Des : DSB65 ~ 13 ab Standard Test Method for Gross Calorific Value of Coal and Coke’ This sandr is asa wr the he design ntl flowing the de Spersrp pion (eines oer change ice the I 1, Scope* 1.1 This test method pertains to the determination of the gross calorific value of coal and coke by either an isoperibot or adiabatic bomb calorimeter. 1.2 ‘The values stated in SI units are to be regarded as dard. No other units of measurement ane included in this standard 1.3 This standard does not purport to adress all of the safety concerns, if any, associated with its use. Mis the responsibility of the user of tis standard to establish appro priate safety and health practices and determine the applica- bility of regulatory limitations prior to use. Specific hazard statements are given in Section 8 2. Referenced Documents, 2.1 ASTM Standards? DI21 Terminology of Coal and Coke D346 Practice for Collection and Preparation of Coke Samples for Laboratory Analysis D388 Classification of Coals by Rank 1D1193 Specification for Reagemt Water 2013 Practice for Preparing Coal Samples for Analysis 1D3I73 Test Method for Moisture in the Analysis Sample of Coal and Coke 13177 Test Methods for Total Sulfur in the Analysis Sample of Coal and Coke (Withdrawn 2012)" D310 Practice for Calculating Coal and Coke Analyses from As-Detormined to Different Bases 14239 Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion ist at con speed Oe. 203, abit Comer 013. vay mye 253 oe pi aio poe 0d eb Bh coats i Caueas tateen euonaty fk aly a te a med eae fon of ohn stra Sande 56 reer os xe © ASTI neti Bir Hn, PO 700, Ws Co Sono esp 1D7582 Test Methods for Proximate Analysis of Coal and Coke by Macro Thermogravimetrc Analysis E148 Practice for Safe Use of Oxygen Combustion Vessels 178 Practee for Dealing With Ouilying Observations E882 Guide for Accountability and Quality Control in the Chemical Analysis Laboratory 51 Speciication for Liquid-in-Glass ASTM Thermom cers with Low-Hazard Precision Liquids 3. Terminology 3.1 For additional definitions of terms used method, refer to Terminology D121. 3.2 Definittons: 3.2.1 adiabatic calorimeter—a calorimeter that operates in the adiabatic mode and may or may not use a microprocessor The initial temperature before initiating the combustion and the final temperatures are recorded by the operator or the micro processor, 3.22 automated calorimeter—a calorimeter which has a ‘microprocessor that takes the thetmometric readings and cal- culates the Calibration Value and the Heat of Combustion Values. 3.23 British thermal unit (Bix}—is the amount of heat required to raise the temperature of one pound - mass (tbm] of liguid water at one atmosphere pressure one degree Fahrenheit ata stated temperature. The results of combustion calorimetic, tests of fuels for steam power plants may be expressed in terms of the 1956 International Steam Table calorie (IT. cal) which is defined by the relation, 1 LT. cal = 4.1868 J. The Blu used in modern steam tables is defined by the means of the relation, 1 LT eal /g= 18 LT. Btu/ Ib. Thus, 1 LT. Btu / Ib = 2.326 18. 3.24 calorific value—ihe heat produced by combustion of a unit quantity of a substance under specified conditions 3.25 calorimeter—a device for measuring calorific value consisting of 2 bomb, its contents, & vessel for holding the bomb, temperature measuring devices, ignition leads, water, stirrer, and a jacket maintained at specified teraperature con- ditions. this test 326 gross culorifc value (gross hear of combustion at constant volume), Q, (gross)—the heat produced by complete ‘combustion of a substance at constant volume with all water formed condensed to « liquid. sry of Changes section appenry st the end of thi standard (VWWVSON) VWYS48 VAZIHVEaS ISvwadoy MUN « IEUORCUIAIUT WLSY ISHESI! YeME IP NSB YaI0 IeNgIp IU AdoD "vSN ‘SZbET Vd ‘UBYDOYOYSUOD ISEM ‘AUG INOUE} 44eG OT ‘TeUoReWeIUT WISY Id} 4H,Ally vsses - 13 3.2.7 hear of formation—the change in heat content result- ing from the formation of 1 mole of a substance from its elements at constant pressure 3.2.8 isoperibol calorimeter —a calorimeter that operates in the isoperibol mode and uses a microprocssor to record the inital and final temperatures and make the appropiate heat leak ons during the temperature rise. [t determines when the orimeter is in equilibrium and ignites the sample and determines when the ealorimeter hus reached equilibrium afier ignition, 3.29 net calorific value (net heat of combustion at constant pressere). Q, (ret) the heat produced by combustion of a substance at 2 constant pressure of O.1 MPa (1 atm), with any water formed remaining us vapor 33 Definitions of Terms Specific to This Standard: 33.1 comected temperature vise—the calorimeter tempera ture change cased by the process that oceurs inside the bomb ‘corrected for various effects. 3.3.2 hear eapacity—the energy required to raise the wem- perature of the calorimeter ene arbitrary unit 3.32.1 Discussion —The heat eapacity can also be referred the energy equivalent or water equivalent of the calorim te eter 4, Summary of Test Method 4.1 The host capkeity of the calorimeter is determined by. burning a specified mass of benzoic acid in oxygen. A comparable amount of the analysis sample is burned uncer the same conditions in the calorimeter, The caloric value of the analysis sample is computed by multiplying the corrected temperature rise, adjusted for extraneous heat effects, by the heat capacity and dividing by the mass of the sample. 42 Oxidation of coal after sampling can result in a redue- tion of caloric value. In particular, lignite and sub bituminous rank coal samples may experience greater oxidation effects than samples of higher rank coals. Unnecessary exposure of the samples fo the air For the time of sampling or delay in analysis, shall be avoided. (See X2.1.) nd Use ignificance 5.1 The gross calorific value can he used 10 compute the (otal calorific content of the quantity of coal oF coke repre: sented by the sample for payment purposes. 5.2 The gross calorific value can be used for computing the calorific value versus sulfur content to determine whether the coal meets regulatory requirements for industrial fuels 5.3 The gross calaritic value can be used t0 evaluate the effectiveness of beneficiation processes. 54 The gross calor coals according to Classi ic value can be requited to classy fication D388, 6, Apparatus and Facilities GI Test Areo—An arca free from drafts, shielded from direct sunlight and ether radiation sources. Thermostatic con- ‘rol of room temperature and controlled relative humidity are desirable 62 Combustion Bomb—Constructed of materials that are not affected by the combustion process or the products formed {o introduce measurable heat input or alteration of end prod- ‘ucts. The bomab shall be designed so that all iguid combustion products can be completely recovered by washing the ianer surfaces, There shall be no gas Jeakage. The bomb shall be capable of withstanciing a hydrostatic pressure test to 20 MPa (3000 psigi at room temperature without siressing any part beyond its specified clastic Fim. 6.3 Balanee—A laboratory balance capable of weighing the analysis sample to the nearest 0.0001 g. The balance shall be checked weekly, at a minimum, for accuracy. 64 Calorimeter Vesset—Made of metal with a tamish- resistant coating, with all outer suctaces highly polished. Its size shall be such that the bomb is completely immersed water during a determination. A stirer shall be provided for un nixing of the water. The immersed portion of the stirrer shall be accessible to the outside through a coupler of low thermal conductivity. ‘The stirrer speed shall romain ‘constant to minimize any temperature variations due to stirring. Continuous stirring for 10 min shall not raise the calorimeter temperature more than 0.01°C when starting with identical temperatures in the calorimeter, test area and jacket. For calorimeters having a bucket it can be a separate component oF integral eomponent of the bomb. The vessel shall be of such construction that the environment of the calorimeter’s entire ‘outer boundaries can be maintained at @ uniform temperature, 65 Jacket—A container withthe inner perimeter maintained at constant temperature +0.1°C (isoperibol) or at the same temperature £0.1°C as the calorimeter vessel (adiabatic) luring the test. Tor minimize convection, the sides, top and botiom ofthe calorimeter vessel shall nat he more than 10 mam from the inner surface of the jacket. Mechanical supports for te calorimeter vessel shall be of low thermal conductivity 66 Thermometers: 66.1 Plarinum resistance or thermistor shermomerers— shall be capable of measuring to the nearest 0.0001°C, These types of thermometers consist of two major subsystems. The first and mest obvious is the temperature sensing probe itself. ‘The second and equally important aspect is the measurement subsystem, For both subsystems, the relationship between the thermometer resistance ancl temperature shall be well charac: terized. The absolute temperature shall be known to * 0.1. Cat the temperature of the calorimetric measurement, 6.6.2 Assessing the valid working range of the es 8 outlined in 10.9, is sufficient to demonstrate that all important aspects of the calorimeter functionality, including the thermometry, ae in goed working order. The traceability of the heat of combustion measurement is governed by the luaceability of the heat of combustion of the benzoic acid calibrant in addition to meeting the aforementioned criteria, 6.6.3 Liguid-in-Glass Thermomerers—Conforming 10 the requirements for thermometers S36C, SI16C, or SH7C as proscribed in Specification F225) (viWvSoN) VHSuaa VUaLHVraS ISvuadou IMU Ieuonewiequr WASy Isu9si| Yemed Ip NSB YeIO yeNaIp It AdoD "WSN ‘SZPBT vd ‘UB¥DOYOUSUOD 359M ‘AIG INOGIeH WER NOT ‘PUoNeUIAIUT WIsy Id 4eH,,Aly vsses - 13, 6.63.1 Thermometer Accessories—A magnifier is required for reading liquid-in-glass thermometers to one tenth of the smallest seale division. The magnifier shall have a lens and holder designed s0 as to minimize errors asa result of parallax. 6.7 Sample Holder—An open crucible of platinum, quartz, or base metal alloy. Before use in the calorimeter, heal treat ‘base metal crucibles for a minimum of 4 h at 500°C to ensure the crucible surface is completely oxidized. Base metal alloy crucibles are acceptable, if after three preliminary firings, the ‘weight does not change by more than 0.0001 68 Ignition Fuse—Ignition fuse of 100-mm length and O.16-tm (No, 34 B&S gauge) diameter or smaller. Nickel- chromium alfoy (Chrome! C) alloy, cotton thread, or iton wire are acceptable, Platinum or palladium wire, 0.10-mm diameter (No. 38 B&S gauge), can be used provided constant ignition energy is supplied. Use the same type and length (or mass) of ignition fuse for calorific value determinations as used for standardization 699 Ignition Circuit—A 6 to 30N alternating or direct ccurtent is requited for ignition purposes. A step-down trans- former connceted to an alternating current circuit, capacitors, ‘or batteries can be used, For manually operated calorimeters, the ignition ciscuit switch shall be of the momentary double- contact type, normally open except when held closed by the ‘operator. An ammeter o pilot light can be used in the citeuit to indicate when current is flowing 6.10 Controller—For automated calorimeters, capable of charging the bomb; filling the calorimeter vessel; firing the ignition cireuit: recording calorimeter temperatures. before, during, and after the test; recording the balanee weights; and. carrying out all necessary corrections and calculations. 6.1L Crucible Liner—Quartz fiber or alundum for fining the crucible to promote complete combustion of samples that do not bum completely during the determination of the calorific value 7. Reagents Tl Reagent Water—Conlorming to conductivity require meats for Type LI of Specification D119 for preparation of reagents and washing of the bomb interior. 22 Purity of Reagents—Use reugent grade chemicals con- forming to the specification of the Committee on Analytical Reagents of the American Chemical Society in all tests* 7.3. Benzoic Acid—Standant (CgHsCOOH)—Peliess made from benzoic acid available from the National Institute of Standards and Technology (NIST) or beozoie acid calibrated ‘against NIST standard material The calorific value of benzoic acid, for use in the calibration calculations, shall be traceable to a recognized ca icate value, opponting dita ho! hn et ASTM nero Hepa nd ay eon ny repsting Reve Kept RK D025, “Resort Chemicals. American Chea Sacicy Speciieatone , American ‘Chemical Secey, Wanhngon, DC. For suggestions on he eng of eg Tinted by the Arian Chemis! Sos. ee Aner Smads for Lanny Chenicl. BOM LL, Poole, Danek. U.K. and the Uri Sates Pharcepea fan Bovina! Fron: US. Pharell Converin. Ins. (USPC, Roskl 7.4 Oxygen—Manufactured from liquid sir, guaranteed to be greater than 99.5 % pure, and free of combustible matter. ‘Oxygen _made by the electrolytic process contains small amounts of hydrogen rendering it unfit unless puritied by passage aver copper oxide at 500°C. 7.8 Turation Indicator—Methyl orange. methyl red, or ‘methyl purple for indicating the end point when titrating the acid formed during combustion. The same indicator shall he used for both calibration and calorific value determinations. 7.6 Standard Solution—Sodium carbonate (NasCO,) or ‘other suitable standard solution. A convenient standard solution may be prepared as follows, Dissolve 3.706 g of sodium carbonate, dried for 24 h at 105°C, in water and dilute f0 1 L. ‘The resulting concentration (0699 N) assumes the energy of formation of HNO, under bomb conditions is -59.7 k¥/mol (143 keal/mole) (SeeX 1-1). One milliliter of this solution is ‘equivalent to 4.2.3 (1.0 cal) in the acid titration. Alternatively, LO mi of a 0.1000 N base solution is equivalent t0 6.0 J (4 cal) in the acid titration. In general. one milliliter of an arbitrary standard cirant solution is equivalent to its concentration (equivalents / liter or normality [N]) times 59.7 J (14.3 eal). 8, Hazards 8.1 The following procsutions are recommended for safe calorimeter operation. Additional precautions sre-noved in Practice 1-H. Also consult the calorimeter equipment manu- facture's installation and operating instructions before using the calorimeter 8.1 The mass of sample and sny combustion acl as wall as the pressure of the oxygen aimited to the bomb shall not cexcced the bomb manufacirer's specifications $.12 Inspect the bomb parts carefully after each use Replace cracked or significantly worn pans. Replace O-rings and valve seats in accordance with mannifactorersinstrction For more details, consill the manufacture. 8.1.3 Equip the oxyecn supply eslindse with an approved type of safety device, such asa clit valve, in addition tothe ncedte valve and pressure gauge used in regulating the oxygen feed to the bomb, Valves, gauges, and gaskets shall meet industry safety codes. Suitable reducing valves and adapters for 3 fo 4-MPa (300- to S00-psig) discharge pressure can be biained from commercial sources of compressed gas equip- ment, Chock the pressare gauze annually for accuracy or afer any aocidental over pressures that reach maximum gauge pressure 8.14 Daring ignition of a sample, the operator shal not exten! any portion of the body over the calorimeter 8.1.5 Dont fire the bomb ifthe bomb has been dropped or tumed over after loading 8.1.6 Do not fre the bomb if there is evidence of gas leakage when the bom is submerged in the calorimeter ves 8.1.7 For manually operated calorimeters, the ignition switch shall be depressed only long enough to fire the charg. ualysis sample is the material pulverized to pass 250-um (No. 60) sieve, prepared in accordance with either Practice D346 for coke or Method D201 for coal. (WWWSOM) VWYSUaE VuaLHVEaS ISvuadoN 4NIUN « leUOReUISIUT WISV ISUES!) YeMEG IP NSE Y>IO IENGIp 1UL AdoD "YSN ‘THET Vd ‘UByD0YOYSUOD 3S9M ‘OALIG ANOGUEH Weg DOT ‘eUOREWOIUT HISY Id! HEH,df osses - 13 10. Determination of the Heat Capacity of the Calorimeter 10.1 Sample—Weigh 0.8 10 1.2 g of benzoic acid into a sample holder. Recore sample weight to the nearest 0.0001 ¢, 10.2 Preparation of Bomb: 10.2.1 Rinse the bomb with water to wet internal seals and. surface areas of the bomb or precondition the calorimeter according to the manufacturer's instructions, Add 1.0 mL of ‘water 1 the bomb before assembly. 10.2.2 Connect 1 measured fuse in aceordance with manu facturer’s guidelines. 10.2.3 Assemble the bomb. Admit oxygen to the bomb to a consistent pressure of between 2 and 3 MPa (20 and 30 ot. ‘The same pressure is used for each heat capacity run. Control ‘oxygen flow to the bomb so as not to blow material from the sample hokler. IF the pressure exceeds the 5 pressure, detach the filling connection and exhaust the bomb, Discard the sample. 10.3. Preparation af Calorimeter: 10.3.1 Fill the calorimeter vesse) with water at a temper ture not more than 2°C below room temperature and place the ‘assembled bomb in the calorimeter, Check that no oxyzen bubbles are leaking from the bomb. If there is evidence of leakage, remove and exhaust the bomb. Discard the sample. 10.3.2 The mass of water used for each test run shall be M + 05 g where M is a fixed mass of water. Deviees used 10 supply the required mass of water on & volumetric basis shall he adjusted when necessary to compensate for change in the density of water with temperature. 10.3.3 With the calorimeter vessel positioned in the jacket start the stirrer. 104. Temperature Observaions Auomated Calorimeiers: 104.1. Stabiticasion—The calorimeter vessel's temperature shall remain stable over a period of 30 s before firing. ‘The stability shall be +0.001°C for an adiabatic calorimeters and +0,001°C/s oF less for an isoperibol calorimeter 10.4.2 Extrapolation Medhod—Fire the change, record the emperature rise. The test can be terminated when the observed. thermal curve matches a thermal curve which allows extrapo- lation to a final temperature with a maximum uncertainty of +0,002°C, 104.3 Full Development Method Fire the change ancl re ford the temperature rise until the temperature bas stabilized for 1 period of 30 s in avcordance with the stability require- ments specified in 10.4.1 10S Teraperanre Observations Manual Calorimeters: 15.1 When using ASTM Thormameters $S6C, estimate all readings to the nearest 0.002°C. When using ASTM Thermom- eters SHI6C, o S117C, estimate readings to 0.001°C and 25-2 resistance thermometer readings to the nearest 0.0001 . Tap or vibrate liguid-in-glass thermometers just before reading 10 avoid errors caused by liquid sticking 10 the walls of the capillary, 10.5.2 Allow 5 min for the temperature of the calorimeter vessel (0 stabilize. Adjust the jacket temperature to match the calorimeter vessel temperature within (.01°C and maintain for 3 min, 10.53 Fire the charge. Record the time as @ and the temperature asf, 10.54 For adiabatic calorimeters adjust the jacket tempera- ture to match that of the calorimeter vessel temperature during the period of the rise. Keep the to temperatures as equal as possible during the period of rapid ise, Adjust 10 within 001°C when approaching the final stabilization temperature. Record subsequent readings at intervals no greater than 1 min until three suecessive readings do not differ by more than =0.001°C, Record the first reading after the rate of change has Stabilized as the final temperature f, and the time of this reading as. For isoperibol calorimeters, when approaching the final stabilization temperature, record readings uatil three succes: sive readings do not differ by more than 0.001°C per min. Record the first reading after the rate of change has stabilized as the final temperature 2s f, and the time of this reading as e 10.5.5 Bomb depressurization—When the thermochemical corrections will be made by titration, the depressurization amd subsequent rinse eallection shall be done in a manner ensuring, at least 80% recovery of the acidic combustion products, An effective measure of the recovery is offered by the recovery factor described in the following section® Depressorization at 44 Tale suich that the operation is nol Less than one minute provides effective recovery and does not require validation, ‘There are no special requirements related to the bomb depres: surization if the calculated nitric acid procedure is used 10.5.1 Determine the recovery factor from the slope of the straight line resulting from the regression analysis of the titration results (mg of sulfur vs. meg) using three or more samples with at least vo different sulfur concentrations that span the range of sulfur values typically encountered in the laboratory. One equivalent of sulfuric acid (1000 meq) is formed from 16.03 grams of sulfur, A plot of sulfur (mg) vs, rmilliequivalents (meq) of titrant used to neutralize the bomb rinsings has a theoretical slope of 16.03. The milliequivalents of titrant is the product of milliliters of base used and its concentration (normality). The mass of sulfur inthe sample in milligrams is the product of the sulfur concentration in weight ppercent in the analysis sample, the Sample mass and tcp. A, slope of 16 implies 100% recovery. Increasing values. ane indicative of diminished recovery. For example, a value of 20 indicates 80% recovery (16.03 x 100 £ 20 = 80%. 10.56 After depressurization, open the homb and examine the bomb interior carefully for signs of unburied material or sooty deposits, Discard the test result if either is observed, 106 Thermochemical Corrections (see Appendix XI) 10.6.1 Acid Correction (see XJ-1)—One may use either the titration (10.6.1-1) oF calculated titration (101.6.1.2) procedure for coal and coke samples, 10.6.l.1 Titration Method-—Wash the interior of the bomb ‘with distilled water containing the titration indicator (see 7.5) until the washings are free of acid and combine with the rinse Of the eapsule. Tirate the washings with the standard solutions (see 7.6) using a titration indieator, or a pH or millivolt meter. ~Sopyvting data hae been fled a ASTM Itestonl Henares ss my a bee by tegen Reser Repent RADU OZR, "Inet Stay /SOM) VVSUAS VURLHVIAS ISvHadON AMUN s 6. z nciiiendieiebiieliesent i i t i iAly osa6s - 13 ‘The product of the volume of titrant used in milliliters, the ‘concentration of the standard solution (normality) and 59.7 J (1433 cal) shall be taken as el 10.1.2 Calewlated Nitric Acid Merhod-—For test samples that contain no nitrogen, the nitric acid formed in the bomb during the combustion process is derived from the nitrogen in the air that occupies the bomb prior to pressurizing it with oxygen. The quantity of nitric acid formed is a function of the volume of the bomb, the oxygen filling pressure and the quantity of energy released in the bomb during a test. For a given bomb and filling pressure, the relationship between the punt of nitric acid formed and the energy released can be docermined using the following procedure, The calorimeter should be tested using one-gram pellets of benzoic acid when the bomb volume is nominally 340 milliliters. If the bomb volume differs significantly from 340 ml, the sample weight used should be adjusted as required in order to comply with the bomb manufacturer's safe operating guidelines. Tests should be run in duplicate, Determine the nitric acid correction by tivating the bomb washings as outlined in 10.6,1.1. Divide the correction obtained (e1) by the amount ef energy released in the bomb for the corresponding test, The energy contribution from the ignition fuse (e2) is usually small (<1% of the total eneigy 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 be determined for any arbitrary energy release, 1 = (WAR *energy released forthe test 7 Example: ‘The nitric acid correction for a 340-ml oxygen bomb is found to be 41.9 J (10.0 ealories) when the released energy corre sponcls to that liberated by one gram of benzoic acid, 26.45 KI (6318 calories). The ratio of these quantities is 1.58 J per 1000 joules of released energy or 1.58 calories per 1000 calories of released energy. The nitie acid correction for any calorimetic test can then be expressed as follows: 1 ~ 158 energy released forthe txt (ld ork) — (2) For a given calorimeter, the energy released in the bomb luting a test for the purposes of calculating the nitric acid correction (¢1) may be expressed as the product of the tem- perature rise for the test and the eflective calorimeter heat capacity oF calorimeter calibration factor” 1 = (.59/1000)°r eo ‘The calculated nitric acid method can be applied to samples containing up 19 2% nitrogen without introducing a sigaif cant error in the fesulting heat of combustion value 10.6.2 Fuse Correction (see X/.3}—Determine the fuse correction using one of the wo alternatives: 10,6.2.1 Measure the combined pieces of unburned igni faye and subtract from the original length to determine the fuse consumed in firing according to Ey 4 e2=Kx1 on where: €2 = the correction for the heat of combustion of the firing fase, J —-= the length of fuse consumed during combustion, K, = 0.96 Mmm (0.23 calfmm) for No, 34 B&S gauge Chromel C. K, = 1.13 Yin (0.27 ealimm) for No. 34 BRS gauge iron wite, and K, = 0.00'J/mm for platinum or palladium wire provided the ignition energy is constant. 10,6.2.2 Weigh the combined pieces of unbumed fuse and subtract from the original weight to determine the weight in ‘milligrams of the fuse consumed in firing. (7m). Remove any ball of oxidized metal from the ends before weighing. xm o @2 = the correction forthe heat of combustion of the fring fuse, m = the ‘weight in mg of fuse consumed during combustion, K,, = 5.9 Jima (1.4 calimg) for No. 34 BAS gauge Chromel a Ky = 7-5 Img (1.8 eal/mg) for No, 34 B&S gauge iron wire, and Ky = 0.00 Sime for platinum of palladium wire provided the ignition energy is constant When cotton thread is used, employ the correction in J recommended by the instrument manufacturer 10.7 Calculation of the Corrected Temperature Rise— Compute the corrected temperature rise, ras follows: =1404€ ©) where: t= corrected temperature rise, °C; initial temperature reading at time of firing: final temperature reading; thermometer, emergent siem correction (see Eq AL.6 oor Ey 1.8), radiation correction (see Fy ALI or Fq AL?) 107.1 The temperature rise in isoperibol calorimeters ve quire a radiation correction 108 Calculation of the Heat Capacity—Caleulate the heat capacity (F) of the calorimeter using the following eq = [lH on) Het bere oy where: E = the calorimeter heat capacity, IPC = heat of combustion of benzoic acid, as stated in the certificate, Ig m= mass of benzoie acid, g: el = acid correction from 10.6.1 from cither the titration icthod (10.6.1.1) or the calculated titration (10.6.1.2), €2 = fuse correction from 10.6.2, J; and = corrected temperature rise from 10.7.°C. 18.1 Using the procedures described in 10.1 — 108, complete a total of tem acceptable test runs. An individual test shall be rejected only if there is evidence of incomplete combustion, (vwvsow) vavsuaa WuaLHVras Isvuadoy yMUN Yemed |p NSB Yalo aeNaIP Jul Adod “WSN 'EZHET Wd ‘UayDOYOUSUED 359M ‘AUG INOIeH Weg OT ‘JeUOReUIAUT WIsy EdD 4H,Ally 0586s - 13 108.2 The precision of ten acceptable calibration test runs shall have a relative standard deviation (RSD) no greater than 0.17%, If after considering the possibility of oulliers using criteria established in Practice E178, this limit is not met, 01 should review operation of the calorimeter for any assignable cause. Operating deficiencies should be corrected before per forming aiditional calibration measurements as required. Table | provides an exumple summary of series of calibration tests ‘The formulas used to arrive at the mean value and relative standard deviation are independent of the units used for the calibration measurements 10.9 Valid Working Range for the Calibrarton of the Calo 10.9.1 Iis a generally accepted principle of reliable analy- sis that instruments should be calibrated over the full range of measurement and that measurements be restricied to the range calibrated, It is not good practice to report extrapolated data obtained outside the range of calibration. The range of reliable calibration can be considered as the range of reliable measure- ‘ment and vice versa, 10.9.2 It should be possible to vary the amount of benz acid ealibrant by at least +25 4% without observing a signifi ccant trend ia the values obtained for the effective heat capacity or instrument calibration factor. The working limits for the instrument calibration shall be determined and defined in terms cof the corrected temperature rise. AU subsequent measurements shall be kept within these limits. 10.9.3 A convenient way to check a previously calibrated instrument is 10 use benzoic acid as an unknown, The mean value for the heat of combustion from duplicate runs using 0.7 g and 1.3 g sample masses, respectively, should be within =56 Itg or #24 Buu / Ib of the accepted heat of combustion value 10.9.4 For any given instrument, examination of the appli- ccable range of the insirumeat calibration should be carried out when the instrument is new, moved to a different location oF I. Calibration Verification LL. The calorimeter calibration shall be checked on a regular basis. Renewed determination of the heat capacity is required whenever significant alterations have been made 10 the instrument or to the test conditions. The optimum fre- quency for checking the heat capacity or instrument calibration ‘will depend on the stabifity of the measurement system and the risk involved when the system departs from statistical control Since all deta obtained during the period last-known-in-control to fist-known-out-of-control are suspect, such intervals may need to be minimized, TAL There are several empirical r ‘on how frequently the instrument calibration should be cehecked. The experience of the laboratory may indicate the expected frequency of occurrence of trouble, in which ease reference sample measurements, at least three in mumber, should be equally spaced within such an interval. Another Approach is the length of run" concept. In this, recognizable breaks in the production (of data) process are identified which could cause significant changes in preeision or bias, Such breaks could include change of work shift; rest petiods: change, modification, or adjustment of apparatus: use of new calibration standards; significantly long down-times: use of & new lot of reagents, At least three reference samples should be ‘measured during any of these periods when the periods arc considered to be potentially significant, 11.1.2 Periodic checks of the instrument calibration are a risk-reducing procedure. However, if it involves more than ten percent of a laboratory's measurement effort, either the quality conlrol process may need improvement or too much effort is being exerted in this direction. If less than five perceat of effort & is devoted to such measurements, the laboratory may be taking & too high risk of producing unacceptable data, or may not even @ know the quality of the data it is producing, The above % statements are made with a laboratory making a significant > number of high-quality routine measurements in mind, If a VuaLHVCas Isvafadow MUN a subject to major repai Taboratory’s program involves eccasional or one-of- oi 8 = TABLE 1 Calibration Measurments ‘Colann ak =r ‘can Fun Hunter lest cxpaciy Diterenes orm ac average Squares 1 so28 2 2 0288 2 a sozre mm 4 1958 0 8 soe 2 7 wen 186 8 wee 156 8 1356 2 10 ros 7% Sun 102535 en ‘avenge "258 ‘sum Colon 410 Vorone ” ‘Sun Colurn 9 Santa Onions) alae Sagara Gevaron (RSD) 6 ¢ ‘Sa Vance) 00% sbverage 100 { ‘ } ‘ |Gly 05865 - 13 ‘measurements, the amount of quality assurance effort requited including the number of measurements of reference materials, to be made may he significantly more than that indicated above, L1.13 Two complementary provedures are offered for calorimeter calibratioa verification: Control Chart Method and Rolling Average Method, 11.2 Control Chart Method Jor Calibration Verification: 11.2.1 A control chart is a graphical way to interpret test data. In its. simplest form, a selected reference sample is ‘measured periodically and the results are plotted sequentially (or time-ordered) on a graph. Limits for acceptable values are fined and the measurement system is assumed to be in control (variability is stable and due to chance alone) as long as the results stay within these limits, The residence of the values within expected limits is xceepied as evidence that the pr sion of measurement remains in control. The monitored prec sion of measurement and the aecuracy of measurement of the reference sample may be wansferred, by inference, 0 all other appropriate measurements made by the system while it isin a slate of control 11.2.2 A control chart can be realized by sequentially plotting individual measurement values. The central line is the ‘most probable value for (that is, the grand average) of all the ‘measurements or the accepted measurement value. The limits EWL to UWL (ower and upper warning limits) define the area in which 95 percent of the plotied points are expected to lie ‘The limits LCL to UCL (lower and upper conirol fimits) define the area in which almost all (99.7%) of the plotted points are expected to lie when the system i8 in a state of statistical ‘control. It should be clear that when more than 5 percent of the points (one in twenty} lie outside of the warning limits or when values fall outside of the control limits the system is beh unexpectedly and corrective actions, and even rejection of data, may be required 11.2.3 Results ate expected to scatter with a normal distri- bution within the limits. Systematic trends or patterns in the data plots may be early warning of incipient problems and are cause for concer: hence techniques to identify such should be practiced 11.2.4 Control chants, including the factors for calculating control limits are discussed more thoroughly elsewhere (see Guide E882 and (1)*, The central line is either the known value for the test sample (for example, certified value), or the mean ‘of 10 sets of independent measurements. Control limits are then caleulated aceording to the following relationships, vot Mean or acopte value + 3 sigma /satN) ua Mean or acoptes value +2 signe /satN) xivan secapted vie. tw Mean or accepted vale —2 ign ws 02808 sat 4 a3 200 m7 5 130. O1988 BS 4 wos ors mat a wer O17 2s 10 Maar 07089 Bt 20 87 01470 177 2% 1602 1420. 188 (VWYSOM) VYSuaa VadLHVCaS Isvuadox AMUN « IRYONEUIAIUT WASV ISUASI] YEMEG IP NSB YaIO IeNgIp |U) AdoD "YSN 'SZHET VA ‘UAxDOYOYSUED 359M ‘BALIG INOqIeH Weg OT ‘TEUOREWAIUT WISV EXID AEH.Af vse6s - 13, Calorimeter Heat Capacity X Chart 10290 - 10280 — Result 10270 uc 10260 IN fx uw x « 10250 St S Xbar 40240 | |W 10230 4 | eee 10220 SS 2h 4 oS <6 7 8 9 10 Run Number FIG, 1 Example of X Char for Calibration Runs Benzoic Acid Check Sample X Chart 26560 7— — —— 7 26540 = | 26520 —+* Result 26500 UCL 26480 + Fi | Uwe 26460 26440 + Accepted value 26420 UWL 26400 +-%»—%X— $$$ #§ $$ kh 26300 bye a ee 2900 et io 8 4 Fb 7 Run Number 8 9 10 FIG. 2 Example of X Chart for Check Sample Runs 1.4.1 By internationa ‘cid was selected a8 the chemical sta calibrating bomb calorimeters, Today, it remains as the sole ‘chemical primary standard for this type of calibration. 1.4.1.1 In general, the calibration of an analysis instrument consists of the evaluation of its response function in terms of the composition of the analyte. The instrument responds to some properly of the analyte, the value of which needs to be quantified by use of kaown substances. It is tacitly assumed. that the instrument will respond analogously to the standard and test samples, With this in mind, the coniidence in the measurement process is influenced by the unceriaimy in composition of known samples and the soundness of the analogy. H1.4,1.2 It is desisable to perform check experiments in order to demonstrate confidence im the ability to make mea suremetts on unknavins that are not only acceptably precise but also acceptably accurate. This is especially true in instances where conditions in the calibration and combustion tests differ appreciably. For example, large differences in the rates of combustion between the calibrant and the unknown or signifi- cant differences in combustion chemistries may give tise to systematic errors that are difficult to detect. The use of test substances in such check experiments can help demonstrate that the techniques and procedures used! in determining heats of combustion of unknown materials are reasonably free of persistent errors, { j | j (vison) vivvSwae VANZLHVCaS Isvuadox AMUNGy vsses - 13 11.4.2 For work with solid samples, the following test substances are recommended. sraiv ey ‘uvstanes estan Cis tose Graconnceis The (yen) aly) ama chs rr (#ocHa}s oN fewr 24 Denety = 1.35 ae 2H aoe gaia tails steal wag’ @ gee) a (00012 gee) 1.4.2.1 Both acotanilide and tris (hydroxymethyl) amin- cometliane are available in high purty, are non-hygroscopic and have very low vapor pressure, Acetanilide is available from NIST as. micto-analytical standard for CHON compounds (SRM 141). Tris (hydroxymethyl) aminomethane is also avail able from NIST as an acidimetric standard (SRM 723) 11.422 Both materials are commercially available. When the oforementioned materials are used as secondary thermo- chemical standards or test substances for combustion calorimetry, ensure that the minimum stated purity is at least 99.9% 114.23 Crystalline tis (hydroxymethyl) aminomethane is Gificult to form into a durable pellet. Its relatively low heat of ‘combustion value allows this material 10 be weighed directly into the combustion crucible and combusted in this form. When a consumable metal fuse wire is used, the wire loop shall be in direct contact with the granular sample 1.4.2.4 Acetanilide is easily formed into a 12.5 mm diam ter pellet and shall be burned inthis form due 1 is higher heat ‘of combustion value, 1.4.2.5 The nitric acid correction for tests involving the recommended test substances is approximately 50% higher than what's typically obtained for benzoic acid calibrant samples. This is a consequence of the single nitrogen atom associated with each of the test materials. About 10% of this nitrogen gives rise to aqueous nitric acid during the high pressure combustion process. The remainder appears as cl: femental nitrogen in the combustion produets, The additional correction is accounted for transparently when the titration method is used to arrive at the acid correction. When the calculated nitric acid method is used, the nitric acid factor (NAF) shall be increased by 50% when applied to tests involving these test substances, 115 Use of Laboratory Control Materials: 11.5.1 A laboratory control material (LCM) is similar to a certified reference material in that itis a homogeneous matrix, that offers key characteristics similar to the samples being analyzed. & tue LCM is ane that is prepared and stored in a stable condition strictly for use in-house by a single laboratory. ‘Alternately, the material may be prepared by a central labora tory and distributed (© others (so-called regional or program control materials). Unlike CRMs, the heat of combustion of LCMs are not certified but are based upon a statistically valid umber of replicate analyses by one or several laboratories. In ‘practice, this material can be used to assess the performance of 4 single laboratory, as well as to determine the degree of comparability among different laboratories, 115.2 A significant amount of work is involved with the production and maintenance of any LCM. For example, materials related issues such as stability, homogenization techniques and proper conditions for storage must be ad dressed. For smaller laboratories, tne time and effort involved supporting the use of true LMs may not be justified. In such eaves, the use of CRMs is preferred 11.53 Routine analysis of CRMs or LEMS represent an important aspect of a pesformance-based QA philosophy. At least one CRM or LCM must be analyzed along with each batch of 20 oF fewer samples (that is, QA samples should comprise a minimum of $% of each set of samples). For CRMs, the cetified beat of combustion value wil be Known to te anayst(s) and will be used to provide an immediate chock on performance before proceeding with a subsequent sample batch. Performance criteria for both precision and accuracy must be established for the analysis of CRMs or LCMSs using instrumental technique. Ifthe laboratory fails to mect sion or accuracy control limit ciara fora given ie CRM or LCM, the data forthe entire batch of samples is suspect. Potcatial operating deficiencies must be checked / corrected and the CRM. or LCM uy have to be reanalyzed to confirm the results Ifthe values are stil outside the control limits in the repeat analysis, the laboratory is required to find znd eliminate the source(s) ofthe problem and repeat the analysis ofthat batch of samples until contol limits ‘are met, before final data are reported 12, Procedure for Coal and Coke Samples 12.1 Weigh O08 to 12 g of sample into a sample holder. Record the weight to the nearest 0.0001 g (see 12.6.3) 12.2 Follow the procedures as described in 10.2 ~ 10.5 for ‘determination of heat Capacity. For the calorific value of coke it is necessary to use 3-MPa (30-atm) pressure for both standardization and analysis, ‘The starting temperature for dewerminations shall be within 0.5°C of that sed in the determination of the heat capacity. 12.2.1 For coke, place a clean combustion capsule in the center of a quartz disk and press the capsule to make an impression in the disk. Cut slits from the ouside edge of the disk to the impression. Insert the quartz disk in the combustion capsule so that the slit portion will cover the sides of the capsules, 123 Carry out a moisture determination in accordance with Test Method D3173 of Test Methods 17582 on a separate portion of the analysis sample preferably on the same day but ‘nol more than 24 1 apast from the calorific value determination 0 that reliable corrections to other bases can be made 12.4 Conduct the sulfur analysis in accordance with est, ‘Methods 13177 or D4239. From the weight % sulfur, calculate the sulfur corrections (see X1.2). 12.4.1 When titratign method is used (See 10.6.1.1), the sulfur correction is 63 = 5550/2 XS Xmor(3. call x Sm) oo) (WWVSO)) VWSY3E VEALHVEaS IsvuadoOM AMUN tu Adoo "YSN ‘SZP6T vd ‘UaxPCYOYSUOD 3SaM ‘BAUG ANOGueH 4weg OOT ‘TeUOReWOUT WISY ed) HEH,ily Dse6s - 13 where: 3 = a comeetion for the difference between the heat of formation of H.SO, trom SO, with respect 10 the formation of HNO,, J: 8 = wt % sulfur in the sample; and m= mass of sample from 12.1, . 124.2 When the calculated nitric acid method is used (see 1061.2), the sulfur correction is 63 = 92 Hg XS % on 022 Leallg XS Xm} where: 3 = acorrection associated with the heat of formation of H,80, from SO., J S-= wt sulfur in the sample; and m= mass of sample from 12.1, g. 12.5 For eight mesh samples, analyze coals susceptible to oxidation within 24 b of preparation 12,6 Coal or eoke that do not burn completely can be treated as follows 12.6.1 For coke, use a crucible liner of the type recom. mencied in 6.11 12.6.2 Use a combustion aid such as benzoic acid ethylene ‘alycol, mineral ofl or a gelatin capsule. & minimum of 04 g of Combustion aid shall be used. Record the weight to the nearest 0.0001 g. Calculate the correction for use of a combustion aid using the following: eh = Hax me «ao where ¢4 = conection for use of a combustion aid, Ha = beat of combustion of the combustion aid Ig (calle) and ‘ma = mass of combustion aid, 2. 12.63 Vary the mass of the sample to oblain complete a the combustion while confining the temperature rise wit valid working range of calibration, 13, Cateulatio 13.1 Gross Calorific Vatue—Caleulate the g value Q,,,Agross) using the following equation: O..Agrons) =[(08,) el —e2—e2—etm where: QpedZr0ss) = Bross calorifle yalue at constant volume as. dotermined, Ng (calla), g, = the heat capacity of the calorimeter, JOC (cal°C); ' = correcied temperature rise according to 10.7.° c: al acid correction according to 10.6.1, J 2 fuse correction according to 10.6.2, 3 a sulfur correction determined according to 12.4, 5 4 = combustion aid correction determined ac- cording to 12.6.2, and mass of the sample, g. 13.1.1 See X1.5 for an example calculation, 13.2 Net Calorifie Value et Constant Pressure: 13.2.1 Several steps are required in order to report an as-received net heat of combustion, at constant pressure, derived from an as-determined gross heat of combustion at constant volume. The first step involves calculating a gross heat of combustion at constant pressure from the calorimetri- cally determined gross heat of combustion in the bomb at constant volume. 13.2.2 No work is performed in constant-volume bomb calorimeuy, so the heat measured equals the change in internal energy of the system, When fuel is bummed at constant pressure, there is a change in the volume of the system. A small change in energy accompanies this change in volume. When fuel is ‘burned at constant pressure and the water formed condensed to the liquid state, there is a contraction in the volume of the system. This contraction is equal to the volume of oxygen required (o burn the hydrogen. Work is done on the system by the atmosphere in filling this void in order to maintain a ‘constant pressure, When carbon in the fuel reacts with oxygen, fn equal volume of carbon dioxide results and no change im volume occurs. The exygen and nitrogen in the fuel both give rise to an inerease in volume. The energy associated with this change in the volume of the gaseous phase for the combustion reaction may be expressed ss follows. Ov p= 001TH, 4292-016) ~ 0,/31:9988— 8.0134) Ris the universal gas constant [8.3143 M(mol *K)] and T 3s the standard thermochemical reference temperature (298.15 K) 1322.1 Huy Ong and Nagy are as-determined bydroge oxygen and nitrogen, respectively, %, in the analysis sample ‘The hydrogen and oxygen contributed by the sample moisture ‘are not ineluded in H,, and O,,» respectively. 1 ‘The following formulas may be used to convert hydrogen and oxygen values that include the hydrogen and ‘oxygen io the moisture associated with the analysis sample 10 values excluding the moisture Mae> Hoag ~ OANS as) Oye Ong O88818M, ay 13.2.3 The next steps involve ealeuluting the energy asso. ciated with the heat of vaporization of water that originates from the hydrogen content of the sample [Qh]. the moisture content of the analysis sample [Qmad] as well as the as- received moisture value [Qmar] Qh = 001" Fray (Htatt2016) as) Hap is the constant pressure heat of vaporization of water at 25 € (43985 mol) Qomad = 0.01 Hop (Mea 180158) cas) nae = 0.01" Brander 18.0154) on Mac! and Mar are values for moisture a-determined and as- received, respectively in weight %. 13.24 ‘The as-dotermined net heat of combustion at constant presse is equal to ealorimetcally determined heat of com- Dustion with the addition of the small constant volume to ‘constant pressure correction, less the energy associated with (WWYSOM) VWYSU3a VuaLHVCas TsvaadoX YMUNfly vses - 13, the latent heat of vaporization of water originating from the fuel hydrogen and the sumple moisture. pane) = Qvadl gross) + Ov ~ p= Ol mad 13.25 ‘The dry net heat of combustion at constant pressure is given by the following relationship. 2h)" 10004 100 asi Ma) ay apaines) = (Qvagross)+ Ov ~ p 13.26 The as-eceived net heat of combustion at constant pressure is given by the following relationship, Qparines) ~ (Oral gras) + Ov p— Qh 100 ~ Asor}(LUD — Ata Qnar 205 13.27 For reference purposes, the dry and as-received gross heat of combustion values at constant volume are provided by the following well-known relationships described in Practice DBI80. Qvetlgross) ~ Qvadlgrass)*(4004(100— atu) (19 Qvar( gress) ~ Ova gros(100 ~ Ster)(100— Ata) (22) Example: races) soo we Mas 200% Mer 00% He) e008 Ot) 13.00% Nas) Noo ove 198.39 oh e727 dy Ged seady na 1903. rer aaieas.ia Gpacine 290021 40, pied 29735346 pant) aries Ig 13.3 Net Calorific Value ar Constant Pressure using Dry Basis Values 13.3.1 The energy associated with the change in volume of the gaseous phase for the combustion reaction is expressed as follows: O,., = OUI RIM (22018) ~ 0 431.9988 — N,/28.0130) ey where: R = the universal gas constant (8.3143 Jmol **K)] and T is the standard thermochemi cal reference temperature (298.15 1), Hy Oy and N, = dey basis hydrogen, oxygen and nitrogen, respectively, %, in the analysis sample. 13.3.2. The next steps involve calculating the energy asso- ciated with the heat of vaporization of water that originates from the hydrogen content of the sample [Q,}, and the assreceived moisture valite [Qh] 0, = 000%H,.*(4,:2016) ea Heyy = the constant pressure heat of vaporization of water at 25°C (43985 mel) Qing = HONE, CMSB OES) on M,, = moisture as-received in weight % 13.33 ‘The dry net heat of combustion at constant pressure is equal to the dry basis calorimetrically determined heat of ‘combustion with the addition of the small constant volume to ‘constant pressure correction, less the energy associated with the latent heat of vaporization of water originating from the fuel hydrogen. Q,Aset = O.Agreas)¥ 8, ~ 0. 13.34 The as-received net heat of combustion at cor pressure is given by the following relationship Qpalnet) = (@,dsross}Q._, ~ Q,)*4(100~ M1100) 26) ant On 13.3.5 For reference purposes, the dry and as-received gross hheat of combustion values at constant volume are provided by the following well-known relationships described in Practice DSI80, Qularossd = O,fress)*( 100/100 ~ 44,9) elerass) = @ ,fgmass)*( 100 ~ v,/100 (28) e% Mas = moisture asletermined in weight %. Faxble reno) 20612 We My soos ry a8 ° saa7% N Me 2, 129.9 Ona 1953. fee) 2516909 nina 2erss7 wy Orsined 261 $y 14, Report 14.1. Report the calortfic value as 0, (gr08s) along with the moisture of the sample as determined Af, from 12.3, 14.2 The results of the calorific value can be reported in any. cof a number of bases differing in the manser the moisture is, treated, Procedures. for converting the value obtained on an analysis sample to other bases are described in Practice D180, 15, Precision and 15.1 Precision 15.1.1 Manual Adiabatic Catovimeters 15.11.1250 ym (No. 60) Samples: (1) Repeaiability Limit (r}—The value below which the absolute difference between two test results calculated to a dry basis (Practice D3180) of separate and consecutive test determinations, carried out on the same sample of 250 jim (No. (60) coat and coke in the same laboratory by the same operator using the same apparatus on samples taken at random from a single quantity of homogeneous material, may be expected 10 fcecur with a probability of approximately 95 4. The repeat ability fimit for this test method is 115 J/g (50 Btu/Ib). (2) Reproducibility Limit (R}—The value below which the absolute difference between two test results caewlated to a dey basis (Practice D3180) carried out in different laboratori (vvso) VMVSuad VuaLHVras Isvuadoy yMUN = FeuOReWIOAUT WASY ISUBSII WeMed IP NSB Ye}O IeNqUp 1U1 AdoD “YSN ‘SZHET vd ‘UOYIOYOUSHCD 159M ‘OALIC sNOGueH 44eg OOT ‘1eUONeUIAIUT WASY Ed! HCH,using samples of 250 yun (No. 60) coal and coke taken at randam from a single quantity of material that is as homoge- neous as possible, may be expected to occur with a probability ‘of approximately 95 %. The reproducibility limit for this testis 250 J/g (100 Bruvlb) 15.1-1.2 2.36 mum (No. 8) Samples: (1) Repeccability Limit (r)—The value below which the absolute difference berscen two test results calculated to a dry basis (Practice D3180) of separate and consecutive test decerminations, carried out on the same sample, using the same riffle, determined on a single test specimen of (0 separate 2.36 ‘man (No, 8) test units of eoal reduced entirely to 250 ym (No, (60) und prepared from the same bulk sample coal in the same laborutory by the same operator using the same apparatus on samples taken at random from a single quantity of homoge~ neous material, nay be expected to occur with a probability of upproximately 95 % ‘TABLE 3 Ranges and Limite of Repeatability forthe Caloritic Value of 2.36 mm (No.8) Coal with Manual Adiabatic Calorimeters A ar Topsy na ro im Taam Ba woe Sa {i201 isso stu) (ed sua) SubormnowLigte 26440 12981 ‘iou9 iemow'2 reo ius) 3 (2) Reproducibility Limi (R}—The valuc below which the absolute difference between two test results calculated to a dry basis (Practice D3180) earried out in different laboratories using samples of 2.36 mm (No. 8) coal reduced entirely to 250 jum (No, 60) taken at rancor from a single quantity of material that is as homogeneous as possible, may be expected to occur with a probability of approximately 95 %. ‘TABLE 4 Ranges and Limits of Reproducibikty for the Gross CCaloriic Value of 2.36 mm (No.8) Coal with Manual Adiabatic Calorimeters Tapani coal Fenge ea ‘Btuninaus—~*~*«C RTO Bate (ie 700 14500 Ge) (107 Bly Subbtuminass Lite 29.402 29651 Jig Bebe (@7o010 12750 Gur) (ao stuy 15,1.1.3 Precision statements for 236 mm (No. 8 sieve) samples have not been developed for anthracite coals. 15.1.2 Automated Calorimeters 15.1.2.1 Micropravessar Controlled Calorimeters!” * hn imerabortory aud, evgned camino! with Poetce EO, as or sai in 949. Lig loeionespariptd nhs std Supowig das sre ‘ralele fom ASTM Heatquaners: Regus Repon R&CDOS.10(3 An iereratsy st. designed comsisint wih Pcice ES). wes con sso 8s Puene le etic i ty, Soprng Sala a able trom ASTM Menges equ Rept RR.DOS- D2. Limits of Repeatability for the Gross ‘Calorifie Value of 250 yim (No. 60) Coal and Coke with Microprocessor Controlled Calorimeters as ee Repeaaoiny eit “Gre Nia 080 28. (3040 Buu) (4 eo) Bavminous 280 1 34100 4g Mog (200% 14700 Bue) (er Bu) ‘saxotuminoue Ligne 21980 1627 000 Jig e049 iseeow 11 900 Bure) cr ‘TABLE 6 Ranges and Limits of Reproducibility for the Gross Calorti Value of 250 um (No. 60) Coal and Coke with Microprocessor Controlled Calorimeters cae a Rago oe tin Cae Temnaly 0980 9a aie (are Bw) (Buty ‘miro 2200 34130 Je 258.9 (i000 12700 ab) (HOB) ‘usthuminousLigite 21 88010 27 64 ie satay (aan 1 969 BA) (51 ta) (1) Precision—The precision of this methed for the deter: mination of calorific value in the analysis sample of coal and ! ccoke is shown in Tables 5 and 6. The precision characterized by repeatability (5, and reproducibility (Sj) is described in Table A2.1 and Table A2.2 im Annex A2. (2) Repeatability Limit (r}—250 um (No. 60) Samples-the value below which the absolute difference between two test results calculated 10 a dry basis (Practice D3180) of separate ‘and consecutive test determinations, carried out on the same | sample of 250 ym (No. 60) coal and coke in the same | laboratory by the same operator using the same apparatus with | the same heat capacity on samples taken at random from a} single quantity of homogencous material, may be expected 10 { { ‘occur with a frobebility of approximately 95 %. (3) Reproducibility Lira (R)—250 um (So. 60) Sarmples- the value below whieh the absolute difference between two test | results calculated toa dry basis (Practice D3180) carried out in § Afferent laboratories using samples of 250 pm (No. 60) coal * and coke taken at random from a single quantity of material that is as homogeneous as possible, may be expected to oeeur with 2 probability of approximately 95 % 15.1.22 Precision slaloments have aot been developed for 2.36 min (No.8 sieve) size coal samples or for 250 um (No 60) anthracite coals. 15.2 Bias—Bias in the determination of the gross calorific value is eliminated provided samples are treated identically to the benzoic acid used in the determination of the calorimeter hheat capacity 15.3 The net heat of combustion result and values calculated to other reporting bases are affected by errors incurred im all the deverminations used to evaluate the valuc. AS a result, the repeatability and reproducibility limits set forth in this section are only applicable to dry gross heat of combustion values.lp ose6s - 13 16. Keywords 16.1 adiahatic calorimeter: bomb calorimeters; calorific value; calorimeter: coal; coke: isoperibol bomb calorimeter ANNEXES (Mandatory Information) Al. THERMOMETRIC CORRECTIONS. ALL Thermometer Correciions—The following comee~ tons shall be made: AL.L.1 Calibration Correction, shall be made in accordance ‘with the calibration cortficate furnished by the calibration authority. ALL2 Radiation Corrections—Radiation corrections are required to calenlate heat loss or gain to the isoperibol water Jacket. They are based on the Dickinson formula,(4) the ‘Regnaul(-Pfaundler formuls.(8) or the U.S. Bureau of Mines method(6) The same method of determining the radiation correction sivall be used consistently in the determination of ‘heat capacity and sample measurements ALL21 Dickinson Formula: Cro a)- rle— 0) fanny where: C, = radiation conection; 4) = rate of rise io temperature per minute in the preliminary period, IF temperature is falling, r, is negative Py = tate of rise of temperature per minute in the final period. If temperature is falling, r, is negative: t= firing temperature: ‘= final temperature, being the first temperature after hich the rate of change is constant @ = time at temperature ¢, ‘b= time at temperature ¢, + 0.60 (7, ~1,); and © = time at temperature 1, AL.1.22 Regnault-Praundler Formula: Cle = Mar, (aia) where: C, = radiation correction, Fe (- leo). (anay 4 ay 0 the number of temperature readings in the combustion period after firing: = avorage temperature during the preliminary period average temperature during the final period successive temperature recorded during the combustion period after firing at equal time intervals (for example, 1 mi.) ancl the sum of 4, The remaining symbols are the same as defined in the Dickinson formula, AL12.3 Bureau of Mines Methad—A table of radiati ‘corrections cat be established so that only the initial apd final readings are required to determine the calorific value of a fuel This can be done by curtying out a series of tests using the procedure described in Section 10, using the following condi tions. Regulate the amount of sample burned so that a series of determinations is made in which different temperature rises are obtained. For all determinations, keep the water jacket tem- perature constant, fire the bomb at the same initial temperatun ‘and have the same tine, ~ a, elapse (+2 s) between the initial ‘end final readings. Determine the radiation corrections for each of the series of temperature rises using the Diekinson method (ee AL.L2.1), oF the Regnault-Praundler method (see AL.1.2.2). These corrections are constant for a given tempera ture rise, From the series of readings, a table or graph is plotted fo show radiation correction versus temperature rise. Onee the lable of graph is established, the radiation corrections ean be ‘obtained from it until there is a major change in the equipment. AL.L24 Bxample—See Table ALL ALLS Emergent Stem Correction— The calculation of emergent stem correction depends upon the way the thermometer was calibrated and how it is used. Two conditions are possible, (vbivson) VAYSuaa VuaLHVEas Isvaadoy MUN Nsa yaio aenqyp jul Ado> “ySn ‘EZb6T Vd ‘UaxDOYOYSUCD 3S9M ‘OnRLIG snoqueH JEG OT ‘1PUOREWOIUT WISV edd HEH, leuonewsoquy Wasy Isuasi yemeg 15a Basie 5 5e) Beso 7 Banat 8 basres 5 >aca 0 assis ‘ecee 8 2aesee 4 Mens 1s40) 2as750 ke 16 asi " phere 6 2usaie 19 etree 29 ond) pr (eeasr2 224108) - 00076 (ea.ooeg 246750) /5 = 0020 = eeastas beatae) B= mame eu eB50 + 28.6750) /2= 2.5505, ae tm Beed,erasa Mo emrIELe msm) Gein =- 10-2) ro f6—6) =U) ~ CoN (= 0027 6 (Rograuh Peron = fa) ron 15—5) KOon2S) (284349 zeaeoe)0oa7e) = 09279 Seneran 22s) 00073 = Feahers0 ~ 22a 21059 n+ 12) — 09078 ~ learn ALIB.1 Thermometers Calibrated in Toul Immersion and Used in Parial Immersion— ‘This emergent stem correction is made as follows: (pei L— 7) co= Ke (aL) where: Co = emergent stem correction, K = differential coefficient of thermal expansion for the theemometric liquid, (See Noe A1.L.) 1. = scale reading t0 which the thermometer was immersed, T= mean temperature of emergent stem, i= initial temperature reading, and y al temperature reading Nove Al-| Typically 0.00076 tor thermometers calibrated in °C and filled with lw za thermometic Hg Example: A thermometer was immersed 0 16°C: its initial reading, 1 was 24.127°C; its final reading, f, was 27.876, the mean temperature of the emergent stem, T, was 26°C. 100076 (279 — 24.1) x (279424.1 ~ 18— 26) ce oon» (aL. AL13.2 Thermometers Calibrated and Used in Partial Immersion, Bui axa Different Temperature Than the Calibrated ‘Temperature: Ce = KUT Wlte~ ed aly where: Ce = emergent stem correction, K = differential coefficient of thermal expansion for the thermometric liquid, (See Note A1.2.) initial temperature reading, Final temperature reading, ‘observed stem temperature, and stem temperature at which the thermometer was calibrated. [Nom A.2—Typicilly 0.00076 for thermometers clibated in °C and filed sith & low hazard thoemometie gud Example: A thermometer has an initial reading, 1, 27°C; a final reading, ah, 30°C: the observed stem temperature, fo, 28°C: and the calibration temperature, tc, 22°C Ce= 0.00076 (30-27) x(28~22)= 0014 (ALB) A2, PRECISION STATISTICS A2.L The precision of this test method, characterized by repeatability (S,, 7) and reproducibility (Sp R) has. been determined for the following materials as listed in Table N21, TABLE A2.1 Repeatability (S, 1) and Reproducibility (Sy. A) Paramotors for Coal Samples Tae hems 5, = 7 7 arenn wwiraae jess aes7 S014 Dri wiao 27875 568 90D The zoe Sistas jomarae © 24003578 wat toaN aotmen viere6s 2872 77a wD? SD Siimce fiona 14094750 sa] 281 porate oem §=— oro 56251855 Goyaka vie7a0n ars) 770 Okoe S848 Steaua Medaae 2726 Sod Tous 168m aeaaube ‘eeeros = ars0 Sea 748881 Upmesesaae 06ST 9585.35 Values are Bru, A22 The precision of this fest method for coke samples, characterized by repeatability (S, r) and reproducibility (Se R) has boon determined from the results in Research Report RR:DO5-1025."" The results are summarized in Table A2 2. Values are in Bru, A2.3 Repeatability Standard Deviation (S,)—The standard deviation of test results obtained under repeatability cond tions. r= 2.8 x "© Sugpoing deta ss nen at st AST ltermatonl Hendin a ay baad by uuesing Rss Repo RR-DDS- 1028, Comact ASTM Caster Somice a beeice animeAly vse6s - 13, TABLE A22 Repeatability (5, and Reproducibility (SF) Parameters for Coke Samples ioe weage SS, FReterance? Paracas Wet ——tas aaah —a7e7 a8 78 Ckooot” Furnace 1309700 2a nae ass tase Ckooo2 Breese 29073 20H LBS SATE Hee Gkoot___Furaco _i3o7cas_tssz__ ane ta46_ thee A24 Reproducibility Standard Deviation (Sq)—The dard deviation of test results obtained under reprodi conditions. R = 2.8 x Sg APPENDIXES (Nonmandatory Information) XI. THERMOCHEMICAL CORRECTIONS XI. Energy of Formation of Nitric Acid (HNO4): XI.L.1 A convetion, e1, (106.1) is applied for the forma tion of nitric acid XI.1.2 (1) HNO, is formed in the calorimeter by the following reaction: 126. ES O(g)=12HLO() (XID = HNO, (in $00 m91H,0) X1.1.3 The energy of formation of FINO, in approximately 500) mol of water under bomb conditions is minus 59.7 kJ/mol (14.3 keallmol. (7, 8) The enthalpy of reaction (all values in d/mol @ 208.15 K) is calculated ax 4,1 = 1 (HINO, (in 500 HLO)] ~ ¥ Ad [Ns] ~ % A411 [Oa] ~ Ye AAI [10 ()] = 206.974 2 (0)— 64.059. From the energy of reaction at constant volume is caleulated from the following relationship: AU = A,t1 — RTAn whore R is the tuniversal gas constant (8.514 J /"(enol K)], T is the standard thermochenial reference temperature (288.15 K) and Aa is the change inthe number of moles of gas in the reaction. R= 2ATY AD mol. AU = 64.059 — (2.479) (-7H4) = -59.7 Kal XI.1.4 Normal convention assigns a negative value for a heat of formation that is exothermic. By definition, heat released from combustion processes are expressed as positive values. Hence, the negative factors developed for nitrie and sulfuric acid corrections are expressed as positive values in the calculations X12. Energy of Formation of Sulfuric Acid (H,SO,) —By definition (see Terminology D121), dhe gross culorifie value i ‘obtained when the produet of the Combustion of sulfur in the sample is SO, (g), However, in acwal bomb combustion processes, all the sulfur is found as H,SO, in the bomb washings. X1.2.1 A correction e9 is applied for the sulfur in the test sample that is converted to H,SO,. This correction is based upon the energy of formation of 1,50, from SO, in solutions typically present in the bomb at the end of combustion. This correction is applied in one of two ways depending on whether ated, al I gram sample is burned, the resulting H,S0, condensed with water formed in the bomb will have a ritio of about 15 mol of water to 1 mol of HSO,, For this concentration, the energy of the reaction under the conditions, of the bomb process 1s -297.2 Ki/mol, (8) As a result, a ‘correction of 9.27 kJ (2.21 keal) must be applied for each gram of sulfur converted to sulfuric acid. However, when the Bomb washings are titrated, a correction of 2 x 59.7 Kiimol (2x 14.3 B keal/mol) of sulfur is already included in the toral acid correction, Therefore the correction which aust be applied for 3 sulfur is 297.2 ~ (2 x 59.2) kifmol or 5.35 klfg of sulfur. This isywadoN AMUN ‘vd ‘ua3}204oysUOD ISM “OALIG sNOqUeH WEG OT “| is expressed as 55.5 J (13.3 cal) for each pereentage point of BH sulfur per gram of sample, g 1 z 80.70, (9)+H.0 ()-it $0, (in Smo 1,0) «1.29 = 2 X1.2.2 The values above are based on a sample containing g approximately 5 % sulfur and approximately 5% hydrogen. 3 ‘The assumption is also made that the H,SO, 1s dissolved & entirely in the water condensed during combustion of the sample, (9) The enthalpy of reaction (all valucs in kifmol @ 298.15 K) is calculated as: DH = 8H [80 (in 15 #,0)] ~ A,11[80,) AHO.) — 4,414.0 (0) 883,623 ~ (~206.830) ~ 1 (0) ~ (285.830) 30063 From this, the energy of reaction at constant volume is cal- culated following the same procedure as in XI.1.3. AU = -300.963 ~ (2.479) (-3/2) = -297.2 kW/mol. X1.23. For different sample weights or sulfur content, oF both, the resultant normality of avid formed can be different, and therefore, the normality of titrant must be adjusted accord: ingly. Basing the calculation upon a sample of comparatively large sulfur content reduces the possible overall errors, because, for small percentages of sulfur, the correction is smaller. UOREWAIUT WAS Id! HH, « luo eUsARUT WLSV /SuBS!] YeMed IP NSB Ye/O JeNaUp U1 AdoD “YSN ‘Sz¥6Af] 05865 - 13, X12 Fuse Comection—The energy required 10 melt a platinom or palladium wire is constant for each experiment if the same amount of platinum or palladium wire is used. As the energy is small, its effect is esseatially cancelled out in the relationship betsveen the standardization experiments and the calorific value determinations, and it ean be neglected, X14 Reporting Resulrs i» Other Units X1.4.1 Express the gross calorific value in joules per gram, calories per gram, or British thermal units per pound. ‘The relationships between these units are given below. 1 Inzernational Table (IT) calorie = 4.1868 3 (10) 7 thermochernical calorie 4.1841 LIT cally = 1.8 Bub 1 Bre = 1055.06 J JP? Bru or 1 MB 1.05506 GI Prior to widespread adoption of SL units, the unit MBtu was originally defined as one thousand Bru, presumably from the Roman numeral system where "M" stanly for one thousand, Todlay, this is easily confused with the SI mega (M) prefix, which multiplies by 2 factor of one million. In an attempt at avoiding confusion, many still use MMBtu to represent one million Buu 1 Bush 1000 Brut: 326 My = 2326 Git X1.4.2 The combustion of fuel to produce energy results in the emission of combustion byproducts. The exact levels and types of each emission depend on the type of fuel used, the cfficieney and age of the equipment, emissions contcols that may be mandated by regulatory agencies, und other factors. An ‘emissions factor is a value Ural attempts to relate the quantity of an emission released to the atmosphere with an activity associated with its release, For coal, these factors are often expressed as the mass of the emitted material divided by energy released during the combustion. Such factors facilitate csstimation of emissioas from various sources. Carbon dioxide (CO,) emissions from the combustion of fuel can be deter mined accurately regardless of how the fuel is used as these emissions depend almost exclusively on the carbon content af the fuel. The same is true for sullur dioxide (SO.), where it originates from the sulfur content of the fuel. Both earboo and sulfur are almost completely oxidized during combustion and all carbon and sulfur in the fuel are assuined to be present in the fue gases as CO, and SO, respectively. The energy released ‘may be expressed as either the net heat of combustion or lower heating vilue (LHV) or the gross heat of combustion or higher heating value (HIELV). ‘The net heat of combustion is generally closest to the actual energy yield. The gross heat of combustion which includes condensation of the combustion products is greater by about 5% in the case of coal and depends mainly on the hydrogen content of the fuel. The appropriateness of using LIV or HHV shea calculating emission factors depends upon the application. For combustion where exhaust gases are cooled before discharging, HHY is more appropriate. Where no attempt is made (o exttact useful wrk trom hot exhaust gases, the LIV is more suitable. In practice, many European publ: cations report LHY, whereas North American publications use HIV. General formulas to calculate emission factors for CO2 and SO2 are given below X1.4.2.1 ‘To express carbon as kilograms of carbon dioxide per gi COs, kefG joule, (C. % x 44,/12, / Heat of combustion, Wg) x 10000 This is numerically equal to metric tons (t) of carbon dioxide pet terajoule (TI), The factor 44/12 isthe ratio of the molecular ‘weights of CO, and carbon, The aforementioned factor is used. in routine commercial practice rather than the exact ratio of the molecular weights 44.0098/12,011. This results in an error of the reported value of no more than 0.1%: In non-SI units: (C, 9 x 44,/12. / Heat of combustion, Biu/lb) X1.4.2.2 To express sulfur as kilograms of sulfur dioxide per gigajoule: SOs, KeAGI = (S, S x 64/32. / Heat of combustion, Hg) x 10000} ‘The factor 64/32. isthe ratio of the molccular weights of SO, and sulfur. In noa-SI units SO» WMBtu = (S, fe x 61.52 Bowlby x 10000 } Heat of combustion XLS Sample Calentations: XIS.1 Heat Capacity E [He x m) +el + e2}/t He = 26454 Jie: m Loos7e ef = 7.20 ml x0.1000 N x 59.7 J = 43.0 J acid correction by titration] NAP = 43.0-J f (26.454 kivg x LO047g) = 1.62 J/kI of released enerzy 2 = K, (Chromel C) x $7 mm wire consumed = 0.96 Mmm x $7 mm = 55 J. fuse correction : 2,6006°C E [(26454 Je x 1.0047 g) + 43.0 + 55 J] /2.6006°C, and E 1028 Ire. X1.5.2 Heat of Combustion [sitrarion method): Quai (gross) = (UE) el ~e2 03 ~ef] 1m E 10258 JC. 1 2.4170°C el 12.90 ml x 0.1000 N x 59.7 J = 77.0 J, tora acid correction 2 = K; (Chuomel C) x 54 mm wire consumed 0,96 Jimm x 54 mm = 52 J, fuse correction 3 = 55.5 x 124 S x 0.7423 g = 511 J, sulfur ccorteetion ry = 46025 We x 0.2043 g = 9403 J, combustion aid correction m 0.7423 g, mass of sample Baa [(10258 IC x 2.4170 °C) - 77.05 ~ S25 - 51.1 J — 9403 I] (0.7423 g; and‘ang snoqen 41g OOT ‘ OMPWAUT WISY ISUASH UeAen in. yas MO aeNap ut Ado> “WSN ‘SZPGT Vd ‘Usy204YOYsUOD 35% 4) sees - 13 Di = 20491 He X1.5.3 Heat of Combustion [ealeulated nitric acid method]: vag (91085) = [tL E) ~el ~ e238 ed] m E 102s 1c. 7 24lI0C NAF 1.62 Ad of released energy {from X1.5.1) el 1162 / 1000 x 10258 JMC x 24170°C = 40.2 J, nitrie acid correction 2 K, (Chromel C) x $4 mm wire consumed = 0.96 Jmin x $4 mim = 52 J, fuse correction 3 92.7 x 1.24 % § x 0.7423 w= 85.3 J, sulfur correetion ef 6025 Wg x 0.2043 g = 9403 J, combustion aid correction m = 0.7425 g, mass of sample is = {(10258 IPC x 2.4170 °C) - 40.2 5-524 — 85.3 J - 9403 4) 0.7423 g: and Oana = 20495 Hg 1X2. OXIDATION OF COAL AFTER SAMPLING X21 Gross Calorifie Value Stability of Coal X2.1.1 Table X21 illustrates the trend in the gross calorie value of twelve coal samples over a three and u half year time period. The results are dry basis values expressed in joules / gram, The proficiency test result for each sample represents the Consensus value from $5 to 120 laboratories. ‘The stability sudy was conducted in & single location on a single bottle of ‘each material over the time frame listed in the table. With the exception of the anthracite sample, the heating values cimin- ished anywhere from 250 to 950 J/g, The average monthly degradation is in the range of 6 to 23 J/g. The high end of this range is nine percent of the reproducibility limit of this Standard Test Method for bituminous coal X2.1.2 It is apparent from these results that the heating value of the majority of coals definitely decreases with time, From the time it leaves the mine, coal starts to degrade. All coals, other than anthracites, tend to be very sensitive 10 oxidation, Exposure to air at ambient temperature causes, "WSN ‘SZPGT Ve ‘u@yPOYOYsUOD 359M ‘91 i dy sees - 13, SUMMARY OF CHANGES. ‘Commitice DOS has identified the location of selected changes to this standard since the last issue (D5 that may impact the use of this standard. (Approved Oct, 1, 2013.) 1865-12) (2) Precision and Bias statement, Table S and Table 6 updated (2)Table A2.1 and Table A2.2 added to Annex A2. to reffect repeatability and reproducibility information for (3) Annex A2 revised to include data from RR:DO5-1025. Coke. (4) Section 12.6.3 revised for clarity. Committee DOS has identified the location of selected changes to this standard since the lust issue (5865-112) that may impact the use of this standard. (Approved Sept. 1, 2012.) (1) Revision to ALL2.1 (4) Revision of X14, (2) Addition of AL1.2.4, (5) Revision of 114.2. 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Conahchockan PA 19420-2969, LUntad Sins nfl roping ar mule copes) af Mis standard nay bo eblarws ty contacting ASTM atte abor> ‘adhinss or at BI-8G2-ISES iphone, 10882-9555 (ax, oF sence Dastmer feral): of iweugh the AST watehe ‘arawasim oy). Permesion ght pholexpy the stars rey alo be secured trom the Copyight Clearance Center 222 Fesewood Dive, Bumers, MA 1823. To (78) 46-2500 p.cpyigh cor (viivso) viNvsuaa vaaLHvras Isvuadom AMUN IeUOReUIAIUT WASV ISUESt] YemeG IP NSB YeIO IeNaIP JU Adod "ySN ‘SZHST Vd ‘UByDOYOYSUOD ISOM ‘anu InoqEH 44g OT ‘EUONEWIAIT WIS eIdP eH,