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: D5865/D5865M − 19

Standard Test Method for

Gross Calorific Value of Coal and Coke1
This standard is issued under the fixed designation D5865/D5865M; 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* D3177 Test Methods for Total Sulfur in the Analysis Sample
1.1 This test method pertains to the determination of the of Coal and Coke (Withdrawn 2012)3
gross calorific value of coal and coke by either an isoperibol or D3180 Practice for Calculating Coal and Coke Analyses
adiabatic combustion calorimeter. from As-Determined to Different Bases
D4239 Test Method for Sulfur in the Analysis Sample of
1.2 The values stated in either SI units or inch-pound units Coal and Coke Using High-Temperature Tube Furnace
are to be regarded separately as standard. The values stated in Combustion
each system are not necessarily exact equivalents; therefore, to D7582 Test Methods for Proximate Analysis of Coal and
ensure conformance with the standard, each system shall be Coke by Macro Thermogravimetric Analysis
used independently of the other, and values from the two E144 Practice for Safe Use of Oxygen Combustion Vessels
systems shall not be combined. E178 Practice for Dealing With Outlying Observations
1.3 This standard does not purport to address all of the E691 Practice for Conducting an Interlaboratory Study to
safety concerns, if any, associated with its use. It is the Determine the Precision of a Test Method
responsibility of the user of this standard to establish appro-
iTeh Standards
E882 Guide for Accountability and Quality Control in the
priate safety, health, and environmental practices and deter- Chemical Analysis Laboratory
mine the applicability of regulatory limitations prior to use. E2251 Specification for Liquid-in-Glass ASTM Thermom-
(https://standards.iteh.ai)
Specific hazard statements are given in Section 8.
1.4 This international standard was developed in accor-
eters with Low-Hazard Precision Liquids

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dance with internationally recognized principles on standard- 3. Terminology
ization established in the Decision on Principles for the 3.1 For additional definitions of terms used in this test
Development of International Standards, Guides and Recom- method, refer to Terminology D121.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee. ASTM D5865/D5865M-19 3.2 Definitions:
3.2.1 adiabatic calorimeter, n—a calorimeter that operates
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in the adiabatic mode and may or may not use a microproces-
2. Referenced Documents
sor; the initial temperature before initiating the combustion and
2.1 ASTM Standards:2 the final temperatures are recorded by the operator or the
D121 Terminology of Coal and Coke microprocessor.
D346 Practice for Collection and Preparation of Coke
Samples for Laboratory Analysis 3.2.2 automated calorimeter, n—a calorimeter which has a
D388 Classification of Coals by Rank microprocessor that takes the thermometric readings and cal-
D1193 Specification for Reagent Water culates the Calibration Value and the Heat of Combustion
D2013 Practice for Preparing Coal Samples for Analysis Values.
D3173 Test Method for Moisture in the Analysis Sample of 3.2.3 British thermal unit [Btu], n—the amount of heat
Coal and Coke required to raise the temperature of one pound - mass [lbm] of
liquid water at one atmosphere pressure one degree Fahrenheit
at a stated temperature.
1
This test method is under the jurisdiction of ASTM Committee D05 on Coal
3.2.3.1 Discussion—The results of combustion calorimetric
and Coke and is the direct responsibility of Subcommittee D05.21 on Methods of
Analysis. tests of fuels for steam power plants may be expressed in terms
Current edition approved June 1, 2019. Published August 2019. Originally of the 1956 International Steam Table calorie (I.T. cal) which
approved in 1995. Last previous edition approved in 2013 as D5865 – 13. DOI: is defined by the relation, 1 I.T. cal = 4.1868 J. The Btu used in
10.1520/D5865_D5865M-19.
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
3
Standards volume information, refer to the standard’s Document Summary page on The last approved version of this historical standard is referenced on
the ASTM website. www.astm.org.

*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
 D5865/D5865M − 19
modern steam tables is defined by the means of the relation, 5.2 The gross calorific value can be used for computing the
1 I.T. cal/g = 1.8 I.T. Btu/lb. Thus, 1 I.T. Btu/lb = 2.326 J ⁄g. calorific value versus sulfur content to determine whether the
3.2.4 calorific value, n—the heat produced by combustion coal meets regulatory requirements for industrial fuels.
of a unit quantity of a substance under specified conditions.
5.3 The gross calorific value can be used to evaluate the
3.2.5 calorimeter, n—a device for measuring calorific value effectiveness of beneficiation processes.
consisting of a combustion vessel, its contents, a vessel for
holding the combustion vessel, temperature measuring devices, 5.4 The gross calorific value can be required to classify
ignition leads, water, stirrer, and a jacket maintained at coals according to Classification D388.
specified temperature conditions.
6. Apparatus and Facilities
3.2.6 gross calorific value (gross heat of combustion at
constant volume), Qv (gross), n—the heat produced by com- 6.1 Test Area—An area free from drafts, shielded from
plete combustion of a substance at constant volume with all direct sunlight and other radiation sources. Thermostatic con-
water formed condensed to a liquid. trol of room temperature and controlled relative humidity are
3.2.7 heat of formation, n—the change in heat content desirable.
resulting from the formation of 1 mole of a substance from its 6.2 Combustion Vessel—Constructed of materials that are
elements at constant pressure. not affected by the combustion process or the products formed
3.2.8 isoperibol calorimeter, n—a calorimeter that operates to introduce measurable heat input or alteration of end prod-
in the isoperibol mode and uses a microprocessor to record the ucts. The combustion vessel shall be designed so that all liquid
initial and final temperatures and make the appropiate heat leak combustion products can be completely recovered by washing
corrections during the temperature rise; it determines when the the inner surfaces. There shall be no gas leakage. The com-
calorimeter is in equilibrium and ignites the sample and bustion vessel shall be capable of withstanding a hydrostatic
determines when the calorimeter has reached equilibrium after pressure test to 20 MPa [3000 psig] at room temperature
ignition. without stressing any part beyond its specified elastic limit.
3.2.9 net calorific value (net heat of combustion at constant 6.3 Balance—A laboratory balance capable of weighing the
iTeh Standards
pressure), Qp (net), n—the heat produced by combustion of a
substance at a constant pressure of 0.1 MPa [1 atm], with any
analysis sample to the nearest 0.0001 g. The balance shall be
checked weekly, at a minimum, for accuracy.
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water formed remaining as vapor.
3.3 Definitions of Terms Specific to This Standard:
6.4 Calorimeter Vessel—Made of metal with a tarnish-
resistant coating, with all outer surfaces highly polished. Its

perature change caused by the processDocument

that occurs inside the Preview
3.3.1 corrected temperature rise, n—the calorimeter tem- size shall be such that the combustion vessel is completely
immersed in water during a determination. A stirrer shall be
combustion vessel corrected for various effects. provided for uniform mixing of the water. The immersed
3.3.2 heat capacity, n—the energy required to raise the portion of the stirrer shall be accessible to the outside through
ASTM D5865/D5865M-19a coupler of low thermal conductivity. The stirrer speed shall
temperature of the calorimeter one arbitrary unit.
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3.3.2.1 Discussion—The heat capacity can also be referred remain constant to minimize any temperature variations due to
to as the energy equivalent or water equivalent of the calorim- stirring. Continuous stirring for 10 min shall not raise the
eter. calorimeter temperature more than 0.01 °C when starting with
identical temperatures in the calorimeter, test area, and jacket.
4. Summary of Test Method For calorimeters having a bucket it can be a separate compo-
4.1 The heat capacity of the calorimeter is determined by nent or integral component of the combustion vessel. The
burning a specified mass of benzoic acid in oxygen. A vessel shall be of such construction that the environment of the
comparable amount of the analysis sample is burned under the calorimeter’s entire outer boundaries can be maintained at a
same conditions in the calorimeter. The calorific value of the uniform temperature.
analysis sample is computed by multiplying the corrected 6.5 Jacket—A container with the inner perimeter maintained
temperature rise, adjusted for extraneous heat effects, by the at constant temperature 6 0.1 °C (isoperibol) or at the same
heat capacity and dividing by the mass of the sample. temperature 6 0.1 °C as the calorimeter vessel (adiabatic)
4.2 Oxidation of coal after sampling can result in a reduc- during the test. To minimize convection, the sides, top, and
tion of calorific value. In particular, lignite and sub-bituminous bottom of the calorimeter vessel shall not be more than 10 mm
rank coal samples may experience greater oxidation effects from the inner surface of the jacket. Mechanical supports for
than samples of higher rank coals. Unnecessary exposure of the the calorimeter vessel shall be of low thermal conductivity.
samples to the air for the time of sampling or delay in analysis 6.6 Thermometers:
shall be avoided. (See X2.1.) 6.6.1 Platinum Resistance or Thermistor Thermometers
shall be capable of measuring to the nearest 0.0001 °C. These
5. Significance and Use types of thermometers consist of two major subsystems. The
5.1 The gross calorific value can be used to compute the first and most obvious is the temperature sensing probe itself.
total calorific content of the quantity of coal or coke repre- The second and equally important aspect is the measurement
sented by the sample for payment purposes. subsystem. For both subsystems, the relationship between the

2
 D5865/D5865M − 19
thermometer resistance and temperature shall be well charac- 7.2 Purity of Reagents—Use reagent grade chemicals con-
terized. The absolute temperature shall be known to 6 0.1 °C forming to the specification of the Committee on Analytical
at the temperature of the calorimetric measurement. Reagents of the American Chemical Society in all tests.5
6.6.2 Assessing the valid working range of the calorimeter, 7.3 Benzoic Acid—Standard (C6H5COOH)—Pellets made
as outlined in 10.9, is sufficient to demonstrate that all from benzoic acid available from the National Institute of
important aspects of the calorimeter functionality, including Standards and Technology (NIST) or benzoic acid calibrated
the thermometry, are in good working order. The traceability of against NIST standard material. The calorific value of benzoic
the heat of combustion measurement is governed by the acid, for use in the calibration calculations, shall be traceable to
traceability of the heat of combustion of the benzoic acid a recognized certificate value.
calibrant in addition to meeting the aforementioned criteria.
6.6.3 Liquid-in-Glass Thermometers—Conforming to the 7.4 Oxygen—Manufactured from liquid air, guaranteed to
requirements for thermometers S56C, S116C, or S117C as be greater than 99.5 % pure, and free of combustible matter.
prescribed in Specification E2251. Oxygen made by the electrolytic process contains small
6.6.3.1 Thermometer Accessories—A magnifier is required amounts of hydrogen rendering it unfit unless purified by
for reading liquid-in-glass thermometers to one tenth of the passage over copper oxide at 500 °C.
smallest scale division. The magnifier shall have a lens and 7.5 Titration Indicator—Methyl orange, methyl red, or
holder designed so as to minimize errors as a result of parallax. methyl purple for indicating the end point when titrating the
6.7 Sample Holder—An open crucible of platinum, quartz, acid formed during combustion. The same indicator shall be
or base metal alloy. Before use in the calorimeter, heat treat used for both calibration and calorific value determinations.
base metal crucibles for a minimum of 4 h at 500 °C to ensure 7.6 Standard Solution—Sodium carbonate (Na2CO3) or
the crucible surface is completely oxidized. Base metal alloy other suitable standard solution. A convenient standard solution
crucibles are acceptable, if after three preliminary firings, the may be prepared as follows. Dissolve 3.706 g of sodium
mass does not change by more than 0.0001 g. carbonate, dried for 24 h at 105 °C, in water and dilute to 1 L.
6.8 Ignition Fuse—Ignition fuse of 100 mm length and The resulting concentration (0.0699 N) assumes the energy of

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0.16 mm [No. 34 B&S gauge] diameter or smaller. Nickel- formation of HNO3 under combustion vessel conditions is
chromium alloy (Chromel C) alloy, cotton thread, or iron wire -59.7 kJ ⁄mol [-14.3 kcal ⁄mole] (seeX1.1). One milliliter of this
are acceptable. Platinum or palladium wire, 0.10 mm diameter solution is equivalent to 4.2 J [1.0 cal] in the acid titration.
(https://standards.iteh.ai)
[No. 38 B&S gauge], can be used provided constant ignition
energy is supplied. Use the same type and length (or mass) of
Alternatively, 1.0 mL of a 0.1000 N base solution is equivalent
to 6.0 J [1.4 cal] in the acid titration. In general, 1 mL of an

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ignition fuse for calorific value determinations as used for arbitrary standard titrant solution is equivalent to its concen-
standardization. tration (equivalents/liter or normality [N]) times 59.7 J
[14.3 cal].
6.9 Ignition Circuit—A 6 V to 30 V alternating or direct
current is required for ignition purposes. A step-down trans-
ASTM D5865/D5865M-19
8. Hazards
former connected to an alternating current circuit, capacitors,
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or batteries can be used. For manually operated calorimeters, 8.1 The following precautions are recommended for safe
the ignition circuit switch shall be of the momentary double- calorimeter operation. Additional precautions are noted in
contact type, normally open except when held closed by the Practice E144. Also consult the calorimeter equipment manu-
operator. An ammeter or pilot light can be used in the circuit to facturer’s installation and operating instructions before using
indicate when current is flowing. the calorimeter.
8.1.1 The mass of sample and any combustion aid as well as
6.10 Controller—For automated calorimeters, capable of the pressure of the oxygen admitted to the combustion vessel
charging the combustion vessel; filling the calorimeter vessel; shall not exceed the combustion vessel manufacturer’s speci-
firing the ignition circuit; recording calorimeter temperatures fications.
before, during, and after the test; recording the balance 8.1.2 Inspect the combustion vessel parts carefully after
weights; and carrying out all necessary corrections and calcu- each use. Replace cracked or significantly worn parts. Replace
lations. O-rings and valve seats in accordance with manufacturer’s
6.11 Crucible Liner—Quartz fiber or alundum for lining the instruction. For more details, consult the manufacturer.
crucible to promote complete combustion of samples that do 8.1.3 Equip the oxygen supply cylinder with an approved
not burn completely during the determination of the calorific type of safety device, such as a relief valve, in addition to the
value.4 needle valve and pressure gauge used in regulating the oxygen
feed to the combustion vessel. Valves, gauges, and gaskets
7. Reagents
shall meet industry safety codes. Suitable reducing valves and
7.1 Reagent Water—Conforming to conductivity require-
ments for Type II of Specification D1193 for preparation of 5
Reagent Chemicals, American Chemical Society Specifications, American
reagents and washing of the combustion vessel interior.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
4
Supporting data have been filed at ASTM International Headquarters and may Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
be obtained by requesting Research Report RR:D05-1025. Contact ASTM Customer and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Service at service@astm.org. MD.

3
 D5865/D5865M − 19
adapters for 3 MPa to 4 MPa [300 psig to 500 psig] discharge stability shall be 6 0.001 °C for an adiabatic calorimeters and
pressure can be obtained from commercial sources of com- 6 0.001 °C ⁄s or less for an isoperibol calorimeter.
pressed gas equipment. Check the pressure gauge annually for 10.4.2 Extrapolation Method—Fire the charge, record the
accuracy or after any accidental over pressures that reach temperature rise. The test can be terminated when the observed
maximum gauge pressure. thermal curve matches a thermal curve which allows extrapo-
8.1.4 During ignition of a sample, the operator shall not lation to a final temperature with a maximum uncertainty of
extend any portion of the body over the calorimeter. 6 0.002 °C.
8.1.5 Do not fire the combustion vessel if the combustion 10.4.3 Full Development Method—Fire the charge and re-
vessel has been dropped or turned over after loading. cord the temperature rise until the temperature has stabilized
8.1.6 Do not fire the combustion vessel if there is evidence for a period of 30 s in accordance with the stability require-
of gas leakage when the combustion vessel is submerged in the ments specified in 10.4.1.
calorimeter vessel. 10.5 Temperature Observations Manual Calorimeters:
8.1.7 For manually operated calorimeters, the ignition 10.5.1 When using ASTM Thermometers S56C, estimate all
switch shall be depressed only long enough to fire the charge. readings to the nearest 0.002 °C. When using ASTM Ther-
mometers S116C or S117C, estimate readings to 0.001 °C and
9. Sample 25 Ω resistance thermometer readings to the nearest 0.0001 Ω.
9.1 The analysis sample is the material pulverized to pass Tap or vibrate liquid-in-glass thermometers just before reading
250 µm [No. 60] sieve, prepared in accordance with either to avoid errors caused by liquid sticking to the walls of the
Practice D346 for coke or Practice D2013 for coal. capillary.
10.5.2 Allow 5 min for the temperature of the calorimeter
10. Determination of the Heat Capacity of the vessel to stabilize. Adjust the jacket temperature to match the
Calorimeter calorimeter vessel temperature within 0.01 °C and maintain for
10.1 Sample—Weigh 0.8 g to 1.2 g of benzoic acid into a 3 min.
sample holder. Record sample mass to the nearest 0.0001 g. 10.5.3 Fire the charge. Record the time as a and the
temperature as ta.
iTeh Standards
10.2 Preparation of Combustion Vessel:
10.2.1 Rinse the combustion vessel with water to wet
10.5.4 For adiabatic calorimeters adjust the jacket tempera-
ture to match that of the calorimeter vessel temperature during
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internal seals and surface areas of the combustion vessel or
precondition the calorimeter according to the manufacturer’s
the period of the rise. Keep the two temperatures as equal as
possible during the period of rapid rise. Adjust to within
instructions. Add 1.0 mL of water to the combustion vessel
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0.01 °C when approaching the final stabilization temperature.
before assembly. Record subsequent readings at intervals no greater than 1 min
10.2.2 Connect a measured fuse in accordance with manu- until three successive readings do not differ by more than
facturer’s guidelines. 6 0.001 °C. Record the first reading after the rate of change
ASTMoxygen
10.2.3 Assemble the combustion vessel. Admit D5865/D5865M-19
to has stabilized as the final temperature tc and the time of this
the combustion vessel to a consistent pressure of between
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2 MPa and 3 MPa [20 atm and 30 atm]. The same pressure is
reading as c. For isoperibol calorimeters, when approaching the
final stabilization temperature, record readings until three
used for each heat capacity run. Control oxygen flow to the successive readings do not differ by more than 0.001 °C per
combustion vessel so as not to blow material from the sample min. Record the first reading after the rate of change has
holder. If the pressure exceeds the specified pressure, detach stabilized as the final temperature as tc and the time of this
the filling connection and exhaust the combustion vessel. reading as c.
Discard the sample. 10.5.5 Combustion Vessel Depressurization—When the
10.3 Preparation of Calorimeter: thermochemical corrections will be made by titration, the
10.3.1 Fill the calorimeter vessel with water at a tempera- depressurization and subsequent rinse collection shall be done
ture not more than 2 °C below room temperature and place the in a manner ensuring at least 80 % recovery of the acidic
assembled combustion vessel in the calorimeter. Check that no combustion products. An effective measure of the recovery is
oxygen bubbles are leaking from the combustion vessel. If offered by the recovery factor described in the following
there is evidence of leakage, remove and exhaust the combus- section.6 Depressurization at a rate such that the operation is
tion vessel. Discard the sample. not less than 1 min provides effective recovery and does not
10.3.2 The mass of water used for each test run shall be M require validation. There are no special requirements related to
6 0.5 g where M is a fixed mass of water. Devices used to the combustion vessel depressurization if the calculated nitric
supply the required mass of water on a volumetric basis shall acid procedure is used.
be adjusted when necessary to compensate for change in the 10.5.5.1 Determine the recovery factor from the slope of the
density of water with temperature. straight line resulting from the regression analysis of the
10.3.3 With the calorimeter vessel positioned in the jacket
start the stirrers.
6
Supporting data have been filed at ASTM International Headquarters and may
10.4 Temperature Observations Automated Calorimeters:
be obtained by requesting Research Report RR:D05-1028, “Interlaboratory Study
10.4.1 Stabilization—The calorimeter vessel’s temperature for the Use of Calculated Nitric Acid Correction.” Contact ASTM Customer Service
shall remain stable over a period of 30 s before firing. The at service@astm.org.

4
 D5865/D5865M − 19
titration results (mg of sulfur versus meq) using three or more Example:
samples with at least two different sulfur concentrations that The nitric acid correction for a 340 mL oxygen combustion
span the range of sulfur values typically encountered in the vessel is found to be 41.9 J [10.0 cal] when the released energy
laboratory. One equivalent of sulfuric acid (1000 meq) is corresponds to that liberated by 1 g of benzoic acid, 26.45 kJ
formed from 16.03 g of sulfur. A plot of sulfur (mg) versus [6318 cal]. The ratio of these quantities is 1.58 J per 1000 J of
milliequivalents (meq) of titrant used to neutralize the com- released energy or 1.58 cal per 1000 cal of released energy. The
bustion vessel rinsings has a theoretical slope of 16.03. The nitric acid correction for any calorimetric test can then be
milliequivalents of titrant is the product of milliliters of base expressed as follows:
used and its concentration (normality). The mass of sulfur in e 1 5 1.58*energy released for the test ~ kJ or kcal! (2)
the sample in milligrams is the product of the sulfur concen- For a given calorimeter, the energy released in the combus-
tration in weight percent in the analysis sample, the sample tion vessel during a test for the purposes of calculating the
mass and ten. A slope of 16 implies 100 % recovery. Increasing nitric acid correction (e1) may be expressed as the product of
the temperature rise for the test and the effective calorimeter
values are indicative of diminished recovery. For example, a heat capacity or calorimeter calibration factor.7
value of 20 indicates 80 % recovery (16.03 × 100/20 = 80 %).
e 1 5 ~ 1.58/1000! *E*t (3)
10.5.6 After depressurization, open the combustion vessel The calculated nitric acid method can be applied to samples
and examine the combustion vessel interior carefully for signs containing up to 2 % nitrogen without introducing a signifi-
of unburned material or sooty deposits. Discard the test result cant error in the resulting heat of combustion value.
if either is observed.
10.6.2 Fuse Correction (see X1.3)—Determine the fuse
10.6 Thermochemical Corrections (see Appendix X1): correction using one of the two alternatives:
10.6.1 Acid Correction (see X1.1)—One may use either the 10.6.2.1 Measure the combined pieces of unburned ignition
titration (10.6.1.1) or calculated titration (10.6.1.2) procedure fuse and subtract from the original length to determine the fuse
for coal and coke samples. consumed in firing according to Eq 4.
10.6.1.1 Titration Method—Wash the interior of the com- e2 5 Kl 3 l (4)

iTeh Standards
bustion vessel with distilled water containing the titration
indicator (see 7.5) until the washings are free of acid and
where:
e2 = the correction for the heat of combustion of the firing
combine with the rinse of the capsule. Titrate the washings
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with the standard solutions (see 7.6) using a titration indicator,
or a pH or millivolt meter. The product of the volume of titrant
l
fuse,
= the length of fuse consumed during combustion,
Kl = 0.96 J ⁄mm [0.23 cal ⁄mm] for No. 34 B&S gauge
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used in milliliters, the concentration of the standard solution
(normality) and 59.7 J [14.3 cal] shall be taken as e1.
Chromel C,
Kl = 1.13 J ⁄mm [0.27 cal ⁄mm] for No. 34 B&S gauge iron
10.6.1.2 Calculated Nitric Acid Method—For test samples wire, and
that contain no nitrogen, the nitric acid formed Kl = 0.00 J ⁄mm for platinum or palladium wire provided
in the combus-
ASTM D5865/D5865M-19 the ignition energy is constant.
tion vessel during the combustion process is derived from the
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nitrogen in the air that occupies the combustion vessel prior to or;
pressurizing it with oxygen. The quantity of nitric acid formed 10.6.2.2 Weigh the combined pieces of unburned fuse and
is a function of the volume of the combustion vessel, the subtract from the original mass to determine the mass in
oxygen filling pressure, and the quantity of energy released in milligrams of the fuse consumed in firing (m). Remove any ball
the combustion vessel during a test. For a given combustion of oxidized metal from the ends before weighing.
vessel and filling pressure, the relationship between the amount e2 5 Km 3 m (5)
of nitric acid formed and the energy released can be determined
using the following procedure. The calorimeter should be where:
tested using 1 g pellets of benzoic acid when the combustion e2 = the correction for the heat of combustion of the firing
vessel volume is nominally 340 mL. If the combustion vessel fuse,
volume differs significantly from 340 mL, the sample mass m = the mass in mg of fuse consumed during combustion,
used should be adjusted as required in order to comply with the
Km = 5.9 J ⁄mg [1.4 cal/mg] for No. 34 B&S gauge Chromel
combustion vessel manufacturer’s safe operating guidelines.
C,
Tests should be run in duplicate. Determine the nitric acid
Km = 7.5 J ⁄mg [1.8 cal/mg] for No. 34 B&S gauge iron
correction by titrating the combustion vessel washings as
wire, and
outlined in 10.6.1.1. Divide the correction obtained (e1) by the Km = 0.00 J ⁄mg for platinum or palladium wire provided
amount of energy released in the combustion vessel for the the ignition energy is constant.
corresponding test. The energy contribution from the ignition
fuse (e2) is usually small (<1 % of the total energy released)
and may be ignored. The average value of this ratio is used to
establish a factor (NAF) that allows the nitric acid correction to 7
Supporting data have been filed at ASTM International Headquarters and may
be determined for any arbitrary energy release. be obtained by requesting Research Report RR:D05-1028, “Interlaboratory Study
for the Use of Calculated Nitric Acid Correction.” Contact ASTM Customer Service
e 1 5 ~ NAF! *energy released for the test (1) at service@astm.org.

5
 D5865/D5865M − 19
When cotton thread is used, employ the correction in J forming additional calibration measurements as required. Table
recommended by the instrument manufacturer. 1 provides an example summary of a series of calibration tests.
10.7 Calculation of the Corrected Temperature Rise— The formulas used to arrive at the mean value and relative
Compute the corrected temperature rise, t, as follows: standard deviation are independent of the units used for the
calibration measurements.
t 5 t c 2 t a 1C e 1C r (6)
10.9 Valid Working Range for the Calibration of the Calo-
where: rimeter:
t = corrected temperature rise, °C; 10.9.1 It is a generally accepted principle of reliable analy-
ta = initial temperature reading at time of firing; sis that instruments should be calibrated over the full range of
tc = final temperature reading; measurement and that measurements be restricted to the range
Ce = thermometer, emergent stem correction (see Eq A1.6 calibrated. It is not good practice to report extrapolated data
or Eq A1.8); and obtained outside the range of calibration. The range of reliable
Cr = radiation correction (see Eq A1.1 or Eq A1.2). calibration can be considered as the range of reliable measure-
10.7.1 The temperature rise in isoperibol calorimeters re- ment and vice versa.
quires a radiation correction. 10.9.2 It should be possible to vary the amount of benzoic
10.8 Calculation of the Heat Capacity—Calculate the heat acid calibrant by at least 6 25 % without observing a signifi-
capacity (E) of the calorimeter using the following equation: cant trend in the values obtained for the effective heat capacity
or instrument calibration factor. The working limits for the
E 5 @ ~ H c 3 m ! 1e 1 1e 2 # /t (7) instrument calibration shall be determined and defined in terms
where: of the corrected temperature rise. All subsequent measurements
E = the calorimeter heat capacity, J/°C; shall be kept within these limits.
Hc = heat of combustion of benzoic acid, as stated in the 10.9.3 A convenient way to check a previously calibrated
certificate, J/g; instrument is to use benzoic acid as an unknown. The mean
m = mass of benzoic acid, g; value for the heat of combustion from duplicate runs using

iTeh Standards
e1 = acid correction from 10.6.1 from either the titration 0.7 g and 1.3 g sample masses, respectively, should be within
method (10.6.1.1) or the calculated titration (10.6.1.2); 6 56 J ⁄g or 6 24 Btu ⁄lb of the accepted heat of combustion
value.
e
t
2
= corrected temperature (https://standards.iteh.ai)
= fuse correction from 10.6.2, J; and
rise from 10.7,°C.
10.9.4 For any given instrument, examination of the appli-
cable range of the instrument calibration should be carried out

complete a total of ten acceptable testDocument

runs. An individual test Preview
10.8.1 Using the procedures described in 10.1 – 10.8 when the instrument is new, moved to a different location, or
subject to major repair.
shall be rejected only if there is evidence of incomplete
combustion. 11. Calibration Verification
ASTM D5865/D5865M-19
10.8.2 The precision of ten acceptable calibration test runs 11.1 The calorimeter calibration shall be checked on a
https://standards.iteh.ai/catalog/standards/sist/7a22d800-aed1-4410-9040-ce867c3ed0de/astm-d5865-d5865m-19
shall have a relative standard deviation (RSD) no greater than regular basis. Renewed determination of the heat capacity is
0.17 %. If after considering the possibility of outliers using required whenever significant alterations have been made to
criteria established in Practice E178, this limit is not met, one the instrument or to the test conditions. The optimum fre-
should review operation of the calorimeter for any assignable quency for checking the heat capacity or instrument calibration
cause. Operating deficiencies should be corrected before per- will depend on the stability of the measurement system and the

TABLE 1 Calibration Measurments

Column A Column B
Run Number Heat Capacity Difference from
J/°C Average Squared

1 10 258 20
2 10 249 20
3 10 270 272
4 10 254 0
5 10 245 72
6 10 249 20
7 10 241 156
8 10 266 156
9 10 258 20
10 10 245 72

Sum 102 535 811

Average 10 254 Sum Column A /10
Variance (s2) 90 Sum Column B /9
Standard Deviation(s) 9 Sqrt (Variance)
Relative Standard Deviation (RSD) 0.09 % s/Average * 100