1、Designation: E2781 11E2781 16Standard Practice forEvaluation of Methods for Determination of KineticParameters by Thermal AnalysisCalorimetry and DifferentialScanning Calorimetry1This standard is issued under the fixed designation E2781; the number immediately following the designation indicates the
2、 year oforiginal adoption or, in the case of revision, the 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. Scope Scope*1.1 It is the purpose of this practice to provid
3、e kinetic parameters for reference materials used for evaluation of thermal analysismethods, apparatus, and software where enthalpy and temperature are measured. This practice addresses both exothermic andendothermic, nth order, and autocatalytic reactions.1.2 The values stated in SI units are to be
4、 regarded as standard. No other units of measurement are included in this standard.1.3 There is no International Organization for Standardization (ISO) equivalent to this standard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the res
5、ponsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2E473 Terminology Relating to Thermal Analysis and RheologyE698 Test Method for Kinetic Paramet
6、ers for Thermally Unstable Materials Using Differential Scanning Calorimetry and theFlynn/Wall/Ozawa MethodE1142 Terminology Relating to Thermophysical PropertiesE1641 Test Method for Decomposition Kinetics by Thermogravimetry Using the Ozawa/Flynn/Wall MethodE1981 Guide for Assessing Thermal Stabil
7、ity of Materials by Methods of Accelerating Rate CalorimetryE2041 Test Method for Estimating Kinetic Parameters by Differential Scanning Calorimeter Using the Borchardt and DanielsMethodE2070 Test Method for Kinetic Parameters by Differential Scanning Calorimetry Using Isothermal Methods3. Terminolo
8、gy3.1 DefinitionsSpecific technical terms used in this practice are defined in Terminologies E473 and E1142, includingdifferential scanning calorimetry.4. Summary of Practice4.1 Kinetics is the study of the relationship of the extent of a chemical reaction to the independent parameters of time andte
9、mperature. This relationship is often described using the Arrhenius expression where:d/dt5Z f!exp2E/RT! (1)where: = fraction left to react,f() = some function of (),1 This practice is under the jurisdiction ofASTM Committee E37 on Thermal Measurements and is the direct responsibility of Subcommittee
10、 E37.02 on Standard ReferenceMaterials.Current edition approved March 1, 2011Nov. 1, 2016. Published April 2011November 2016. Originally approved in 2011. Last previous edition approved in 2011 as E2781 11. DOI: 10.1520/E2781-11.10.1520/E2781-16.2 For referencedASTM standards, visit theASTM website,
11、 www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of
12、 what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered
13、 the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1E = activation energy (J/mol),R = gas constant (=8.314 J mol1 K1),T = absolute temperature (K), an
14、dZ = pre-exponential factor (1/sec).4.2 For many reactions of interest the description of the function of amount left to react is of the form:f!5m 12!n (2)where m and n are the overall reaction orders. This form of the concentration dependence is known as the auto-catalytic formor the Sestak-Berggre
15、n reaction reaction.(1).3 If the value of m equals 0, then f() reduces to the form of f() = (1 )n commonlycallcalled nth order reaction.4.3 Eq 1 may be evaluated in either its exponential or logarithmic form:lnd/dt! 5lnZ1lnf!2E/RT (3)4.4 The study of kinetics involves the determination of values of
16、E,Z,m, and n for a given reaction.NOTE 1Activation energy and pre-exponential factor are not independent parameters but are inter-related.NOTE 2The descriptions provided in Eq 1-3 are only mathematical models. That is, they represent the fitting of mathematical equations to often“noisy” experimental
17、 data. In practice, no such model will faithfully describe the complete reaction(s) under all conditions for the materials describedin this practice.4.5 Values for the kinetic parameter are typically in the ranges indicated below:log Z: 8 to 30 with Z in s 1E: 50 to 250 kJ/moln: 0.0 to 2.0m: 0 to 2.
18、0m: 0.0 to 2.04.6 By their nature, thermally reactive materials may change with time. For this reason, certified reference materials are notavailable for use in the evaluation of kinetic parameters. The user of this standardpractice may synthesize or purchase from acommercial laboratory supply house
19、 materials of suitable purity for use in this standard.practice.NOTE 3Storage of reference materials in a refrigerator may prolong shelf life. Observe manufacturersmanufacturers recommendations.4.7 The recommended values for the thermal activethermally reactive materials identified in this standardp
20、ractice are taken from“best values” found in the open literature as described in the accompanyingResearch Report RR:E37-1029tables45. Significance and Use5.1 The kinetic parameters provided in this standardpractice may be used to evaluate the performance of a standard, apparatus,techniques, or softw
21、are for the determination parameters (such as Test Methods E698, E1641, E2041, or E2070) using thermalanalysis techniques such as differential scanning calorimetry, and accelerating rate calorimetry (Guide E1981).The results obtainedby these approaches may be compared to the values provided by this
22、practice.NOTE 4Not all reference materials are suitable for each measurement technique.6. Hazards6.1 Thermally reactive materials evolve heat as part of the indicated reaction. Build up of this heat may lead to a dangerousover-pressure condition or to a self accelerating reaction. Operators shall us
23、e caution when working with such materials. Operatorsshall use as small amount of material as is practical for the measurement.6.2 The reference materials described in this standardpractice and their decomposition products may be explosive, carcinogenic,hazardous, toxic, or corrosive. Handling of th
24、ese materials should be performed by trained workers who are knowledgeable withthe Material Safety Data Sheets (MSDS)(SDS) for each material. Tetramethyl succinonitrile (TMSN), a decomposition product ofazobisisobutyronitrile (AIBN), is considered a very toxic (neurotoxic agent) and hazardous substa
25、nce.7. Procedure7.1 Experimentally determined kinetic parameters are compared to the values described in this practice as their quotient,expressed as percent. Thus values less than unity or 100 % indicate that the determined value is less than the reference value whilethose greater than unity or 100
26、 % indicate that the determined value is greater than the reference value.3 The boldface numbers in parentheses refer to a list of references at the end of this standard.Sestak, and J., Berggren, G., “Study of the Kinetics of the Mechanism ofSolid-Solid Reactions at Increasing Temperature,” Thermoch
27、imica Acta, Vol 3, 1971, pp. 112.4 Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:E37-1029. Contact ASTM CustomerService at serviceastm.org.E2781 1628. Calculation8.1 Conformance = (Observed Value 100 %)(Referenced Value)NOTE 5
28、Generally speaking, experimentally determined kinetic parameters E and log Z are considered to be in agreement if they have conformancebetween 80 and 120 % of the values described in Table 1. Experimentally determined values m and n are considered to be in agreement if they haveconformance between 7
29、0 and 130 % of the values described in Table 1.NOTE 6The value of log Z depends upon the concentration of the reactant.9. Report9.1 Identification of the kinetic method being examined.9.1.1 Identification of the reference material being used for the comparison, its source, and purity.9.1.2 The compa
30、rison quotient (conformance) for each kinetic parameter.10. Precision and Bias10.1 This practice is used to determine the bias of kinetic values determined by other standards or candidate standards.10.2 This practice does not generate experimental data and has no precision.11. Keywords11.1 activatio
31、n energy; kinetics; pre-exponential factor; reaction order; thermal analysisREFERENCES(1) Sestak, and J., Berggren, G., “Study of the Kinetics of the Mechanism of Solid-Solid Reactions at Increasing Temperature,” Thermochimica Acta,Vol 3, 1971, pp. 112.(2) Yasutake, H., Kogyo Kayku (Journal of the I
32、ndustrial Explosives Society (Japan), Vol 52, 1991, p. 350.(3) Wrabetz, K., and Wong, J., Fresenius Zeitschrift fur Analytische Chemie, Vol 329, 1987, p. 487.(4) Torfs, J.C.M., Leen, D., Dorrepaal, A.J., and Heijens, J.C., Analytical Chemistry, Vol 56, 1984, p. 2863.(5) Gimzewski, E., and Audley, G.
33、, “Thermal Hazards: Calculating Adiabatic Behavior from DSC Data,” Thermochimica Acta, Vol 214, 1993, pp.129140.(6) Griffiths, J.F., Gilligan, M.F., and Gray, P., 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
34、 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.TABLE 1 Kinetic Parameters for Kinetic Reference Materials (Derived from Tables 2-6)NOTE 1where:E = activation energy,Z = pre-exponentia
35、l 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) n m H, kJ/g DescriptionDi-t-butylperoxide 158.1 15.80 1.0 0.0 1.34 Generally tested in liquid form as a 10 to20 %solution in toluen
36、e. Kinetic parameters aresolventsensitive. 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 forDSC.Azobisisobutyronitrile 128.5 15.12 1.0 0.0 Suitable for calorimeters and DSC.Phenyltetrazo
37、lthiol 143 20.4 1.7 1.3 Suitable for DSC.E2781 163(9) MacNeil, D.D., Trussler, S., Fortier, H., and Dahn, J.R., “A Novel Hertic Differential Scanning Calorimeter Sample Crucible,” Thermochimica Acta,Vol 386, 2002, pp. 153160.(10) Aldeeb, A.A., Rogers, W.J., and Mannan, M.S., “Theoretical and Experim
38、ental Methods for the Evaluation of Reactive Chemical 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 of Compatibility via Thermal Analysis and Mathematical Modeling,” ProcessSafety Progr
39、ess, Vol 13, 1994, pp. 227233.(12) Towsend, D.I., and Tou, 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, New York, 1994, p. 394.(15) Ba
40、ll, E., Rust, F., and Vaughn, W., Journal of the American Chemical Society, Vol 72, 1950, p. 337.(16) Murawaski, J., Roberts, J.S., and Szwarc, M., Journal of Chemical Physics, Vol 19, 1951, p. 698.(17) Raley, J., Rust, F., and Vaughan, W., Journal of the American Chemical Society, Vol 70, 1948, pp.
41、 1136, 2767.(18) Birss, F.W., Danby, C.J., and Hinshelwood, C.N., Proceedings of the Royal 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) Ja
42、uiss, M.T., Roberts, J.S., and Szwarc, M., Journal of the American Chemical Society, Vol 74, 1952, p. 6005.(22) Pritchard, G.O., Pritchard, H. O., and Trotman-Dickenson, A.F., Journal of the Chemical Society, 1954, p. 1425.(23) Blake, A.R., and Kutschke, K.O., “The Reaction of Methyl Radicals with F
43、ormaldehyde,” Canadian Journal of Chemistry, Vol 37, 1959, pp.14621468.(24) Shaw, D.H., and Pritchard, H.O., “Thermal Decomposition of Di-tert-Butyl Peroxide at High Pressure,” Canadian Journal of Chemistry, Vol 46,1968, pp. 27212724.(25) Lossing, F.P., and Ticker, A.W., Journal of Chemical Physics,
44、 Vol 20, 1952, p. 907.(26) Mulcahy, M.F.R., and Williams, D.J., Australian Journal of Chemistry, Vol 14, 1961, p. 534.(27) Iizuka, Y., and Surianarayanan, M., Industrial or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clea
45、rance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ 2 Literature Values for Di-t-butylperoxide (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
46、pure material,DSC = differential scanning calorimeters, andARC = accelerating rate calorimeter.E, kJ/mol log (Z,1/s) H, kJ/g nA Conditions Reference148 16.15 (2)163 16.45 gas phase (3)154 15.11 DSC, mineral oil (4)158 16.36 ARC, mineral oil, or tolu-ene(5)122.1 2.8 11.51 0.33 1.19 0.02 DSC, 725 psi
47、(6)136 12.87 0.1 M in diesel fuel (7)148 14.87 Neat (8)140 13.74 Neat (9)159.2 9.9 16.3 1.2 30 to 60 % in toluene (10)146.7 7.0 15.0 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 3.4 15.68 0.44 1.29 0.925 0.088 ARC (12)158.2 16.15 1.19 (13)1.335 (14)159 in t-but
48、yl benzene (15)151 in toluene (16)142 in vapor phase (16)163 in vapor phase (17)157 in i-propylbenzene (17)159 in t-butylbenzene (17)E2781 165155 in t-butylamine (17)159.7 0.58 15.94 0.07 in vapor phase (18)157.7 0.63 15.71 0.08 (19, 20)138.4 2.5 13.16 0.31 (16)146.7 6.7 14.04 0.83 (21)161.3 3.1 16.
49、30 0.39 (22)164.5 1.0 16.63 0.24 in diethylketone (23)158.4 1.2 15.82 0.18 (24)152.6 1.5 15.33 0.13 in vapor phase (25)160.1 1.3 16.07 0.14 (26)158.1 0.25 15.80 0.03 (1.00) Gas phase “best” literatureaverage(24)154.7 15.634 Solution (27)163.03 15.95- (28)157.3 2.1 15.94 0.34 (1.00) 15 % in toluene (29)1.25 0.04 (30)152.0 6.1 (1.00) 20 % in toluene (31)158.2 4.9 19.62 0.59 1.0 0.05 20 % in toluene and ben-zene(32)161 (33)A Values in
