ASTM E2781-16
(Practice)Standard Practice for Evaluation of Methods for Determination of Kinetic Parameters by Calorimetry and Differential Scanning Calorimetry
Standard Practice for Evaluation of Methods for Determination of Kinetic Parameters by Calorimetry and Differential Scanning Calorimetry
SIGNIFICANCE AND USE
5.1 The kinetic parameters provided in this practice may be used to evaluate the performance of a standard, apparatus, techniques, or software for the determination parameters (such as Test Methods E698, E1641, E2041, or E2070) using thermal analysis techniques such as differential scanning calorimetry, and accelerating rate calorimetry (Guide E1981). The results obtained by these approaches may be compared to the values provided by this practice.
Note 4: Not all reference materials are suitable for each measurement technique.
SCOPE
1.1 It is the purpose of this practice to provide kinetic parameters for reference materials used for evaluation of thermal analysis methods, apparatus, and software where enthalpy and temperature are measured. This practice addresses both exothermic and endothermic, nth order, and autocatalytic reactions.
1.2 The values stated in SI units are to be 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 responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
General Information
Relations
Buy Standard
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: E2781 − 16
Standard Practice for
Evaluation of Methods for Determination of Kinetic
Parameters by Calorimetry and Differential Scanning
1
Calorimetry
This standard is issued under the fixed designation E2781; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* E2041Test Method for Estimating Kinetic Parameters by
Differential Scanning Calorimeter Using the Borchardt
1.1 It is the purpose of this practice to provide kinetic
and Daniels Method
parameters for reference materials used for evaluation of
E2070Test Method for Kinetic Parameters by Differential
thermal analysis methods, apparatus, and software where
Scanning Calorimetry Using Isothermal Methods
enthalpy and temperature are measured. This practice ad-
dresses both exothermic and endothermic, nth order, and
3. Terminology
autocatalytic reactions.
3.1 Definitions—Specific technical terms used in this prac-
1.2 The values stated in SI units are to be regarded as
tice are defined in Terminologies E473 and E1142, including
standard. No other units of measurement are included in this
differential scanning calorimetry.
standard.
4. Summary of Practice
1.3 There is no International Organization for Standardiza-
tion (ISO) equivalent to this standard.
4.1 Kinetics is the study of the relationship of the extent of
a chemical reaction to the independent parameters of time and
1.4 This standard does not purport to address all of the
temperature. This relationship is often described using the
safety concerns, if any, associated with its use. It is the
Arrhenius expression where:
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
dα/dt 5Zf α exp 2E/RT (1)
~ ! ~ !
bility of regulatory limitations prior to use.
where:
α = fraction left to react,
2. Referenced Documents
f(α) = some function of (α),
2
2.1 ASTM Standards:
E = activation energy (J/mol),
E473Terminology Relating to Thermal Analysis and Rhe- –1 –1
R = gas constant (=8.314J mol K ),
ology
T = absolute temperature (K), and
E698Test Method for Kinetic Parameters for Thermally
Z = pre-exponential factor (1/sec).
Unstable Materials Using Differential Scanning Calorim-
4.2 For many reactions of interest the description of the
etry and the Flynn/Wall/Ozawa Method
function of amount left to react is of the form:
E1142Terminology Relating to Thermophysical Properties
m n
f~α! 5α ~1 2α! (2)
E1641TestMethodforDecompositionKineticsbyThermo-
gravimetry Using the Ozawa/Flynn/Wall Method
where m and n are the overall reaction orders. This form of
E1981Guide for Assessing Thermal Stability of Materials
the concentration dependence is known as the auto-catalytic
by Methods of Accelerating Rate Calorimetry
3
formortheSestak-Berggrenreaction. Ifthevalueof mequals
n
0, then f(α) reduces to the form of f(α)=(1–α) commonly
called nth order reaction.
1
This practice is under the jurisdiction of ASTM Committee E37 on Thermal
Measurements and is the direct responsibility of Subcommittee E37.02 on Refer- 4.3 Eq 1 may be evaluated in either its exponential or
ence Materials.
logarithmic form:
Current edition approved Nov. 1, 2016. Published November 2016. Originally
approved in 2011. Last previous edition approved in 2011 as E2781 – 11. DOI: ln~dα/dt! 5 lnZ1ln~f~α!! 2 E/RT (3)
10.1520/E2781-16.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Sestak, and J., Berggren, G., “Study of the Kinetics of the Mechanism of
Standards volume information, refer to the standard’s Document Summary page on Solid-Solid Reactions at Increasing Temperature,” Thermochimica Acta, Vol 3,
the ASTM website. 1971, pp. 1–12.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
---------------------- Page: 1 ----------------------
E2781 − 16
4.4 The study of kinetics involves the determination of obtained by these approaches may be compared to the values
values of E, Z, m, and n for a given reaction. provided by this practice.
NOTE1—Activationenergyandpre-exponentialfactorarenotindepen- NOTE 4—Not all reference materials are suitable for each measurement
dent parameters but are inter-related. technique.
NOTE 2—The descriptions provided in Eq 1-3 are only mathematical
6. Haza
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it 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 version
of the standard as published by ASTM is to be considered the official document.
Designation: E2781 − 11 E2781 − 16
Standard Practice for
Evaluation of Methods for Determination of Kinetic
Parameters by Thermal AnalysisCalorimetry and Differential
1
Scanning Calorimetry
This standard is issued under the fixed designation E2781; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Scope*
1.1 It is the purpose of this practice to provide kinetic parameters for reference materials used for evaluation of thermal analysis
methods, apparatus, and software where enthalpy and temperature are measured. This practice addresses both exothermic and
endothermic, nth order, and autocatalytic reactions.
1.2 The values stated in SI units are to be 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 responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2
2.1 ASTM Standards:
E473 Terminology Relating to Thermal Analysis and Rheology
E698 Test Method for Kinetic Parameters for Thermally Unstable Materials Using Differential Scanning Calorimetry and the
Flynn/Wall/Ozawa Method
E1142 Terminology Relating to Thermophysical Properties
E1641 Test Method for Decomposition Kinetics by Thermogravimetry Using the Ozawa/Flynn/Wall Method
E1981 Guide for Assessing Thermal Stability of Materials by Methods of Accelerating Rate Calorimetry
E2041 Test Method for Estimating Kinetic Parameters by Differential Scanning Calorimeter Using the Borchardt and Daniels
Method
E2070 Test Method for Kinetic Parameters by Differential Scanning Calorimetry Using Isothermal Methods
3. Terminology
3.1 Definitions—Specific technical terms used in this practice are defined in Terminologies E473 and E1142, including
differential scanning calorimetry.
4. Summary of Practice
4.1 Kinetics is the study of the relationship of the extent of a chemical reaction to the independent parameters of time and
temperature. This relationship is often described using the Arrhenius expression where:
dα/dt 5 Z f~α!exp~2E/RT! (1)
where:
α = fraction left to react,
f(α) = some function of (α),
1
This practice is under the jurisdiction of ASTM Committee E37 on Thermal Measurements and is the direct responsibility of Subcommittee E37.02 on Standard Reference
Materials.
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 referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
---------------------- Page: 1 ----------------------
E2781 − 16
E = activation energy (J/mol),
–1 –1
R = gas constant (=8.314 J mol K ),
T = absolute temperature (K), and
Z = 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:
m n
f~α!5 α ~12 α! (2)
where m and n are the overall reaction orders. This form of the concentration dependence is known as the auto-catalytic form
3 n
or the Sestak-Berggren reaction reaction.(1). If the value of m equals 0, then f(α) reduces to the form of f(α) = (1 – α) commonly
callcalled nth order reaction.
4.3 Eq 1 may be evaluated in either its exponential or logarithmic form:
ln dα/dt 5 lnZ1ln f α 2E/RT (3)
~ ! ~ ~ !!
4.4 The study of kinetics involves the determination of values of E,Z,m, and n for a given reaction.
NOTE 1—Activation energy and pre-exponential factor are not independent parameters but are inter-related.
NOTE 2—The descriptions provided in Eq 1-3 are only mathematical models. That is, they represent the fitting of mathematical equations to often
“noisy” experimental data
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: E2781 − 16
Standard Practice for
Evaluation of Methods for Determination of Kinetic
Parameters by Calorimetry and Differential Scanning
1
Calorimetry
This standard is issued under the fixed designation E2781; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* E2041 Test Method for Estimating Kinetic Parameters by
Differential Scanning Calorimeter Using the Borchardt
1.1 It is the purpose of this practice to provide kinetic
and Daniels Method
parameters for reference materials used for evaluation of
E2070 Test Method for Kinetic Parameters by Differential
thermal analysis methods, apparatus, and software where
Scanning Calorimetry Using Isothermal Methods
enthalpy and temperature are measured. This practice ad-
dresses both exothermic and endothermic, nth order, and
3. Terminology
autocatalytic reactions.
3.1 Definitions—Specific technical terms used in this prac-
1.2 The values stated in SI units are to be regarded as
tice are defined in Terminologies E473 and E1142, including
standard. No other units of measurement are included in this
differential scanning calorimetry.
standard.
4. Summary of Practice
1.3 There is no International Organization for Standardiza-
tion (ISO) equivalent to this standard. 4.1 Kinetics is the study of the relationship of the extent of
a chemical reaction to the independent parameters of time and
1.4 This standard does not purport to address all of the
temperature. This relationship is often described using the
safety concerns, if any, associated with its use. It is the
Arrhenius expression where:
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
dα/dt5 Z f~α!exp~2E/RT! (1)
bility of regulatory limitations prior to use.
where:
α = fraction left to react,
2. Referenced Documents
f(α) = some function of (α),
2
2.1 ASTM Standards:
E = activation energy (J/mol),
–1 –1
E473 Terminology Relating to Thermal Analysis and Rhe-
R = gas constant (=8.314 J mol K ),
ology
T = absolute temperature (K), and
E698 Test Method for Kinetic Parameters for Thermally
Z = pre-exponential factor (1/sec).
Unstable Materials Using Differential Scanning Calorim-
4.2 For many reactions of interest the description of the
etry and the Flynn/Wall/Ozawa Method
function of amount left to react is of the form:
E1142 Terminology Relating to Thermophysical Properties
m n
f α 5 α 1 2 α (2)
~ ! ~ !
E1641 Test Method for Decomposition Kinetics by Thermo-
gravimetry Using the Ozawa/Flynn/Wall Method
where m and n are the overall reaction orders. This form of
E1981 Guide for Assessing Thermal Stability of Materials
the concentration dependence is known as the auto-catalytic
by Methods of Accelerating Rate Calorimetry 3
form or the Sestak-Berggren reaction. If the value of m equals
n
0, then f(α) reduces to the form of f(α) = (1 – α) commonly
called nth order reaction.
1
This practice is under the jurisdiction of ASTM Committee E37 on Thermal
Measurements and is the direct responsibility of Subcommittee E37.02 on Refer- 4.3 Eq 1 may be evaluated in either its exponential or
ence Materials.
logarithmic form:
Current edition approved Nov. 1, 2016. Published November 2016. Originally
ln dα/dt 5 lnZ1ln f α 2 E/RT (3)
approved in 2011. Last previous edition approved in 2011 as E2781 – 11. DOI: ~ ! ~ ~ !!
10.1520/E2781-16.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Sestak, and J., Berggren, G., “Study of the Kinetics of the Mechanism of
Standards volume information, refer to the standard’s Document Summary page on Solid-Solid Reactions at Increasing Temperature,” Thermochimica Acta, Vol 3,
the ASTM website. 1971, pp. 1–12.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
---------------------- Page: 1 ----------------------
E2781 − 16
4.4 The study of kinetics involves the determination of obtained by these approaches may be compared to the values
values of E, Z, m, and n for a given reaction. provided by this practice.
NOTE 1—Activation energy and pre-exponential factor are not indepen- NOTE 4—Not all reference materials are suitable for each measurement
dent parameters but are inter-related. technique.
NOTE 2—The descriptions provided in Eq 1-3 are only mathematical
models. That is, they represent the fitting of mathematical equations to 6. Hazards
often “noisy” experimental dat
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.