1、Designation: E2781 11Standard Practice forEvaluation of Methods for Determination of KineticParameters by Thermal Analysis1This standard is issued under the fixed designation E2781; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, t
2、he year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 It is the purpose of this Practice to provide kineticparameters for reference materials used for evaluation
3、 ofthermal analysis methods, apparatus and software where en-thalpy and temperature are measured. This Practice addressesboth exothermic and endothermic, nth order and autocatalyticreactions.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included i
4、n thisstandard.1.3 There is no International Organization for Standardiza-tion (ISO) equivalent to this standard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate sa
5、fety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2E473 Terminology Relating to Thermal Analysis and Rhe-ologyE698 Test Method for Arrhenius Kinetic Constants forThermally Unstable Materials Using Differential
6、ScanningCalorimetry and the Flynn/Wall/Ozawa MethodE1142 Terminology Relating to Thermophysical PropertiesE1641 Test Method for Decomposition Kinetics by Ther-mogravimetryE1981 Guide for Assessing Thermal Stability of Materialsby Methods of Accelerating Rate CalorimetryE2041 Test Method for Estimati
7、ng Kinetic Parameters byDifferential Scanning Calorimeter Using the Borchardt andDaniels MethodE2070 Test Method for Kinetic Parameters by DifferentialScanning Calorimetry Using Isothermal Methods3. Terminology3.1 DefinitionsSpecific technical terms used in this prac-tice are defined in Terminologie
8、s E473 and E1142, includingdifferential scanning calorimetry.4. Summary of Practice4.1 Kinetics is the study of the relationship of the extent ofa chemical reaction to the independent parameters of time andtemperature. This relationship is often described using theArrhenius expression where:da/dt 5
9、Zfa! exp E/RT! (1)where:a = fraction left to react,f(a) = some function of (a),E = activation energy (J/mol),R = gas constant (=8.314 J mol1K1),T = absolute temperature (K), andZ = pre-exponential factor (1/sec).4.2 For many reactions of interest the description of thefunction of amount left to reac
10、t is of the form:fa! 5am1a!n(2)where m and n are the overall reaction orders. This form ofthe concentration dependence is known as the auto-catalyticform or the Sestak-Berggren reaction (1).3If the value of mequals 0, then f(a) reduces to the form of f(a) =(1a)ncommonly call nth order reaction.4.3 E
11、q 1 may be evaluated in either its exponential orlogarithmic form:ln da/dt! 5 ln Z 1 ln fa! E/RT (3)4.4 The study of kinetics involves the determination ofvalues of E, Z, m, and n for a given reaction.NOTE 1Activation energy and pre-exponential factor are not indepen-dent parameters but are inter-re
12、lated.NOTE 2The descriptions provided in Eq 1-3 are only mathematicalmodels. That is, they represent the fitting of mathematical equations tooften “noisy” experimental data. In practice no such model will faithfully1This practice is under the jurisdiction of ASTM Committee E27 on HazardPotential of
13、Chemicals and is the direct responsibility of Subcommittee E27.02 onThermal Stability and Condensed Phases.Current edition approved March 1, 2011. Published April 2011. DOI: 10.1520/E2781-11.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serv
14、iceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The boldface numbers in parentheses refer to a list of references at the end ofthis standard.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Cons
15、hohocken, PA 19428-2959, United States.describe the complete reaction(s) under all conditions for the materialsdescribed in this practice.4.5 Values for the kinetic parameter are typically in theranges indicated below:log Z: 8 to 30 with Z in s1E: 50 to 250 kJ/moln: 0.0 to 2.0m: 0 to 2.04.6 By their
16、 nature, thermally reactive materials maychange with time. For this reason, certified reference materialsare not available for use in the evaluation of kinetic parameters.The user of this standard may synthesize or purchase from acommercial laboratory supply house materials of suitablepurity for use
17、 in this standard.NOTE 3Storage of reference materials in a refrigerator may prolongshelf life. Observe manufacturers recommendations.4.7 The recommended values for the thermal active mate-rials identified in this standard are taken from “best values”found in the open literature as described in the
18、accompanyingtables.5. Significance and Use5.1 The kinetic parameters provided in this standard may beused to evaluate the performance of a standard, apparatus,techniques or software for the determination parameters (suchas Test Methods E698, E1641, E2041,orE2070) using thermalanalysis techniques suc
19、h as differential scanning calorimetry,and accelerating rate calorimetry (Guide E1981). The resultsobtained by these approaches may be compared to the valuesprovided by this practice.NOTE 4Not all reference materials are suitable for each measurementtechnique.6. Hazards6.1 Thermally reactive materia
20、ls evolve heat as part of theindicated reaction. Build up of this heat may lead to adangerous over-pressure condition or to a self acceleratingreaction. Operators shall use caution when working with suchmaterials. Operators shall use as small amount of material as ispractical for the measurement.6.2
21、 The reference materials described in this standard andtheir decomposition products may be explosive, carcinogenic,hazardous, toxic, or corrosive. Handling of these materialsshould be performed by trained workers who are knowledge-able with the Material Safety Data Sheets (MSDS) for eachmaterial. Te
22、tramethyl succinonitrile (TMSN), a decompositionproduct of azobisisobutyronitrile (AIBN), is considered a verytoxic (neurotoxic agent) and hazardous substance.7. Procedure7.1 Experimentally determined kinetic parameters are com-pared to the values described in this Practice as their quotient,express
23、ed as percent. Thus values less than unity or 100 %indicate that the determined value is less than the referencevalue while those greater than unity or 100 % indicate that thedetermined value is greater than the reference value.8. Calculation8.1 Conformance =(Observed Value 3 100 %)(Referenced Value
24、)NOTE 5Generally speaking, experimentally determined kinetic pa-rameters E and log Z are considered to be in agreement if they haveconformance between 80 and 120 % of the values described in Table 1.Experimentally determined values m and n are considered to be inagreement if they have conformance be
25、tween 70 and 130 % of the valuesdescribed in Table 1.NOTE 6The value of log Z depends upon the concentration of thereactant.9. Report9.1 Identification of the kinetic method being examined.9.1.1 Identification of the reference material being used forthe comparison, its source and purity.9.1.2 The co
26、mparison quotient (conformance) for each ki-netic parameter.10. Precision and Bias10.1 This practice is used to determine the bias of kineticvalues determined by other standards or candidate standards.TABLE 1 Kinetic Parameters for Kinetic Reference Materials (Derived from Tables 2-6)NOTE 1where:E =
27、 activation energy,Z = pre-exponential factor,n = reaction order,m = reaction order,H = enthalpy of reaction of the pure material, andDSC = differential scanning calorimeters.Material E, kJ/mol log (Z,1/s) nmH, kJ/g DescriptionDi-t-butylperoxide158.1 15.80 1.0 0.0 1.34Generally tested in liquid form
28、 as a 10 to 20 %solution in toluene. Kinetic parameters are solventsensitive. Suitable for calorimeters.Azidotriphenylmethane 165.1 19.00 1.0 0.0 Suitable for DSC.Azobenzene 102.5 11.98 1.0 0.0 0.254 Solid material, endothermic; Suitable for DSC.Azobisisobutyronitrile 128.5 15.12 1.0 0.0 Suitable fo
29、r calorimeters and DSC.Phenyltetrazolthiol 143 20.4 1.7 1.3 Suitable for DSC.E2781 11210.2 This practice does not generate experimental data andhas no precision.11. Keywords11.1 activation energy; kinetics; pre-exponential factor; re-action order; thermal analysisTABLE 2 Literature Values for Di-t-b
30、utylperoxide (DTBP) from which the Recommended Values for Table 1 are ObtainedNOTE 1where:E = activation energy,Z = pre-exponential factor,n = reaction order,H = enthalpy of reaction of the pure material,DSC = differential scanning calorimeters, andARC = accelerating rate calorimeter.E, kJ/mol log (
31、Z,1/s) H, kJ/g nAConditions Reference148 16.15 (2)163 16.45 gas phase (3)154 15.11 DSC, mineral oil (4)158 16.36 ARC, mineral oil, or toluene (5)122.1 6 2.8 11.51 6 0.33 1.19 6 0.02 DSC, 725 psi (6)136 12.87 0.1 M in diesel fuel (7)148 14.87 Neat (8)140 13.74 Neat (9)159.2 6 9.9 16.3 6 1.2 30 to 60
32、% in toluene (10)146.7 6 7.0 15.0 6 0.9 30 to 60 % in benzene (10)158.5 16.1 1.31 ARC (11)145.5 15.1 1.82 DSC (11)147.3 6 3.4 15.68 6 0.44 1.29 0.925 6 0.088 ARC (12)158.2 16.15 1.19 (13)1.335 (14)159 in t-butyl benzene (15)151 in toluene (16)142 in vapor phase (16)163 in vapor phase (17)157 in i-pr
33、opylbenzene (17)159 in t-butylbenzene (17)155 in t-butylamine (17)159.7 6 0.58 15.94 6 0.07 in vapor phase (18)157.7 6 0.63 15.71 6 0.08 (19, 20)138.4 6 2.5 13.16 6 0.31 (16)146.7 6 6.7 14.04 6 0.83 (21)161.3 6 3.1 16.30 6 0.39 (22)164.5 6 1.0 16.63 6 0.24 in diethylketone (23)158.4 6 1.2 15.82 6 0.
34、18 (24)152.6 6 1.5 15.33 6 0.13 in vapor phase (25)160.1 6 1.3 16.07 6 0.14 (26)158.1 6 0.25 15.80 6 0.03 (1.00) Gas phase “best” literature average (24)154.7 15.634 Solution (27)163.03 15.95- (28)157.3 6 2.1 15.94 6 0.34 (1.00) 15 % in toluene (29)1.25 6 0.04 (30)152.0 6 6.1 (1.00) 20 % in toluene
35、(31)158.2 6 4.9 19.62 6 0.59 1.0 6 0.05 20 % in toluene and benzene (32)161 (33)AValues in parenthesis are assumed.E2781 113TABLE 3 Literature Values for Azobenzene from which the Recommended Values for Table 1 are ObtainedNOTE 1where:E = activation energy,Z = pre-exponential factor,n = reaction ord
36、er, andH = enthalpy of reaction of the pure material.E, kJ/mol log (Z,1/s) H, kJ/g nAConditions Reference103.4 6 1.6 12.2 6 0.25 264.5 6 1.6 (1.00) (34)103.5 6 1 (1.00) (35)102.5 6 0.2 11.98 6 0.1 253.7 6 5.4 (1.00) Melt (36)AValues in parenthesis are assumed.TABLE 4 Literature Values for Azidotriph
37、enylmethane (Trityl azide) from which the Recommended Values for Table 1 are ObtainedNOTE 1where:E = activation energy,Z = pre-exponential factor,n = reaction order, andH = enthalpy of reaction of the pure material.E, kJ/mol log (Z,1/s) H, kJ/g nAConditions Reference145 6 11 17.0 6 1.7 (1.00) Test M
38、ethod E698 RR:E27-1002B165.1 6 17 19.0 6 2.0 1.32 6 0.30 Test Method E2041 RR:E37-1028CAValues in parenthesis are assumed.BSupporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:E27-1002.CSupporting data have been filed at ASTM Interna
39、tional Headquarters and may be obtained by requesting Research Report RR:E37-1028.TABLE 5 Literature Values for Azobisisobutyronitrile (AIBN) from which the Recommended Values for Table 1 are ObtainedNOTE 1where:E = activation energy,Z = pre-exponential factor,n = reaction order, andH = enthalpy of
40、reaction of the pure material.E, kJ/mol log (Z,1/s) H, kJ/g nAConditions Reference182 (37)129 15.20 (1.00) (38)121.3 6 9.2 14.42 6 1.3 1.02 (39)117.9 6 2.7 14.11 6 1.0 1.03 (39)99.7 13.24 (1.00) Test Method E698 (39)128.5 6 8.4 15.12 6 1.1 1238 6 78 (1.00) (40)AValues in parenthesis are assumed.TABL
41、E 6 Literature Values for Phenyltetrazolthiol from which the Recommended Values for Table 1 are ObtainedNOTE 1where:E = activation energy,Z = pre-exponential factor,n = reaction order,m = reaction order, andH = enthalpy of reaction of the pure material.E, kJ/mol log (Z,1/s) H, kJ/g nmConditions Refe
42、rence143 6 17 20.4 6 2.4 1.68 6 0.49 1.32 6 0.14 Test Method E2070 RR:E37-1029AASupporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:E37-1029.E2781 114REFERENCES(1) Sestak, and J., Berggren, G., “Study of the Kinetics of the Mechanis
43、mof Solid-Solid Reactions at Increasing Temperature,” ThermochimicaActa, Vol 3, 1971, pp. 112.(2) Yasutake, H., Kogyo Kayku (Journal of the Industrial ExplosivesSociety (Japan), Vol 52, 1991, p. 350.(3) Wrabetz, K., and Wong, J., Fresenius Zeitschrift fur AnalytischeChemie, Vol 329, 1987, p. 487.(4)
44、 Torfs, J.C.M., Leen, D., Dorrepaal, A.J., and Heijens, J.C., AnalyticalChemistry, Vol 56, 1984, p. 2863.(5) Gimzewski, E., and Audley, G., “Thermal Hazards: CalculatingAdiabatic Behavior from DSC Data,” Thermochimica Acta, Vol 214,1993, pp. 129140.(6) Griffiths, J.F., Gilligan, M.F., and Gray, P.,
45、Combustion and Flame,Vol 24, 1975, p. 11.(7) MacNeil, D.D., Christensen, L., Landucci, J., Paulsen, J.M., and Dahn,J.R., Journal of the Electrochemical Society, Vol 147, 2000, p. 970.(8) Oxley, J.C., Smith, J.L., Rogers, E., Ye, W., Ardai, A.A., and Henly,T.J., Energy Fuels,Vol 14, 2000, p. 1252.(9)
46、 MacNeil, D.D., Trussler, S., Fortier, H., and Dahn, J.R., “A NovelHertic Differential Scanning Calorimeter Sample Crucible,” Ther-mochimica Acta, Vol 386, 2002, pp. 153160.(10) Aldeeb, A.A., Rogers, W.J., and Mannan, M.S., “Theoretical andExperimental Methods for the Evaluation of Reactive Chemical
47、Hazards,” Transactions of the Institution of Chemical Engineers,Vol 80, 2002, pp. 141149.(11) Hofelich, T.C., Frurip, D.J., and Powers, J.B., “The Determination ofCompatibility via Thermal Analysis and Mathematical Modeling,”Process Safety Progress, Vol 13, 1994, pp. 227233.(12) Towsend, D.I., and T
48、ou, J.C., Thermochimica Acta, Vol 37, 1980,pp. 130.(13) Whiting, L.F., LaBean, M.S., and Eadie, S.S., Thermochimica Acta,Vol 136, 1988, pp. 231245.(14) Grewer, T., Thermal Hazards of Chemical Reactions, Elsevier, NewYork, 1994, p. 394.(15) Ball, E., Rust, F., and Vaughn, W., Journal of the AmericanC
49、hemical Society, Vol 72, 1950, p. 337.(16) Murawaski, J., Roberts, J.S., and Szwarc, M., Journal of ChemicalPhysics, Vol 19, 1951, p. 698.(17) Raley, J., Rust, F., and Vaughan, W., Journal of the AmericanChemical Society, Vol 70, 1948, pp. 1136, 2767.(18) Birss, F.W., Danby, C.J., and Hinshelwood, C.N., Proceedings of theRoyal Society A, Vol 239, 1957, p. 154.(19) Blatt, L., and Benson, S.W., Journal of Chemical Physics, Vol 36,1962, p. 895.(20) Blatt, L., and Benson, S.W., Journal of Chemical Physics, Vol 38,1963, p. 3031.(21) Jauiss, M.T., R
