g 5 ' MANUAL No. 154 ‘ Cm I XN I | | INSTRUCTIONS FOR THE 1451 SOLUTION CALORIMETER® tb eid beWY i = eww A MULTLPURPOSE CALORIMETER Utilizing @ unique rotating sample cell and a sensitive electronic thermometer, the Parr 1451 Solution Calorimeter provides a moderately priced and easily operated Instrument for measuring: + Heats of Reaction + Heats of Mixing » Heats of Solution > Heats of Dilution + Hoats of Wetting with a precision which is adequate for most analytical and exploratory research applications. Measurements are made at room temperature and atmospheric pressure in elther liquid-tiquid or liquid-solid systems covering energy changes ranging {rom 2 to 1000 calories. All operations are straightforward and simple, with temperature changes plotted on @ strip chart for easy interpretation and analysis. WITH MANY USES. Tere are many uso for iis convenient, Benchtop calorimeter: ‘As a teaching Instrument it has an Impoctant place in college and university laboratories for demonstrating and teaching the fundamentals of thermochemistry In a student laboratory, As an analytical tool it has many applications in Industrial laboratories for product evaluation and quality control. Such applications may extend beyond the range of pure calorimetry to include tests in any system in which there is a direct relationship between the heat of reaction and a chemical or physical property of one of the reactants, ‘AS a research instrument it offers a convenient and rapid means for oblaining vasic thermochemical data with a precision that will be adequate for most preliminary research and exploratory applications, “mi i FON MANY DIFFERENT REACTIONS Any liquid-liquid or tiquid-solid chemical reactions in which heat is evolved or absorbed at or near room temperature can be studied in the 1451 calorimeter. Hoats of reaction, either endothermic or exothermic, can be determined in many different systems, ranging from simple acid-base reactions to more complicated redox, chelation, hydrolysis, protonation and other reactions. The calorimeter is particularly effective for assays of weak acids and weak bases which do not respond readily to other detection methods, It can also used for rapid specific fon determinations by thermochemical methods, as best illustrated by the determination of sulfur using barium chloride to recipitate barium sulfate from a sulfate solution. The heat of solution produced when a solid dissolves in a liquid can be measured easily. Similarly, the calorimeter can be used to measure the heat of dilution produced by diluting a solution with a solvent or with a solution of lower concentration. It will also measure the heat of mixing produced when two liquids are combined The heat of wetting as measured with this calorimeter serves not only as a thermochemical measurement, but also as a rapid metfod for determining the surface area of a solid, since th heat released when a powdered solid is treated with a wetting agent will be proportional to the exposed surface area,iD » BHwUUUEH YY YY io www 2 2 2 3S ea 4 COMPACT, BENCH TOP INSTRUMENT ‘The Parr 1451 Solution Calorimeter consists of a glass Dewar reaction chamber with a rotating sample cell, thermistor probe and a specially designed temperature measuring bridge, all assembled in a compact cabinet. Temperature changes are piotted directly in Celsius degrees using an accessory strip chart recorder. All operations are straightforward and easily handled by any technician or student with minimal training EASY TO OPERATE The operation of this calorimeter is classically simple. At the start of a test, one liquid is held in a glass Dewar while the other reactant, either solid or liquid, is held in a sealed glass rolating cell which is immersed in the first liquid. The system comes to equilibrium quickly with only a slight temperature drift rom the heat of stirring and from any heat leak into or out of the calorimeter. After recording the initia! drift and without interrupting the rotation of the sample cell, the operator starts the reaction by depressing a push rod which drops the contents of the cell into the surrounding liquid. The reaction then proceeds to completion under the vigorous stirring action of the rotating cell Throughout the test, temperatures are sensed by a thermistor anc recorded on a strip chart. These dala can then be used to calculate the enthalpy change sroduced by the reaction by simply multiplying the observed temperature change by the known energy equivaient of the system. An instruction manual furnished with the calorimeter explains these steps in detail and describes suggested standardization procedures, A130C Sample Ceil with 126C Bottom Se Sellu os seeealsteuagllss PAB2 =) 2 2 > Fad = AN EFFECTIVE STATIC INSULATING JACKET Excellent thermal insulation is obtained in the 1451 calorimeter by conducting all reactions in @ fully silvered glass Dewar, 48 mm inside dia, x 103 mm deep. The Dewar is supported within a stainless steel air can trom which it is easily removed for filling or cleaning. A plastic foam block surrounds the air can, with the entice assembly mounted in a sturdy wooden case, 16 x 13x 14 inches high, waterproofed with a hard, bonded laminate nish THE ROTATING CELL A two-piece, closed glass bell with a detachable bottom hholds the solid or liquid sample and also serves as the stirrer for the liquid in the Dewar. The Teflon dish which forms the botlom of this cell fits snugly ia the glass bell without requiring a gasket or sealing ring. Solid samples (up to 2 grams) can be weighed directly into this dish before it is attached to the bell. Liquid samples (up to 20 ‘mi} can be added to the closed cell from a pipette inserted through the top stem. The glass rod which is used to open the cell to start the reaction is inserted from the top of the calorimeter through the stirring shalt and into a socket in the sample dish. When this rod is pushed downward, the dish slides out of the cell and remains attached to the rod, held at a fixed distance above the bottom of the reaction vessel. In this position the rod and dish rotate with the cell, stinging the reactants into the solution and serving as an additional impeller in the stirring system. Heat leak from the cell to the non-wetted parts of the system is held to a minimum by a low conductivity, thin- walled glass stem on the sample cell and a plastic coupling which fastens the cell to the stirring shaft. The call is easy to load, easy to clean and, if broken, it can be replaced at minimum expense since the sample dish and other parts are interchangeable. The dish itself is made of Teflon reinforced with glass fiber for excellent resistance to-most chemical agents and for good dimensional stability. THE STINRER DRIVE The stirring mechanism consists of an externally mounted elgctric motor with a drive bell which turns the stirring shaft at a constant speed (approx. 450 rpm) with no slippage and very tittle bearing friction. The hollow drive shait terminates at the underside of the calorimeter cover where it joins a low conductivity coupling on the end of, the sample cell, A UNIQUE TEMPERATURE MEASURING SYSTEM Temperature measurements in the 1451 calorimeter are made with a unique thermistor bridge system developed specifically for this application to provide direct temperature readout on a conventional sirip chart recorder. It has a resolution of 0.001* C over a working range from 20° to 30° C. The sensor for this system consists of a special thermistor network, sealed in a glass sheathed probe for maximum chemical resistance to ine reactants in the calorimeter. A fixed bushing on the probe stom ensures repeatable tip placement at the proper level. A similar probe in a rugged stainless steo! sheath is available for users who want to use this unique thermometer with a Parr 1341 calorimeter er in other laboratory applications. The bridge for this thermometer is installed as a unit in the calorimeter case, It is:designed to operate with any. strirgghart recorder having an internal impedance of 100 ‘ohms.or.more.and a:10 millivolt full-scalessensitivity. Full scale temperature ranges of 0.1, 4iQsand.10.0 degrees Celsius are.oblained by selting the recorder sensitivity to. 10, 100 and 1,000 millivolts, respectively.Base line temperatures'can be set at any appropriatetemperature: Top View 1451 Calorimeter using the digital decade switches and a 15-tum potentiometer an the bridge. Convenient switches and adjustment potentiometers are provided to zero, calibrate ‘and null the combined thermometer and recorder. It is also easy to shift, expand or magnify the temperature readout using the standard controls on the bridge and recorder. A recorder Is gt furnished with the calorimeter since many laboratories will already have a suitable recorder that can be used with this instrument. If the user does not have a recorder, a suitable unit can be purchased from a laboratory supply dealer. Parr does not manulacture or sell a recorder for these calorimeters. There are several important advantages offered by this graphical temperature measuring system: 1. Temperatures can be read directly from the strip chart with no cumbersome cross-over switching or manual temperature balances to be made during a run. ‘The user is therefore free to concentrate on the calorimetric determination and not on the thermometry 2. Differential temperature measurements can be resolved to +/— 0.001" C with excellent linearity and repeatability without a large investment in expensive temperature measuring instruments. 3, Graphical temperature recording permits easy identification of steady state or equllibrium conditions in the calorimeter. - 4, The nel temperature rise, corrected for any heat leak into or from the calorimeter, can be obtained directly from the thermogram by a Graphical method without mathematical calculations. Jase 7 alu dpa LaLAIUUR i ye awe PAlaupaglluoiasdlullsy aiuigypueducuiiluaugy PALSY dss fall? were fava) aout WAUSAU) | Viuinwinrastuicadiits, 9 : Uelasiwluusakais “Wyle taveet! ibb i ib webi 2 STANDARDIZATION Three different procedures are available for standardizing the calorimeter: (1) chemical standardization using a "Tris" sample which is furnished with the calorimeter, Pnecision ‘The precision obtainable with several scale ranges, characterized by one Ceviation from the mean and expressed as a per cent v' the measured enthalpy change, will be as follows. Typicat Full Seale Range Energy Deviation from millivolts temperature Release the Mean 10 G1C —Bcal~ less than 1.0% 160 10° 60 less than 0. 1000 100° 600 less than 0.4% STANDARD PARTS Each 1451 solution calorimeter consists of a complete Dewar reaction vessel with glass cell and sample dish, push rod, thermistor probe and thermometer bridge SD corparan stanaeaton using sarplea wi oem Gr sta sample cal wit Oh and 8D ty Chemical standardization is readily accomplished with _dettle of Parr standard “Tris” are furnished with each aS ee ere nr Tanicl rE} obtained trom Parr, or the basic reference material can be —_ without temperature recorder. way Biased op the Natons Bureau of Standards 3S Soci yotage, eter 118 y SED He or 200 SEO He ‘Comparison standardization involves the use of known Spare parts are available, including! 42 samples supplied by the user. By selecting samples rote eat wth coupling ess 126C bottom sihoveanttalpyahanges are krona whose ‘1900 Sample cel with eoupling 58 4 m__ermeneriga bores silat tho utrown Beal Ne camels canbe slontardced by sino 4286 Cal Bltom, Teton Tung duptiate tats wit leown ond unkrown runing pet 11296 Push 04 glass ee ee rte ee een eee probe, a uniform power supply, a high precision voltmeter and a precise interval timer. This equipment is not sold by 3421 “Parr, but most of the items can be obtained from 22 commercial sources, Tris (hydroxymathy) aminomethane, Parr standard for solution calorimeter, 59 gram bottleBost J 23 qi es 4 = BB a Bl a fl : Instructions for the PARR 1451 SOLUTION CALMURIM INTRODUCTION ‘The 1451 Solution Calorimeter describe in these instructions is an easily operated instrument which can br used to measure the heat evolved or absorbed by chemical reactions in a Liquid media. Measure ments are made at room temperature aud atmospheric pressure for systems producing energy changes ranuing from 2 to 1000 calories. At the start of a test in this calorimeter one liquid is held in a glass Dewar while the other reactant, either selid or-liquid, is held in a sealed glass rotating cell which is immersed in‘the first liquid. After both reactants come to ther nal equilibrium, the operator starts the reactiou by depressing a push rod to drop the contents of the cell into the surrounding liquid. ‘The reaction tten proceeds to completion under (he vigorous stirring action of the rolating cell. Throughout the test, temperatures in the calorimeter are sensed by a thermistor and read from a bridge which is built into tie calorimeter case. Deviations from the bridge reading are traced by « potentiometric strip chart recorder to produce a thermogram shoving the temperature change produced by the reaction. Data from the thermogram can then be used to compute the change in enthalpy. ‘The instructions given in this Manual cover the basic steps to be followed in: setting up and operating th: calorimeter; recording temperature changes; standardizing the calorimeter and computing energy values.5 B et ‘The unit of heat used in this Manual is ho thermochemical calorie, which js equal to 4. 1140 absolute joule Unpack the calorimeter carefully and check the individual parts against the packing list. MU shipping damage is liscovered, report it imnediate- ly to the delivering carrier. Handle the glass sample cell and the thermis- gle and easily broken. Set the tor prole with care as these parts are fr calorimeter on a bench or table in a lovation that is free from drafts and protected from souvees of radiant heal. ‘temperature changes in the room should be minimal, Attach the motor _to the rear of the calurimeter-case using the two mount- ings screws which are provided. Set the cover on the calorimeter air can; drop the geared drive belt over ihe motur and stirrer pulleys; connect the motor 9 a 115/ 120 volt, 50/60 Hz grounded outlet and start the motor. The drive system should cun freely. Atihough the bell may appear to be unusually loose, it is intended to operate under very light tension to minimize friction in the stirrer beariny, ‘The gearing on the belt and pulleys will prevent slippage. Turn the selector switch on the thermoiseter panel to the OFF position; then connect the power cord to a 115/120 Volt, 50/60 Hz grounded outlet. Plug the lead wire from the thermistor probe into the jack on the thermometer panel and lay the probe on the table nea the calorimeter, Handle the probe very carefully as the glass tip will bree! easily and, if broken, it cannot be repaired. Recorder Requirements. Instead of ren-ling temperatures directly from thess 2 8 eg 24 A a aa ee thermometer bridye with the aid of a-ull indicator, it will be best in most applications to operate tits enlorimeter with a potentiometric strip chart recorder to produce a theruogram showing the temperature changes which occurred during a run, The recorder to be used with this calorimeter should have an internal impedance of 100 ohms or of 10, 100 and 1000 millivolts more, and it should have plotting rau full.scale. Most laboratory recorders meet these requirements. Connect the recorder Lo the polarized lerminals at the top of the thermometer panel and plug the power cord from the recorder into a 115/120 volt, 50/60 Llz grounded outlri, Run a ground wire from the grounding terminal on the panel te a similiar terminal on the recorder. If there is no grounding terminal on (he recorder it may be necessary to connect the ground wire to the instrument case but, in doing so, do grounding is very important, not only as a safey measure, but also io ensure satisfactory thermometer not introduce a ground loop circuit. 9 and recorder performance. If there i: any question about the reliability of the ground connection through the power cord, run a separate wire from the grounding terminal on te calorimeter to a good earth ground. Before starting to use the caloriteter ov the first time it will be well run with the calorimele completely assembled but with no liquid inthe Dewar and no sample iu the rotating cell. This will give the user an opportunity to become familiar with the individual parts of the calorimeter and the manner in which they must be handled. De- tailed instructions are given in the operating sections which follow. 4j 4 q 4 j seh CALORIMETER OPERATIONS Sample Size. ‘The rotating sample cel! will hold up to 20 ml of Liquid samplo or a solid satnple weighing up lo one gram, More than one gram of solid may be used in some cases, but sinaller samples are preferred so that the heat capacity and ionic strength of the system will not change significantly when the reactants are mixed, ‘The Dewar must be filled with not less Uian 90 ml and not more than 120 ml of Liquid to properly cover the rotatin:: cell. Filli av. ibis best to Lift (hy Dewar out of the air can during the filling operation. Th liquid (o be placed in it can be measured volumetrically, or the Dewar can be placed on a solution or trip balance and filled by weight. After filling the Vewar, set it in the air can and gently push the spacer ring down as for as it will go. Loading a Solid Sample. Solid samples should be suitably ground so that they will dissolve quickly or mix uniformly with the liquid in the Dewar. Place-the 126C Teflon dish on an analytical balance and weigh the sample directly into the dish. Be careful not to drop any of the sample into the push red socket. After the final weighing, set the dish on a flat surface and carefully press the glass bell over the dish to assemble the cell, Do not grasp or pregs the thin-walled glass stem during this operation; it is fragile an’ will break-easily. Instead, grasp the bell and press it firmly onto the dish. ‘Then lift the cover from lite caiorimeter and attach the ec)I lo the stirring shaft by slid- ing the plastic coupling onto the shaft as far as it will go and turning the thumb screw finger tight. mud lower iL carefully until the Hold (he cover in a horizontal po bottom of the rotating cell rests on a fim, flat surface; then insert the= = oa an x ime push rod through the pulley hub and press the cud of the rod into the sockel in the 126C sample dish. Loading a Liquid Sample. Liquid sarples ean be measured into the rotating cell cither by volume or by weight. Best precision is obtained by weighing, but filling from_a volumetric pipet may be adequate in come cases, Sct the 126C ‘Teflon disl: on a flat surface and press the glass hell over the dish, handling the glass carefully as described above. If ti sample is to be weighe/, tare the empty cell on a lab- oratory balance; insert a pipel throuy! the glass stem and add the Liquid; then reweigh the cell, Attach the cel! to the stirring shaft and insert the push rod. Install ‘obe in the cover opening and press the bushing firmly into place to anchor the probe iu its proper position, Handle the cover carefully after installing tle probe since the glass stem will break easily. enibly with the ceil and thermistor probe into the Dewar and set the cover in place on tr: air can; then drop the drive belt over the pulleys and start the inotor, Combining the Reactants. Bach lest in a solution calorimeter can be divided into three distinct time period (1) @ preperiod during which the renctants are allowed to come to tuermal equilibrium; (2) a wreac- tion period during which the reactants are combined and an enthalpy change oceurs in the system; and (3) « postperiod during which the calorimeter again comes to equilibriu'n. At the end of the preperiod, start the reaction by pressing the pus! rod downward to drop the sample out of ihe rotating cell. This should b done quickly without interrupting Gthe rotation of the red without undve friction from the finger. Push the rod down as far as it will go; after which it should continue to rotate with the pulley. Let the stirrer continue to run during tue postperiod until a uniform slope is established, as explained later in these instruc- tions. AND RACONDER OPERATIONS THERMOMETE ‘The temperature measuring system in this calorimeter consists of a gned for use within the ten- thermistor probe and a special bridge tes degree span from 20° to 30° G, Within this range the response of the thermometer is lineal, with each 100 :1icrovoltschange in output repre- 01°C, Thus, when the out- senting a temperature change of exactly put signal is fed to a recorder and plotted on a 10, 100 or 1000 millivolt chart, temperatures can be read directly from the chart without apply- ing a conversion factor. ‘The followiny values will apply when equating changes in thermometer output to tempebetureschanges: 100 microvelts (U,00UL V) ROOICIGE a Oileavae 10 millivolts (W010 V) = = 100° 4 = det] &€ 100 millivolts (0.100 V) = 1, 000° 1000 millivolts (1,000 Vi = 10. 00° Once these basic relationships are wil-rstood the bridge can be balanced — y9.: to a.zero output at any baseline temperature from 20° to 30° C and a recording range can be selected to provluce a full-scale trace correspond- ing to a temperature change of 0,1°, 1.0? or 10°C, The true tempera- ture at any point on the chart can then be determined byadding the chart reading to the baseline setting shown hy the unit temperature switch and digital potentiometer located within the marked box on the thermometer panel,23 ge sep ce eo sue g ‘There sve five switch positions on the stleclor switch in the center o: the thermometer panel, the middle there of which have adjusting knobs. OFF ZBRO NULL CAL READ In the OFF position no power is supplied to the thermometer and the system is dead. ‘The switch should remain in this position whenever the calorimeter is nol in use. The ZERO control adjusts the oulpul of the bridge to zero voltage. fs the bridye to indicate a temperature of The NULL control adjus' exactly 20° C at zero voltage output. The CAL adjustment sets the full scale output of the bridge at exactly 1000 millivolts (1,000 V), corresponding to a temperature exactly 10° C ove the bridge pull. ‘The READ position is used to feed Lee Hermmomeler signal to the recorder. Calibrating the recorder, Most strip chart recorders can be set to produce a full scale trace with inputs of 19, 100 or 1000 millivolts, which cover the ranges yenerally used for the (461 Calorimeter. The recorder should have a chart speed selector and an adjustment for setting the pen toa zero baseline. Auy specific instructions furnished by the recorder manufovturer should be observed when using this equipment. After connecting the recorder to the thcrmnometer bridge, balance the bridge «and calibrate the recorder using the procedure described below. These cleps should be taken in sequence when using the recorder for the first time. It is not necessary to reper, these adjustments in each sub- gequent run, but the settings should be checked from time to time to be 8 Seen anette eae aei a Ma sure tliat they have not changed. 1, ‘Turn the recorder on and turn Lbe thermometer selector switeh to ZERO for a warm up period before making any adjustments. Although the thermometer will usually wari up in teu minutes, +edonger period up to thirty minutes may be required to reach maximum stability. 2. Start the chart drive at a speed of one inch per minute, Wee 2» 3. Move the recording pen to the oro baseline on the chart as in- structed by the recorder manufaciurer Set the range swilch on the recerder to 1000 millivolts (1,000 volt) full se In this position the full scale of the chart represents a span of 10° &, 5. With the thermometer selector switch in the ZERO position, use the ZERO adjustment on the thermomelor bridge to bring the pen back to its 2 2vo baseline. 6, ‘Turn the selector switch lo NUi.L and bring the pen to its zero baseline with the NULL. adjustment. ‘urn the selector switch to CAL, aud use the CAL adjustment to move the pen to its full scale position. 8 Now set the unit temperature switch and the digital potentiometer to read exactly 20.000°C and turn the selector switch to the READ position. ‘The pen will then move to a position on ihe chart indicating the temperature sensed hy the thermistor. Exampl- If the chart paper has 10 major units in its ruling and the recorder is set at 1000 millivolts (10. 00°) full sesle, each major unit on the chart represents 1°C. ‘Therefore a reading o 4.92 units on the chart indicates 9g on 29 2) ee oo oe = 5 a Se a a temperature of 24.52° C in the calorimeter (20° baseline + 4, 52° on the chart scale) Beller precision can now be oblained by changing the baseline set- ting and increasing the sensitivity of the recorder after it is known that the temperature being measured is near 24,52", Move the temperature setting on the bridge to exactly 24.0007, then change the range selector on the recorder to 100 millivolts (1.000%) full scale. If the pen then moves to 5,23 major divisions on the chart, the temperature in the calorimeter is 24,523° (24° basi 2 + 823° on the chart) Or, for best precision, set the temperature dials to exactly 24. 520° and change the range selector on the rcorder to 10 millivolts (0. 100°) full scale. Now use the recorder as o null indicator and adjust the digital potentiometer to bring the pen back to the zero paseline. If the digital meter then reads . 625, the temperature in the calorimeter is 24, 525° C. PRODUCING ‘Ihe THERMOGRAM. Choosi ge run, try to estimate the total the Range. Before star energy change involved in the experiment so that the recorder can be set in a range which will produce the best (hermogram, The following set- tings are recommended: Up to 10 calories, set at 0.01 V (0. 100°) full scale. 10 to 100 calories, set al 0.10 V (1. 000°) full scale. 100 to 1000 calories, set at 1.00 V (10, 00°) full scale. If the sign and magnitude of the enthalyy change cannot be estimated before starting an experiment, set the recorcrr at 0.1 V (1, 000°) full scale and in the middle of the chart. The make a trial run starting with a baseli: temperuture change observed in this e:periment can then be used as aguide for setting the recorder to a dificvent renge and baseline te produce a better thermogram in a subsequent rio. Resetting the Pen. If the reaction lo he examined is expected to be endotliermie, the pen must be raised ly a higher position in order to record a temperature drop during the /eaction, To raise the pen, simply turn the unit temperature switch or thy: digital potentiometer to a lower setting. ‘This change can be made at ay lime without affecting the range j and calibration of the recorder. { In exothermic experiments, a baseline adjustment may be desirable at this time if the temperature in the calvrimeter has changed significantly during the initial equilibration period. Beginning the ‘tra ‘Phe ‘liquid 4w'the Dewar and the sample in the rotating cell must reach thermal equil brium, and the recorder must trace a straight line for at least ‘| or“eminutes before starting the re- action, To minimize this equilibration period, the reactants should be i at approximately the same temperaturs when they are placed in the calori- , meter. This is particularly importan! when working with reactions which produce low enthalpy changes. In such cases any temperature difference between the two solutions in a Liquid-li system should not exceed 0, 2° when the calorimeter is loaded. ‘The culorimeter should then be allowed to run for about 15 minutes before starting the trace. Solid-liquid systems will usually come to equilibrium within a shorter period. a St Completing the Jeace. Having established the initial drift, start the reaction by depressing the push rod to pen the rotating cell, This will Soel produce a distinct temperature change hich will soon taper off to a uni- form drift as the calorimeter again cores to equilibrium, . Continue the trace until the drift line becomes straiyht and remains straight for at canoe et easei wea pace i a S g 5 Jeast three minutes. Usually this coudition will be reached within ten minutes or less aller slartinys the reaction, At the conclusion of the test, stop the recorder; Lift the pen and turn the thermometer selector switch to ZERO. Remove the chart from the re- corder and mark it to identify the run gud the reactants involved. Also, write in the baseline temperature and show the recorder range setting for this run. Emptying the Calorimeter. Stop the cilorimeter motor; raise the cover carefully and wipe any excess liquid from the parts that were immersed inthe Dewar. Remove the thermistor probe from the cover and remove the sample dish from the end of the push rod; then remove the rod and release the glass cell from the drive shalt. Lift the Dewar out of the air can aud empty it; then wash aud dvy all wetled parts ‘carefully. JOGRAM In order to determine the net temperature change produced by the reaction it is necessary to locate a point on the (hermogram at which the temper- ture reached 63 per cent of its total rise (or fall). ‘This can be done easily using the graphic procedure which is described below, although other variations of this method can be used as well. 1. Viace a straight edge over the preperiod drift line and extend this line well past the point at which the cel! was opened to start the reaction. 2. Move the straight edge to the pesilperiod drift line and extrapolate this Line backward to the time when the cell was opened. If there are fluctuations in the drift lines due to noise or other variations in the signal, use the hest average when drawing these extrapolations.Sg Seed Sreeeereerenee eee er eee 2 { 3. Using a centimeter scale, mene the vertical distance, R, between the two extrapolated lines al a seint near the middle of the reaction period. 4. Multiply the distance, R, by 0.4, then 5. Set the zero end of the centimeter seale on the extrapolated preperiod drift line and move (ie svale along this line to locate a verti intercept with the thermogram which is exactly 0. 63R above the preperiod drift line. Draw a vertical line through this point lo intercept both drift lines. 6. Read the initial temperature, ‘I, , and the final temperature, Ty, at the points of intersection with the drift lines and subtract to determine the corrected temperature rise, AT, : AT, Althougi the thermogram shown on pag? 14 to illustrate this graphic method is taken from an exothermic reaction, the same steps can be used to estalilish the corrected Lemperoture change for an endothermic reaction. If it was necessary to resct the pen during the lest, the graphic procedure can still be used by taking into account tle two different baseline tempera- tures when reading the intercepts. Iowever, in such cases it usually will be desirable to re-run the experiment using a different baseline or a higher span on the recorder to produ-e an unbroken thermogram.asyy eanyeradura, SIL eee TUOLVULIMLS, \ \ALCULATID CHANGE change, Q, measured in ibis calorimeter is calculated by multiplying the net corrected temperature change, AT, by the energy equivalent, e, of the calorimeter and its contents. Q =. CAT Me) If AT, is measured in degrees C and o is expressed in calories per degree C, Q will be reported in calories. The-energy equivalent, c, is determine:t by a calibration procedure which is described below under Stendas dization. .n reaction température is equal ‘The change in enthalpy, AH, at the m | + to -@ divided by the amount of sample "sed in the experiment, expressed either in moles or grams. Le tM | Atty apm where ‘I is the temperature at the 0. 6 point on the thermogram. Enthalpy values are usually expressed iu kilocalories per mole, Pro~ 3 i cedures for converting enthalpy change, AI, to thermodynamic stand- 4 ard conditions and for using AH in otler computations can be obtained i 4 from thermodynainics or thermochemislry textbooks, or from literature references. A SVANDARDIZING ‘THE CALORIMETER | a As explained above, in order to calcul.:te the energy change, Q, involved in A reaction, the energy equivalent, ¢, of the calorimeter and its con- tents must be Inown. Values of ¢ are determined by running several a < _scoasscsmeeensue ss saan eo aNBes woe ES He“ eee a calibration experiteents in which the calorimeter is operated in the usual manner but wilh reactants which #elease (ov absgrb) a known amount of eneryy. ‘The energy equivalvut is then calculated by dividing the known energy input, Q y+ -by-the corrected temperature rise, AT, - 2 = Qf e Qf AT, Standard A sample of Lris(hydroxymetiyl)aminomethane, tion with TR ed TRIS, is furnished with the 1451 calorimeter to provide commouly ¢: a reliable standardizing reagent. ‘THI! is furnished as a dry powder which can be used directly from the bottle as supplied without further preparation, but undue exposure to air and moisture should be avoided in order to pre- serve the integrity of the standard. . solid TRIS can be dissolved in For standardizing the 1451 catorime' dilute hydrochloric acid in a controlled reaction’for which the amount of heat evolved is well established, Jule: recommended standardization procedure described below, 0.5 gram vf TRIS is dissolved in 100 ml of 0.1 N IICL to evolve 56. 748-calories per yeam of THIS al 25°C. This is the procedure 1, ‘fare the Dewar on a solution or trip balance and add exactly 100.00 + .05 grams of 0.100 N IC. 2. Weigh 0.50 £ 01 gram of ‘IRIS into the 126C Teflon dish on an of = 0001 g. analytical balance to an accuracy it in the calorimeter and start 3. Assemble the rotating cell; pla the motor. 4, Let the calorimeter come to equilibrium; then set the recorder at 0.10V (1. 000° C) full scale; set the baseline at the bottom of the chart for an exothermic reaction and trace « thermogram as previously described. 16| } \ é to determine net corrected temp~ Analy: the Lhermograr erature rise, AT. 6. Calculate te know! put by substituting in the equation: 28 60. 34838(25 -'P +63R where, 2 the energy input in calories the weight of TRIS in grams = the lemperature at the 0, 63R peint on the thermogrant e temperature, 7. Caleulate the enery gy equivalent of the cakorimeter and its contents by substituting in the equation e + Gf AT, where ¢ will be expressed in calories per °C. 8, Determine the et f the empty calorimeter by sub- tracting the heat capacity of the 100 g of 0.1 N HCl from e, as follows: et =e (100. 00)(. § 9294) where, ec! = the energy equivalent of the empty calorimeter in calories per °C. 100. 00 lhe weight of 0. 100 N HCL in grams .99894 = the specific heat of 0.1 N HCl at 25° C xample A standardization reaction involving: 0.5017 grams of TRIS, and 100, 00 grams of 0.100 N TICL