper end of the curve). Number of points for calculation Relative and absolute accuracy for integration of differential equations Select one of 6 solvents for integration of differential equations Correlation coefficient Sum of the squares of deviations Mean residual t-value Durbin-Watson value Durbin-Watson test F-test for fit quality 3 5
Model-Based Methods for Multi-Step Reactions (Non-Linear Regression Professional Only) Multi-step analyzing engine Unique features Kinetic models s Kinetic results Statistical results The Thermokinetics Basic version allows just analyzing one-step kinetic processes. However, approximately 95% of all chemical reactions are multi-step reactions. This requires the multi-step analyzing engine of the Thermokinetics Professional software. The model-based kinetic analysis is based on 79 models which include up to six-step processes and in which the individual steps are linked as independent, parallel, competing or following. Multi-step models can describe the reversing reactions or processes with inhibitor. Single-step: 1 model Double-step: 8 models Triple-step: 18 models Four-step: 21 models Five-step: 16 models Six-step: 15 models Each individual reaction step in each model an be one of 21 reaction types (see model-based for single-step reactions). Software determines the kinetic models including Number of reaction steps Step contribution to the total effect Correlation coefficient Sum of the squares of deviations Mean residual t-value Durbin-Watson value Durbin-Watson test F-test for fit quality F-test for number of steps Predictions (Basis and Professional) Isothermal predictions, single-step only Isothermal prediction, single und multiple step TTT diagram User-defined temperature program for prediction Conversion curves as a function of time with temperature as parameter Isoconversional curves with degree of conversion as parameter Tabular output of the reaction rate and the time for half of conversion as a function of temperature Signal curves as a function of time with temperature as parameter (with selectable temperature) Partial reaction curve as a function of time with temperature as parameter Tabular output of the time as a function of partial reaction with temperature as parameter Concentration over time of the formal reactants with temperature as parameter Final product over time with temperature as parameter Tabular output of the time as a function of conversion with temperature as parameter Curves as a function of time with temperature as parameter Time-Temperature-Transition (TTT) diagram is used for the description of the isothermal curing behavior of thermoset resins. Temperature program consists of one or several temperature segments of the following types: Isothermal Dynamic Isothermal with daily temperature oscillations Dynamic with daily temperature oscilliations Segment oscillations of user-defined amplitude and duration The user should input the temperature program and the software will make a simulation of the system behavior. The following values can be simulated: Measurement output (signal) Results of prediction according Partial reactions to the user-defined temperature Partial mass loss program Partial area, etc. Concentration of the reactants Reaction rate for individual reaction steps 4 5
Optimization (Basics and Professional) Condition for optimization Results of optimization Goal: Finding of the temperature program for a given system behavior (optimization). This is a typical problem for the production process when the suitable temperature program for an optimal production time and an optimal product quality has to be developed. Without Thermokinetics software, it is necessary to make an adjustment of the temperature program and to measure several times hoping to achieve the expected signal curve (trial and error). The software saves time and finds such a temperature program: for a given reaction rate for a given output signal for a given rate of final product production Temperature program Measurement output (signal) Partial reactions Partial mass loss Partial area, etc. Concentration of the reactants File Operations, Graphics and Export Graphical presentation of data and results Graphical options Export Presentation of data in graphical format having X-axes as temperature, time, logarithm of time, square root of time, Y-axes in absolute scale, relative scale from minimal to maximal value for each curve, in differential (DSC, DTG) or integral (conversion, TGA) view. ARC can be presented in TMR view. Set color and type for each data curve Set color and font for graphical text and for report text Add grid Add legend Add kinetic model Add arbitrary text to the graphics For all data, analysis results, predictions and optimization, the following operations are enabled: ASCII export of results, including measured data and simulated curves as well as activation energies and pre-exponential factor for model-free analysis Copy graphics to clipboard Save graphics as a picture in EMF, JPEG and BMP format 5 5