2CHETAH® Computer Program for Energy Release Evaluation and Prediction of Chemical Thermodynamic Properties.The CHETAH® program is a unique tool for predicting both thermochemical and flammability properties and certain reactive chemicals hazards associated with a pure chemical, a mixture of chemicals, or a chemical reaction. The calculations are made using only information concerning the molecular structure of the components
3Capabilities of CHETAH Gas phase thermochemistryheats of reactionheat of combustionequilibrium constantsmisc. thermodynamic properties“Energy Release Evaluation”tendency for a material to “explode”Predicts Lower Flammable Limit and other flammability properties
4Unique CapabilitiesLargest Database for Benson Groups (886!) Suggests substitutes for missing groups!Prediction of Reactive Chem. Hazards (ERE)Large whole molecule database: from DIPPR (1200 species!)
5Benson’s Method Example Atom Benson Contribution to Group DfH(g), kcal/mol1 NH2 - ( C)2 CH2 - ( N, C)3 CH2 - (2C)4 CHCl - (2C)5 CH - (O, 2C)6 OH - (C)7 CH3 - ( C)Total:
6Don’t Know How to Specify Benson Groups. Don’t Despair Don’t Know How to Specify Benson Groups? Don’t Despair! Graphical User Interface May Be Used:Uses ChemDraw®Molecular DrawingSoftwareSave structureas “SMILES” stringCut and Pasteinto CHETAHAutomatically converts to Benson groups!
8Main Screen for CHETAH. The user can directly enter the molecules from the database or use Benson groups to describe the new molecule.
9As an alternative, we can describe the molecule using an appropriate molecular drawing program. Here we draw a molecule in ChemdrawTM Software (
10Next we select the drawn molecule and copy it as a SMILES string
11We now return to the CHETAH program and choose SMILES Input We now return to the CHETAH program and choose SMILES Input. Next we paste the SMILES string we that copied from the other application and choose OK.
12Now we see a screen showing the Benson groups composing the molecules. We select Next.
13Select “Thermodynamic Table” from the “Calculations” menu.
14Next we see a screen asking for information relating to the Thermodynamic Table that we wish to calculate. Select “Calculate”.
15The following is the resulting table of calculated thermodynamic values
17CHETAH Heat of Combustion CHETAH can calculate heat of combustion for any compound or mixture composed of any of approximately 70 elements.CHETAH calculates the heat of combustion based on the reactant(s) being ideal gases at 298 K.CHETAH chooses combustion products based on a standard set of rules.
18On this screen the user can enter molecules from the database or from Benson groups. Here we search for the chemical Phenol.
19The search box was used to locate phenol in the gas molecules database The search box was used to locate phenol in the gas molecules database. The component phenol is then selected and “Add Group” is clicked.
20Note the changes. Phenol has been added in first row of the first column with its molecular weight shown above.
21Select the name bar above the first column and enter the desired name for the component.
22Choose “Combustion Heat” from “Calculations” menu.
23Next we see a screen asking for information related to Combustion Calculations. Select “Calculate”.
24These are the results for the combustion calculations.
26CHETAH for Reactive Hazard Evaluation Conservative screening toolEnergy related hazards frequently not knownExperimentally determined thermochemical data are often not availableCHETAH® can perform an energy releaseevaluation based on structure onlyCan give the maximum energy of decompositionHazard evaluations are valid for gas, liquid, or solid materials
27On this screen the user can enter molecules from the database or from Benson groups. Here we will enter Tri Nitro Toluene (TNT) from Benson groups.
28For TNT, select Benson Groups as shown on the following slides. Enter the numbers of each group in the ‘Count’ column.
37Maximum Heat of Decomposition Easiest to understand and most intuitively soundIn a material capable of harmful energy release, all of the energy is obtained from the material itselfCHETAH chooses products which maximize the enthalpy of decomposition
39Reaction Thermochemistry in CHETAH Build all speciesClick on Reaction buttonSpecify stoichiometryCH3-(C)CHCl-(2C)CH2-(2C)CH2-(C,O)OH-(C)CH3 - (C)CHCl - (C, =C)=CH - (C)=CH2
40Think Simplification!!! Example: R(g) + Cl2(g) => R-Cl(g) + HCl(g) "Analog Reaction Hypothesis" states that the heats of reaction for structurally similar reactions are identicalExample: R(g) + Cl2(g) => R-Cl(g) + HCl(g)Species, R rH, kcal/mol, 25 CEthaneOctaneTolueneNaphthalene
49Phase Effects CHETAH Calculations are gas phase values! If chemistry takes place in condensed phase (i.e. in a solvent), corrections need to be consideredmany times these corrections cancel but not always!Rule of thumb: vaporiz. heat = 100cal/g (150 cal/g for a H-bonded species, 80 cal/g for a chlorinated species)Estimation methods for heat of vaporization are available.
51CHETAH FlammabilityCHETAH calculates LFL, LOC, MIE and a number of other flammability parameters using Britton’s method.CHETAH will calculate LFL at temperatures besides 298 K.CHETAH also calculates LFL by Bothwell’s method.CHETAH can calculate LFL for mixtures.
52To find the flammability parameters of a gas mixture, the user should enter molecules from the Gas Molecules database or enter molecules by the use of Benson Groups.
53Here Propane and N-butane have been selected from the Gas Molecules database.
54After selecting the components, choose “Flammability” from the “Calculations” menu.
55Next we see a screen asking for the composition of the mixture. Choose the amount of each chemical. Select “Calculate”.
56The first part of the results page for this flammability example The first part of the results page for this flammability example. This part shows results from Britton’s method.
57This section highlights predictions by Bothwell’s method.
58Clicking on “Definitions” will display a list of definitions LFL: The Lower Flammable Limit is the minimum concentration of a combustible substance that is capable of propagating a flame through a homogeneous mixture of the combustible and a gaseous oxidizer under specified conditions.LOC: The Limiting Oxygen Concentration of a fuel-oxidant-inert system is the oxygen (oxidant) concentration at the limit of flammability for the worst case (most flammable) fuel concentration.Etc. for LLFT, T-max, Su, qd, MIE
59For more information or to purchase CHETAH 8 For more information or to purchase CHETAH 8.0, please visit this link: