Thermal Analysis of Carbon Allotropes An Experiment for Advanced Undergraduates D.M. Crumpton, R. A. Laitinen, J. Smieja, and D. A. Cleary Gonzaga University, Spokane, WA 99258 ‘The recent plethora of articles on Cao both in the scien- tific literature and popular press (1) provides an opportu nity for the introduction of new undergraduate experi- ‘ments utilizing this interesting allotrope. Several articles ‘on C4p, have appeared in this Journal (2-7). This paper describes a laboratory experiment designed for upper divi- sion chemistry majors which compares the thermal stabil- ity of Ceo with that of graphite and diamond using thermo- gravimetric analysis (TGA), In addition, the reactivity of these three forms of carbon with oxygen is investigated, ‘This experiment ean serve as an introduction to the use of a thermogravimetrie analyzer or can be performed sub- ‘sequent to such an introduction.’ The graphite and dia- ‘mond (both powders) are purchased. The Coo ean either be purchased or isolated from soot. In addition to providing fan interesting vehicle for instruction in thermal analysis this experiment provides students with a rare opportunity to compare and contrast the empirical behavior of several allotropes of a given element. Experimental Section Powdered samples of graphite, diamond, and Coo were used. The graphite and diamond are available from Johnson Matthey, and Cso is available from Materials and Electrochemical Research (MER) Corporation, Tucson, AZ. ‘The graphite used in these experiments was carbon graph- ite powder, microcrystal grade, < 1 u, 99.9995% (Johnson Matthey stock no. 14739). ‘The diamond was carbon dia- ‘mond powder (natural), micron, 99.9% (Johnson Matthey Stock no, 13401). The Ceo was purified Cay 99.9% (MER produet code C60), Alternatively, Cao can be isolated from Soot (MER) using a Soxhlet extraction followed by column chromatography (8, 9). Several milligrams of sample were ‘used for each thermogravimetrie analysis. Two analyses ‘were made with each earbon allotrope: one in a nitrogen atmosphere and one in an oxygen atmosphere. ‘The TGA instrument used in our laboratory is a Perkin-Bl- ‘mer model TGA-7 thermogravimetric analyzer interfaced to ‘4 1020 series TA controler. We have found that a Statiemas- ter ionizing unit (NRD Inc,, model no. 2U500 available from VWR Scientific) is important when dealing with the pow- dored samples. The unit is used to discharge static electricity from sample containers, the glass envelope surrounding the ‘microbalance, and the balance pan itself. Following the procedure deseribed in the manufacturer's documentation, students performed thermogravimetric ‘analysis on the three allotrope samples, The thermograms executed in nitrogen are shown in Figure 1. Sample masses were typically 2-5 mg. The scan rate was 20 SCimin, and the range was 20-1000 °C. Using fresh sam- ples and the same experimental conditions, thermo- TA good inroducton to thormogiavimeiric analysis is provided by the dehydration of copper(i) sulfate pentanyarste. Copper sulata Pentanyerate, reshiy reerytalized fom water to insur ulation, provides an excelent sample fo stime TGAusers. At stow enough heating rates, one dlscovers that 2 waters come of, then 2 more, and finaly fe last one in a stopwise fashion. 590 Journal of Chemical Education gravimetzic analyses were repeated in oxygen, Figure 2 For an isothermal soak, a fresh sample was brought to a given temperature at a specified rate and then held there {or a predetermined length of time, followed by a rapid cool down, For the thermogram shown in Figure 3, the ramp up rate was 20 °Cimin, the isothermal soak was held for 744 h ‘at 750 °C, and the cool down was done ballisticaly. Discussion Graphite and diamond have similar behavior and will be discussed first. Comparing the nitrogen versus the oxygen ‘thermograms, essentially no mass loss was observed as a Function of temperature in a nitrogen atmosphere, yet all of the mass was lost in an oxygen atmosphere. The conelu- sion drawn by the students is that the graphite and diamond a 100 8 10 Weight % ee ar a Co) Temp. (°C) Figure 1. Thermogravimatic analysis (TGA) in nitrogen of (A) di ‘end powder, (B) grapite powder and (C) Cye powder. nal cases, ‘he esting rae wae 20 “Cimin. Tho esidue om Cy Was 12% of the orginal mass. 100 Xow z so 2 2 ra ° ‘200 400 ‘000 ‘a0 +1000, Temp. (°C) Figure 2. Thermogravimetic analysis (TGA) in oxygen of (A) ca ‘mand power, (3) graphite powdor, and (C) Cyp powaer In al cases, the heating rate was 20 "Cimin. All samples ha 100% weight loss ‘The order of stably (Cyp < damond < graphite) is consistent with jaublshed repos, s9e re 14.0 iy ze = 3 0 = ® 5 a 4 6 8 Time (hrs.) Figure 3. sothermal soak of Cy at 750°C. The xiginal sample nase ‘was 3.0™mg. The fl resiaue was 12% oft inl mass, were oxidized to carbon monoxide andior carbon dioxide when heated in an oxygen atmosphere, The gaseous oxides leave with the sample gas purge (Oz) and the mass remain- ing in the pan goos to zoro. The assumed reactions are Ca + Og) > COxy 206g) + O35)» 200) ‘The dramatic weight loss in the presence of oxygen al- losis students to ennelude that in the case of the nitrogen experiments (see below) no air leaks were present in the system. The stability of diamond and graphite at 1000 °C requires a vigorously anaerobie atmosphere. oo des not show the same thermal stability as graphite or diamond. The nitrogen thermogram (seo Fig. 1, trace C) Indieates that at temperatures greater than 775 °C weight. loss begins. From the behavior ofthe system with graphite and diamond in nitrogen traces B and A, respectively), the students know that air leaking into the system ia not re- sponsible for the weight loss. In addition, careful inspec tion ofthe thermogram reveals that the weightloss for Cop in nitrogen does not go to zero, Ifthe loss were dus to the presence of oxygen, the weight loss would go to zero as all Of the material would be converted to oxide gases. Indeed, the residue (approximately 12% of the original mass) ‘quickly disappeared when oxygen was introduced. In Figure 3, the weight lows of Cgo as a function of time at a constant temperature (750 °C) is shown. The same 12% residuo was observed for this isothermal experiment ssintherampd experiment Bure Tha eridon in both ‘assumed tobe graphitiedike earbon resu {Ee Demukdown of the Cin spheres The reside lak afar por pressure in a nitrogen atmosphere is consistent with the high temperature behavior of graphite. The volatile component responsible for the weight loss inthe Cap-nitro- {gen atmosphere TGA experiments was not analyzed. Te is Assumed tobe gas phase Cap andlor thermal decomposition products of Cp “Turning now to the oxygen thermograms, Figure 2, 0 see that all three allotropes were converted to gaseous ox ides at sufficiently high temperatures. Graphite is the ‘most resistant with Ceo being the least resistant, consis: tent with previously reported results (10). In analvaing this trend, students are challenged to consider the variety of possibilities that might individually or collectively ex plain this trend, For example, one must consider that ox dation ofa solid occurs at the surface. In the ease of dia. ‘mond or graphite, this surface will likely contain carbon-oxygen and possibly carbon-hydrogen bonds. renee, these samples are not pure carbon: a surface layer is present that may affect the temperature at which oxida tion begins, Alternatively, Co will possess the highest con- formational strain, and diamond will possess the highest percentage of dangling bonds. ‘The diamond thermogram (Fig. 2A) is particularly inter- esting because the rate uf oxidation changes abruptly at 770°C. This feature has been reported previously (11) Stuldents with some training in solid state chemistry who are familiar with Miller indices and crystal faces will ind it interesting that the rate of oxdation is face-dependent (12-13). The exact morphology of the erystallites in the powder sample will determine where (or even if a change In oxidation rate will be observed. "To complete the lab, students search the chemical ltera- ture to find references to thermal analysis of Coo, Alterna tively, some citations ean be provided in the laboratory handout. A number of investigators have examined the thermal and oxidation behavior of Cap (10,14-16), As is often the ease in materials analysis, the exact history of the Ceo sample appears to influence the results of thermal analysis. For example, the question of whether Cap chemi- sorbs oxygen at temperatures below eombustion (resulting ‘in a woight gain for the sample) has been addressed using TGA (24), Different investigators have drawn different conclusions. In our experiments, we abserved a slight in- erease (2-4%) in weight before the Ceo was converted 10 CO and 602, Conclusions In this laboratory experiment, students are introduced to the thermogravimotrie analysis technique. The samples uused were three allotropes of carbon: graphite, diamond, and Cap. Graphite and diamond behave qualitatively simi: lar and distinetly different from Coo, Hence, this Inbora- tory also serves as an introduction to some of the interest- ing properties of Ce. Students have the opportunity to ‘work with a material that has received an enormous amount of attention. Finally, this laboratory presents stu- dents with a unique opportunity to examine the physical and chemical properties of several different allotropes of the same element. ‘Acknowledgment ‘The authors gratefully acknowledge the support of the ‘National Science Foundation, Instrumentation and Labo- ratory Improvement Program (ILI Grant DUB-9350788), Literature ced copie scant 1 EEE cient ccm poe me inom 4, Je A; Gage Ft Che. Be. 1986, 65,7. Leer ee mcm ime trek hon ho 4 00 1m Samba Chai ean AJ Vl A MWh, MA Pg 1 aeons © Wee Aca D.C. a. el. 062,13, 12 eho, Cs Mang AC. Se Wd Mat Ra 1, 1S Bran Pua © re Cnt Caron 6 Ona Prk 1? tn 1 1 Sie Nah 5 Rr A vo 8 Caan 15 che 5, Ro Ss BC luna DA Pn. ho, 0 8 16 tat 1M ACS Pa Cho. 80, 35,028 Volume 73 Number6 June 1996591