Properties of Materials and Systems of Importance to Environmental Fates and Remediation. Ill. Review of Previous Thermodynamic Property Values for Chromium and Some of its Compounds Duane R. Kirkin” Physical and Chemical Properties Divvion, National Insiut af Standard and Technology, Goithershurg, Maryland 70800 Recsved February 4 1999; Sal vevision received Apel 28,199) Tweu seven (27) crystalline and aguevus chro species from the NBS Tables of ‘Chemical Thermodynamic Properties were selected based upon their possible importance to environmental fate and remediation processes. Their NBS files were studied to deter- ‘mine the sources of information and the methodology used to determine the NBS selected thermodynamic values. The NBS tables for chromium were compiled in 1966. A litera- ture search was performed to determine the existence of additional data for these species. ‘Documentary data are presented for the thermodynamic properties of these twenty-seven (27) species. {50047-2689(99)00205-6) © 1999 American Institute of Physics and American Chemical Society. Any word: aqueo hin chemin Semidymanin propenon Contents 1. Introduction. 1675 1.1. Environmental Considerations of Chromium. 1676 12. Uncertainty Considerations. 1676 1.3. Acknowledgments. .......+++ 1678 14, References for the Introduction, 1678 2. Crfer) 1579 3 ce*(ag. : 1679 4, [Cr(HLO)20KJ-mol~!, This type of treatment overestimates the un- certain, Consider the SSGAT/KIN reaction: [CrC1,(H,0),]Claq)=[CrCK(H,0)s]Ch(aq). (5) The uncertainty in the enthalpy of formation of CYC, (HO) _\Clag) could be calculated as the propagation ‘ofthe uncertainties of all the preceding reactions that were combined to lead to its value. Call this uncertainty iy and fecophiaw that ila vals would U2 pica thaw 10 MPa ‘The uncertainty in AH, for [CrCIH,O)sIC,(aq) would be the propagation of up and the uncertainty in the enthalpy for reaction (5). given by S8GAT/KIN as 1 kI-mol”'. Therefore the tabulated enthalpies of formation would have tabulated ‘uncertainties of up and (j++ 1 KF-mol"?)"*, Now, consider if one takes tabulated values forthe enthalpies of formation and attempts to calculate the enthalpy of reaction (5) and its ‘uncertainty. Then the calculated uncertainty would be (21 +1kJ-mol~))”, of approximately 144. Thus, the caleu- tated wonetainy it reaction (3) would Ye gteter dia 14 ‘KJ-mol”', which is not the correct value; its correct value is ‘only 1 kJ-mol~', The end result then is that the wrong un- certainty, wrong hy at least an onder of mapnitnde, was ale calated Whether tabulated uncertainties for thermodynamic val tes. where the thermavtynenin volar tone hte i 8 sequential analysis, result in correct calculated uncertainties for a reaction depend upon how much of the sequential analysis isnot in common fr the substances involved in the reaction. In other words, the calculated uncertainty will be correct only if the sequential pathway for all members ofthe Phys Cem et Dats, VOL 2, 90.8, 1 DUANE R. KIRKLIN reaction have no preceding reactions in common with each other. S2WAG/EVA cautions that calculation of uncertainty is the squate oot of the sum of the squaics of the individual uncertainties will lead to gross overestimates of the uncertainty ofthe value forthe given reaction. (One of da ne nypuntat cider or prediction of chromium migration through the environment is the redve- tion of Cx(vt) to Cx(tm) in aqueous solution. Al ofthe en- Alalpy of fonmaion sad cxteopy selacs for apeons enon. ions of Cr(vi) depend on calorimetric measurements reported by Muldrow and Hepler (S7MULIHEP). One of the calri- metrically studied reactions was: C40j(ce) +201 (aq)=CrOF (aq) +H,0(aq). (6) STMULIHEP reported that the enthalpy of reaction (6) was ([t1sazu.9) mol" suosequent to tac measurement, ‘Hepler and coauthors (76DEL/HEP) reported that measure- ment of the enthalpy of reaction (6) gave (—1209 0.8) kJ-mol“!, These two measurements from the same laboratory, but performed with different calorimeters, differ by 38 kJ-mol”!. This difference is much more than the claimed uncertainties. Is certainly reasonable to expect that the difference reflects calorimetric biases of one or both of Hepler’s studies. If not, then the preparation of materials andor the nature of reactions are in doubt in one ofthe other fticle, There 18 no @ prion! ceason to expect that the 38 ‘kJ-mol™! must be a relative error, ie., a percentage of the measured enthalpy. Ifthe earlier calorimetric results from [STIMULATED ee in eror, then thowe calories cor pt {nto doubt all of the enthalpies of rection in that study. Errors in those enthalpies of reaction would directly translate into erors of unknown amounts inthe tabulated enthalpies ‘of formation and entropies of CxO} (aq), CrOz (aq), HCIO; (ag), K,Ce0,(ct), as well as several other sub- stances. 1.3. Acknowledgments “The author wishes to recognize the effons of Rhoda Levin and Tamar Thome in the collection of many of the literature articles and some of the formatting for this article. The au- thor especially wants to thank De. Donald G. Archer for his ‘many suggestions and encouragements during the prepara- tion ofthis article 1.4, References for the Introduction 1882THO Thomsen, J., Thermochemische Untersuchun- en von Julius Thomsen QJ. Bails Vetlag, Leipzig, 1882-1886). 1886REC — Recoura, A., Compt. Rend. 102, 865 (1886). TONRECA Revers, A, Compe Rond 1105, 1000-1037 (1890) 1890RECb —Recoura, A., Compt. Rend, 110, 1193-1196 (1890). 1889PET Petersen, E., Z. Physik. Chem, 4, 384-412 (1889).PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT S4MAH Mah, A.D... Am, Chem. Soc. 76, 3363 (1954). STMULIHEP Muldrow, O. N., Hepler, L. GJ. Au Soe. 79, 4095 (1957). STNEU/MAR Neugebauer, C. A., Margrave, JL. J. Phys. ‘Chem. 61, 1429 (1957). S8GATIKIN: Gates, H. S., King, E.L., J. Am. Chem. Soc. 80, 5011 (1958). Hepler, L. G., J. Am. Chem. Soc. 80, 6181 (2958). 68WAGIEVA Wagman, D. D., Evans, W. H., Parker, V. B., Hialow, L, Bailey, S. M., Schumm, R. H., Natl. Bur, Stand. (U.S,) Tech. Note 270-3, (1968). 6®WAGIEVA Wagman, D. D., Evans, W. H., Parker, V. B., alow, Tx Bailey, 8. May Schumm, Te Hy Natl. Bur, Stand. (U'S.) Tech. Note 270-4 (1969). ‘T6DELMEP Dellien. I. Hepler. L. G.. Can. J. Chem. 54. 1383 (1976), S2WAGIEVA Wagman, D. D., Evans, W. HL, Parker, V. B., Schumm, R. H., Halow, 1, Bailey, S. M., ‘Chumey, K.'L,, Nuttall, RL. J. Phys. Chem, Ref. Data 11, (2) (1982). SBSLOIKRI Slobodov, A. A., Kritski, A. V., Zarembo, V. 1, Puchkov, L. V., Russ. J. Appl. Chem. 66, 39 (1993) [Translated from Zhurnal Priklad- ‘noi Khimii 66, 47 (1993)] 9SBALINOR Ball J. W... Nordstrom. D. K.. J. Chem. Eng. Data 43, 895 (1998). Chem, S8HEP 2. Cr(cr) A. Selected Values, NBS Tables ‘The NBS tables have selected values for three (3) thermo- dynamic properties of the crystalline chromium metal. The thermodynamic functions and their selected values are: (298.15) ~H,(0_K):4.058 KI-mol™ (0.970 keal-mol™!) $4298.15 ):23.77 J-K-Imol (5.68 cal-mol“-K™) 5_.(298.15 K):28.35 J-K~!mol“! (5.58 cal-mol KY, ‘The actual data used was from 37ND, which reported mea- surements of C;,», from 56 to 291 K. B. Comments on NBS Selected Values NBS values selected were the same values selected by 6SHUL/ORR. However, 73HULIDES, which is an update of 63HULORR, uses 5.65 cal-mol-'-K™ for S, while in 1963, they used 5.68 cal-mol~'-K™, The original compilation of | chromium data was from 61KEL/KIN. 1679 C. Auxiliary Values Required for Data Pathway Nome D. Other Thermodynamic Measurements Consi None. E. Additional Determinations of the ‘Thermodynamic Properties SSWOL measured the low temperature heat capacity of ‘chromium from 1.20 to 20 K. OUBEA/LHI measured the neat capacity on a 1.990% pure sample of chromium from 268 to 324 K. ‘73HULIDES contains a bibliography that includes some ‘more recent papers and lists tne authors trom whom the cat- Tier data were selected. TOWILIGOP measured the heat capacity of chromium above ZANIMa0N) K. F. Bibliography 3TAND Anderson C. T., J. Am. Chem, Soe. 59, 488 (1937). SSWOL __Woleott, N. M., Proceedings Conference on Physics Des Basses Temperature, Institute In- ternationale Froid, 1995, pp. 286-289, GOBEA/CHI Beaumont, R. H., Chiara, H., Morrison, J A., Philos, Mag. 8, 188 (1960). 6IKELKIN Kelley, K. K., King, B. G., U.S, Bur. Mines Bull. 592, 149pp. (1961). OSHULIORK: Hultgren, KR. Ort, R.L., Anderson, P. D., Kelley, K. K., Selected Values of Thermady- namic Properties of Metals and Alloys (Wiley, Now York, 1969). Holtgren, R.R., Desai P. D, Hawkins, D.T., Geiser, M., Kelley, K. K., Wagman, D. D., Selected Values af the Thermodynamic Prop erties of the Elements (American Society of Metals, Metals Park, OH, 1973). Williams, 1. S., Gopal, ES. R., Street, RJ Phys. F9, 431 (1979). ‘73HULIDES OWILIGOP 3. Cr*(aq) A. Selected Values, NBS Tables "The NBS tables have selected values for only one (1) ther modynamic property of the aqueous chromium (u) ion. The thermodynamic function and its selected value is: Ajfy( 298.15 K).-143.5 R-mol* (—343 heals” "The NBS selected value was calculated as 4. Phys, Chom. Ret. Data, Vol 28, No.6, 19091680 AyH, (CP*, 9) = A ply C1Cly ay) —2 AH (CI™, 24) = [(-477.8 Ki-mol™!) 2X (— 167.159 KI-mol“")] = 1495 Kb-mol"- 34.3 keal- mot), from the data of I886REC based on reaction (1): CxCIyfaq)=Cr "(aq +21 (aq). 0) B. Comments on NBS Selected Values The NBS selected value was derived with the ‘AHf,(CrCly.aq) which appears to have a transcription esror of $4.6 KF mol”? (41.1 keal mol”). The AyHi,(CrCl,,8q), value should have been —473.2 K-mol! (—113.1 ‘Keal:mol™!) and not the —477.8 ki-mol™! (114.2 ‘keal-mol—") used in the 1966 calculations. Therefore, Ayta(C2*ag)=—1389 K-mol-* (-332. heal) stould have been the calculated valve. . Auxiliary Values Required for Data Pathway A fl{C=C 99) AH a9) D. Other Thermodynamic Measurements Considered S3GRE/BUR measured the Aff, of CrCl (er)=~77.8 KF -mol>(—18.6 keal-mot™”) ‘The AyH,(CrCl;,aq) would be equal to ~475.0 kI-mol! that would Tead 10 a Ayffy(Ce* aq)=— 140-7 KI-mol“! (390 xea-mor"), E. Additional Determinations of the ‘Thermodynamic Properties TIGRUIRRE made electromotive force (EME) meacine- sents of CP"ICe* potentials in sulfate solutions at 19°C. ‘Their standard potential for C"/CE™ reaction was ~0:612 Vs F. Bibliography I886REC___Recoura, A., Compt. Rend. 102, 865 (1886). 27GRU/BRE Grube, G., Breitinger, G., Z. Electrochem. 33, 112 (1927), SIGRE/BUR Gregory, N. W., Burton, T. MJ. Am. Chem. Soe. 73, 6053 (1953). 3. Phys. Chem, Ret, Data, Vol 28, No.6, 1998 DUANE R. KIRKLIN 4. [Cr(H,0).}**(aq,violet) A. Selected Values, NBS Tables ‘The NBS tables have a selected value fr only one (1) thermodynamic property of the aqucous chroniam. (0) exanydte fon, Te temodynae Rion and is 3 lected vale is (298,15 K):—1999.1 S-mol (—477.8keal-mol) Nine enthalpies of formation, AyH',, were considered during the seletion of the NBS selected value. The enthal- ‘ics of formation of five aqueous compounds and the cathal- pies of formation of the accompanying anions were used to caleulate an enthalpy of formation for the aqueous chromium (an) hexahydrate ion. The sulfate, chloride, bromide, fluoride. and the monohydrogen difluoride compounds produced AyHf,=[(~ 1994.9) — 1999.74),(~ 1998.49),(— 19903), (15987) kd-mol~"}; [(-476.8), (477.95), (477.5). (4157), and (=472.7) keal-mol"], respectively, for the aqueous chromium (it) hexahydate in, SEGATIKIN presented data for the AjgHfy=27.6 Ad-mol” (6.6 keal-mol™) for the following reaction: CxO} (ag)+ CI (aq) =CHCHO)SCP*(aq)+440, (0) which yielded a A pH, (Cr(H;0)g* ,9q)= — 2006.2 KI-mol" (41955 keal-mot) S8SCHIKIN presented data for the Mra = =4531 K-mol! (—10.83 keal-mol™) for the following reaction: CHLOE oH) CHB O00) +3CI(69). which yielded « A #,(Cr(H,0)3" 29) ($4722 keal-mot).” 4TEVA presented data forthe Ayalf’, =~ 146.63 kJ-mol™! (~178.45 kcal-mol~') for the follow- ing reaction: 1,0} Hore?" +1481" =2Ce*+6Fe!*+7H,0, @) 1996.6kI-mol™ which yielded a A#',(CP*,aq) which when combined with the ApH, of 6 moles of HO. 1 yield a AyH,(CH{H,0)3* aq)=— 1953.9 kI-mol(—467.0 ‘kcal-mol”'), 49EVA presented data ~ for the Brag =—740.99 kJ-mol! (—177.10 keal-mot™') for the same reaction in 47EVA that. yielded a A/#(CP".aq) = 7243.6 kI-mol~* (—38.7 keal-mot~'). When six (0) AsT(H,0.)= ~285.83 Ki-mol™! (~68315 keal-mol”) are" added to this value, they obtained 4 MglEH(H,0)3" a) =~ 1060.6 Wiemat A686 keal-mol™” ‘The average of these eight (49EVA was a correction for the 47EVA value) values is —1993.2 KJ-mol ' (-4764 keal-mol~’). However, the NBS selected value is ~ 1999.1 KJ-mol™! (~477.8 keal- mol)PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT B. Comments on NBS Selected Values In the consideration of values wsod to decide the NBS selected value, the NBS evaluators considered measurements ‘of 47BVA and 49EVA that dealt with the aqueous Cr’* ion and not the hexahydrated Cr°* ion. 49EVA was a recalcula- tion of the 4TEVA results and thus should be considered as ‘only one value. The NBS sheet showed the addition of six AyH(H2O1) to the ApHf(CP*.aq) to yield the hexahy- , and (NHY),Cr,0, and aqueous CrO;~ and Cr,0} were caleu- lated’ to be’ ~1388.7, -2035.1, “17782, ~868.6, and 1444.3 Kl-mol! respectively. Using the literature Ky and entropy data they calculated the entropies of the aqucous ebm and bletrortae ons to BE 293.0 and 200.0 J-mol”"-K"", respectively. The A/G, of the aqueous chro- tate, dichromate, and bichromate Were calculated 10 be 1117, ~1260.4, and —748.9 1mot, respectively In many of the following studies, AH, of aqueous C10, was measured and the AjHy(CiO, 89) was cal Jnted by eubtnetion of two. AyMy(K tag), 252.98, Ki-mol!, 40PER measured enthalpies of solution of K,CiO, from which @ Ay2fq of aqueous KyCrOy wa0 calculated to be 1385.0 Km Using he fa), oe oie 2 value for AEf(CrO,aq)=~ 880.24 kS-mol™!. 1876MAR measured enthalpica of solution of K,CiO, from which Af, of aqueous K,CrO, was calulated to be = 1383.6 KF -mot Using the AH (K*, aq), one obtains @ value for AyH(CeOR” aq)= — RIA RT-m S6YATIVAS measured enthalpies of solution of K,C1O, in aqueous H;S0, from which a Ay of aqueous K;C10, J. Phys. Chom. Ref. Data, Vol 28, No. 6 19861684 was calculated to be 13854 Ku-mol"! Using the AyHg(K?, ag), one obtains a value for AjH(CrO% aq) Ss0.6iu-mol STTER measured enthalpies of solution of K:CO, from which a A/if, of aqueous K;CiO, was calculated to be 1387.1 Kimo. Using the Affq(K",aq, one obtains value for Aj#(CrO}” ,aq)=—880:340- mol" 34KOLIGUS measured enthalpies of solution of KjCiOy from which aA 2, of aqueous KyCrO, was calculated to be 13848 Kimo!" Using the Aytf(K*, ag), one obtains a value for AH (CrO%" aq)= —880,0F- mol"! 1878MOR measured the enthalpy of formation of aqueous K,C10, by the reaction of aqueous CrO, and KOH. The A/H, of aqueous K,CrO, was calculated to be ~13836 AF-mOI*, Using me Ayia), one obtams a value for Aylly( CoO} ,9)= = 878 KF -01!, 28ROTISCH measured enthalpies of solution of KjCO, ‘om wnieh af, of aqueous KyLsO, was calculated to be 1385.2 mol" Using the A, f(K*, ag), one obtains 2 value for A,H,(CrO}” aq) = — 880.4 kJ-mol”* OUIKIVPRA measured emf data on AgyC'O, at 35 They had an emi=~ 0.4468, 37SMUPIT measured heat capacity, entropy, and fre en- ‘eray of formation for Ag,CiO, fom’ which S° =43.91-K"!-mol™! was calculated for C102 E. Additional Determinations of the ‘Thermodynamic Properties TSOHABOE measured the AyeiHy of C2jCtO, and re- computed and tabulated the thermodynamic data for the for- mation of the other alkali metal chromates. These thermo- chemical data were combined with solubility and equilibrium data to recalculate the thermodynamic properties ofthe aque- ‘us chromate, bichromate, and dichromate ions. The Aji, of the chromate ion was taken from SSHEP. The following values were selected: Ayttad Coreg) 577421 ~882532188 —7314 HOO) 1950275 = B7R6H29—~7684 GO} Gy AEBS —14920263 13088242 F. Bibliography 1876MAR —Marignac, C., Ann. Chim. Phys. 8, 410 1876). 1S7SMOR —_Morges, F., Compt. Rend. 86, 1443 (1878). I886SAB Sabatier, P, Comp. Rend. 103, 267 (1886) 2SROTISCH Roth, W. A, Schwarz, 0, Ber. 61B, 1539 1028). YROLIGUS Kolosovskit, N, Gushkun, B. Vi, Zh. Ob- schchei Khim, 4, 1289 (1934). J. Phys. Chem. Ret. Data, Vol. 2, No. 6, 1999 DUANE R. KIRKLIN 37SMUPIT Smith, W. V., Pitzer, K.S., Latimer, W.M.,J. ‘Am. Chem, Soc. 59, 2642 (1937). 40PER ——_Perreu, J., Compt. Rend. 211, 136 (1940) S4PAN Pan, K,, J. Chin. Chem. Soc. Taiwan 4, 1 (1954), SOYAT/VAS Yatsimicskii, K. B., Vasil'eviy V. Nu Zi Neorg. Khim 1, 984 (1956). STMULIHEP Muldrow, C. N., Hepler, I G., J. Am, Chem. Soe. 79, 4nd§ (1957) STTER Terasaki, Y., Nippon Kagaku Zasshi 78, 1774 (1957). SSHEP Hepler, L. G., J. Am. Chem. Soc. 80, 6181 (1958). 6OENIPRA Jena, P. K., Prasad, B., J. Indian Chem. Soc. 37, 634 (1960). TSOHAMUE U' tare, F. A. U., BoeTo, 1, J. Chem. ‘Mher- modyn. 7, 1195 (1975). 6. HCr0; (aq) A. Selected Values. NBS Tables ‘The NBS tables have selected values for three (3) thermo- dynamic properties of the hydrogen chromate ion, bichro- ‘mate ion, The thermodynamic functions and theit selected values ae: A/H(298.15.K):—878.2 Ki-mol™'—(209.9 keal-mol™) B,G5(298.15 K):—7648 KS-mol”'=(182.8 keal-mol~*) (298.15 K):184.1 J-mot'K (44.0 cal-mol™'). Enthalpies of reaction were calculated for three (3) reac- tions containing the bichromate ion in SSHEP using experi- ‘mental enthalpies of reaction determined in STMUL/HEP ‘and equilibrium constants determined in S3TON/KIN. Three standard molar enthalpies of formation, AH, were caleu- lated using these three equations: KC, 0,(e}+11,00 yap, = 86.6 KS-mol™' (20.7 keal-mol™ (NH,)2Cr,0,(cr)+H,0()=2NH; +2HCr0,, Spentlg= 69.9 KI-mol™ (16.7 keal-mol~), (2) K,C1O4or)+H*=2K*428Cr0; yoy = 20.9 KI-mol™ (5.0 keal-mol (3) The enthalpy of formation values of ~2061.9, ~140333, and ~1806.7 KJ-mol™' (492.8, —335.4, and -431.8 kkeal-mol”') for KCr,0,(cr), _K,CrO,(er), and (NHJCUs le), respectively, were sed to calculate the en- thalpy of formation ofthe bichromate fon from these reac- tions. The tree values calculated, 878.18, 878.1, and 877.64 ki-mol™! (—209.89, 210.04, and 209.76 keal-mol~') were averaged to yield the selected value of 878.2 kJ-mol™! (209.9 kcal-mol” 2K*+2HCO; woPROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT [A five energy of dissociation was calculated for the Vihromate ion ia SBHEP, C10; (aq)=CrOF (oq) +H1"(0a) sang A107 eLemal! (RE Kealmal). (4) ‘This value was used with the standard molar free energy of formation of the chromate ion, —727.85 kJ-mol' (~173.96 eat'uct™}), to ealoulte th standard malar five energy of formation of the bichromate ion, HCrO;, equal to -764.8 W-mol! (1828 keal-mol”. AGe—Aylly—TAS, wos used, to calculate AS; 380.28 J-mol™' (—90.89 cal-mot") for the formation of the bichromate ion fom its elements at 298.15 K r(er)+20;(8)+1(@)=H (ay) +HCLOG (a). () Using this AS, andthe standard entropies of Cr, O and Ha, the standard entropy of 184.1 J-mol”!-K™ was calculated for the bichromate ion. The 5,(HCO,)=ASq5(C1) 2% S(O.) + Se (H)=[~380.28++23.7742% (204.999) ++(130'374) Jomo K!=184.1F-mol i KA B. Comments on NBS Selected Values SHEP had a A.5;, of ~1343 J-mol™!-K™ for reaction 6: HCIO; (ag) =C10F aq) +H (ag). © Using this value and Eq. (5), Sg(HCH0, aq) = 184.5 J-mol”!-K"". This value supports the selected value of 184.1 J-mol™!-K Values of & Bf, for K,CrsOer) and KyCrO (er) used in the calculations didnot match the values tabulated ~2061.5 and ~1403.7 KI-mot~!, respectively. The differences were not dic to founding cor but du insted to the method of calculation, because values for these two substances were calculated once on worksheets for chromium compounds and then again some time later on worksheets for potasium com- pounds. The calculations on the two different worksheets ‘were not the same, ‘The Ai value for K,Cr,O,(cr) in reaction (1) was ob- ‘tained from subtraction of the enthalpies for the reactions: K,CO,(c2) +100) =2K(aq)+2HC04 (aq), (7) (NHL); C1,0,(e) +100) =2NHY (aq) +2HC10, (aq) @) given by SSHEP to obtain the enthalpy change for the hypo thetcal rection: KC, {e+ 2NHY(aq)=2K" (aq) +(NHY:CHOKe. @) ‘The enthalpy for reaction (9) was combined withthe en- thalpy change for (NH);Cr0,(e +08) =COW)+NKe)+4H00) (10) determined by STINEUIMAR and the tabulated enthalpy of formation for Cr0,(e) to obiain AyH, for K,Cr0(cr). Because the enthalpy change for reaction (7) was used 10 1685, determine Ajtf, for K,Cr,0,(ex) it eannot also give an ine dependent value of A/H;, for HC1O; (ay) and sbould wot have been included in the average. "The A Hy for KjC+O4(ct) was obtained ina similar fash- fon in whic the entnaipy change tor K,Cr04(cr)+H,0()}=2K (aq)+H1Cr0j (aq) (11) ‘was combined with enthalpy changes for reactions (!)~(1U) and the 4H, for Cr,03(t) to obtain dH, for KaCrO,(cr). ‘Thus reaction (3) is also not an independent equation for detcrmination of Ay Ff, for HCc0; (cr). Beceuse nether of reactions (1) and (3) were independent, only reaction (2) should have been used for determination of the enthalpy of formation. This would, change A,#f, to ~8788 kI-mol~? (210.04 keal-mot) and the "entropy to 181.95 JK mol"! ‘The Giths enerey of reaction (4) given by SSHEP was calculated in an unspecified way from values given in S3TON/KIN, 34NEURIE, and SSDAV/PRU. The enthalpy of Sr dependent on te ie ener of ration ©. Auxiliary Values Required for Data Pathway AMAR CEOs, 2) AyH,(H;0, 1) Aytin(K*, 29) Atl a((NH):C130y, 8) AVENE an) ApHg(KaC10,, ct) Agr, 99) A/G.ACOr) AYHE,(HCIO5) AYG(HC10;) SulCH, SOs. 2) Sq(Hay 8) saci, a) D. Other Thermodynamic Measurements Considered None, 4 Phys. Chem Ret. Dats, Vol, 28, No 6, 1999E. Additional Determinations of the ‘Thermodynamic Properties ‘The speciation of the Cr°* species is largely dependent upon the reaction conditions. Many of the following studies were performed to determine which chromium species are present under certain experimental conditions The followit ‘studies present Kq, to adequately identify the proper chemi- cal reaction that coresponds to the measured thermal energy. ‘These speciation studies deal with several Ce°* species. Al- though they are referenced with respect to HCr0,, much of the data are also relevant to other CA species. 28SAA studied the dichromate to chromate reaction under alkaline, neutral, and acidic conditions. The reactions studied were: Ce0}-OH-=Cr02" (alkaline) cof sg HCO; (neural) Crs0F HH +H,0=HCH0; +10 (acidic HCq0; +H,0=2HC10; +H" (acidic) ‘The usual reaction of interest is: CeO} +H HCO; K, 019. ‘This study indicated thatthe chromium equilibrium reactions (C,0%") from the following relationship yanG"=2 A/G (HCrOy)— A /G',(Cr,03-) = A/G(110) Therefore, 8.83 KI-mol"!=2x(~7648 kI-mol~)~A,G3(Cr,07-) =(-237183 Kd-mol™) AVG; (Cr,0F) (8.83) +2x(—7648) ~(=237.183)] KI-mol™! 1301.2 K-mor, ‘The standard molar entropy change of AS;,=—6343 Semol!-K"! (151.6 cal-mol-K™}) was calculated for the following reaction: 2Cx(c#}+ 720g) +H(@)=2H"+Cr,0;?—Q) using the relation of A G%,= A Hj,~TA,Sy, at 298.15 K and the standard free energy and enthalpy changes. The molar entropy of the aqueous dichromate ion was then calculated ‘our te futtowing retatonsnip: S(C0} AS, 2%S,(H)+ 2% Si(C)+ I %Sq(O2) +S, (Hh). Gig COF)=[-G94.9~ 2% (0) +2 (29.8) +72 (204.999) + 130.574] J-mol”!-K! to yield a value of 261.9 J-mol.K™ cal-mnol!-K~), the NBS selected value. 6 ‘J. Phys. Chem. Het. Data, Vol 28, No. 6, 1999 DUANE R. KIRKLIN B. Comments on NBS Selected Values The Gibbs free energy of formation for the aqueous dichromate jon was calculated wsing the SSHEP reaction, reaction (1). S3TON/KIN, 34NEU/RIE and SSDAV/PRU had measured Ky a 98 K that all were in fri good agree- rent. However, 3SHEP chose 0.029 forthe equilibrium con- stant. MNEUIRIE gave 0023, SSTON/KIN gave 00283, and SSDAV/PRU gave 0.0303. The value used in SSHEP is fpparentiy te average ofthe 3SIUNVKIN and 3SDAVIPRU ‘values with no contribution in 34NEUIRIE. Cystine K,Cr,0) isnot stein any’of the above path- ays but the enthalpy of formation ofthe aqueous KaCt0} isnot independent ofthe enthalpy of formation of crystalline KC, C. Auxiliary Values Required for Data Pathway Afg( HCO; , a9) 2440, 1 GACH, 0 4 /G(HC0; 29) BOu{C2077, a) A(COF, 9) Su(Ce, €#) Sq(Ox 8) Salt, @) Sq(Ht, a9) . Other Thermodynamic Measurements Considered ‘The NBS table value for the molar enthalpy change was derived purely from the results of SSHEP, STMUL/HEP, and ‘S3TON/KIN. The selected value agrees quite well with the average Valle obtained fom the KaLF,U; STUaHes OF 30A1/ |, 1882THO (1994.89 K-mot™), 1886SAB (=1997.11 K-mot”'), and 40PER (1997.86 Kf-mol™!). Where the AjH°,(Cr,0}” aq) AE (K,CeOy,9)-2X ApH, (R89) 1995.08) =2("252.38)] "Kl-mol”'=—1490.3 ki-mol”!. Many [Na,CrsOy and (NH,),CesO. studies wee also considered but not used. The following is list of other measurements and the species that were studied ‘The calculation of the A,H’,(Cr503~ aa) was performed with methods similar to dhse used to calculate the AyHTg(C1O%- 2g). The enthalpy of formation of the aque-PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT cous alkali dichromate salt was determined and the enthalpy ‘of formation of the aqueous alkali ion was subtracted to ob- tain the desired quantity, SOYAT/VAS measured the enthalpy of solution of K,Cr0, in aqueous H,S0, that resulted in a Aff, == 1990.29 kF-mol~ for aqueous KyCrsO>. This resulted in a ApH, (Cr,O} ,aq)=— 1485.5kJ-mol”!. 1882THO measured the enthalpy of solution of KsCts0r in H,0 that resulted in a A,H,=~ 1994.89 k-mol”? for aqueous K,Cr0;. This resulted in a AsH",(Cr,0} ,aq) 1490.1 kI-mol”!, They also measured the enthalpy of solution of Na,Cr0; that resulted ina Aydy 1990.291-mmol™ for agueous NayCr,0;, This resulted in a AjH,,(Crg03- aq) ~ 1493.1 F-mol 1886SAB measured the enthalpy of solution of KyCrs0> in ‘aqueous KOH that resulted in a Ad, 1997.11 kJ-mol™ for aqueous K,CrsO,. This resulted in 8A Hiy( C0 aq=— 1492.4 KF-mol 40PER measured the enthalpy of solution of KzCr,0; that resulted in a A/H,=—1997.861I-mol"' for aqueous K,Cr0;, This resulted in a AyH(Cr07 ,aq) 1493.11-mol™ that resulted in a Ay, for aqueous K,Cr,07. This resulted in a Agffig(Cr 0} .9q) 1489.7 I-mol!. They also measured the enthalpy of solution of NasCiQ; that resulted in a yd, 1965.2 KJ-mot for aqueous Na,Cr,0>, This resulted in 8 A/ffg(Cts0}”, 2g) = = 1485.010- mol! They also mea- sured the enthalpy of solution of (NH,),Cr0, that resulted in a 4,H,,=—1757.3k0-mol” for aqueous (NH),C*,0 ‘This resulted in a A pH,(Cr0}- , aq) =~ 1492.3 kJ-mol” 1898VON measured the enthalpy of solution of KzCr,O; that resulted in a Ayt1,=—1996.9KJ-mol™ for aqueous K,CrO;, This resulled in a AyHf,(C0} ,ag) = 492.1 kd-mot 1884BER measured the enthalpy of solution of K,Cr,O; that resulted in a AjE1,=—1998.5KJ-mol™ for aqueous K,Cr,0;. This resulted in a AgH5,(Cr0% ,aq) 1493,81J-mol"!. They also measured the enthalpy of solution of (NH);Cr,0; that resulted in a Ad, 1791-3I-mot * tor Aqueows (NHy)aLU. Ins. re salted in a A,ff,(Ct0F-, aq) =~ 1492.3 kJ-mol SMKOLIGRI measured the enthalpy of solution of KyCh0; that resulted in a AjH,= ~1997.31-mol* for aqueous K,Cr,0;. This resulted in a Ayff(Cr,0} , a9) 1492.5kI-mol-?. GONELIMOS measured the enthalpy of solution of 1Na,Cr0, that resulted in a Hiy= ~1979,0ki-mol for aqueous NaCt0y, This ese in a A (COF a) preehrceon S4HER/LAU measured the enthalpy of solution of 1689 [Na,Cr,Oy that resulted in a Aj¥’,=—1965.61I-mol™! for aqueous NajCiyOy, This resulted in a &yH,(Cr,0} aq) == 1485.4kd-mol" SOLAMIREA measured the enthalpy of solution of 'NasCr,0; that resulted in a A,H’,=~2003.7 KJ-mol~ for aqeous NayCr,0y, This resulted in a Ay#ly(Ces05~ 29) == 1523.5 d-mol™ GISHUVAL measured the enthalpy of solution of 'NayC1,O, that resulted in a AyHZ,=—1964.41-mol for aqueous NajCr,Oy. This resulted in a &H,(Cxs0 aq) == 1484.1-mol“!. SSTNEUIMAR measured the enthalpy of decomposition of ((NH)}:Cr,0,,cf) from which they calculated the enthalpy of formation of (NH):Cr0>.60),— AyFly ==1860kI-mot * trom the’ tollowng reaction: (NHL);Cr,0(ct)=Cr0y(c)+Nalg) +4400). This value is used to determine the enthalpy of formation of erysaline NoyCn,0y thet was then waed in the calculation ofthe valve for the aqueous Na,C,0, SSKAPISHI measured the enthalpy of decomposition of cryaalline (NH,);CrO, based on the aaine action ax STNEUIMAR. A &yj,=~1812.5kI-mol was calculated for crystalline NaCi,6), IPER nvasused dhe etal of solution of QW1L):CH407 that resulted in a AyHy=~1757.8kI-mol* for aqueous (NHsCr0;. This resulted in a AyHfy(Cs,0 aq) |490.8itemot! 23MOLIGON measured the enthalpy of solution of (NH).CrO, that resulted in a A/Fhy=—17548I-mol for "aqueous (NH):Cr,0;, This, meted ina AsHy(Cr05- aq) =~ 1489.8 kJ-mol™ STMULIHEP measured the enthalpy of solution of (NHD,CA, that eocniad inon A, Hy= —1748.61S-mol™! for " aqueous (NH,);Ch0;, This resulted in a Apt (Cr,0F . aq) == 14803 KJ-mol! ‘ASHAIGER. weed 2 Ca/CuO slastrode to determine 0” jon concentration in molten KNOs, The CuO electrode was used to titrate K3Crs0, with NajO in molten KNOs, Sharp Potential drops were recorded atthe equivalence point. The equilibrium constant of the reaction: Cr,0% +0" =2C0} was calculated a5 Kag= 1.8% 10", E. Additional Determinations of the ‘Thermodynamic Properties F. Bibliography 1878MOR —__-Morges, I, Compe, Rend. 86, 1443 (1878). 1882THO Thomsen, J., Thermochemische Untersu- chungen von Julius Thomsen (J. Barth Ver- lag. Trinvig. 18871886) 1884BER Berthelot, M, Ann. Chim. Phys. 1, 92 (ass). 4. Phys, Chem. Ret. Data, Vol. 28, No 6, 1999,1690 1886SAB Sabatier P., Compt. Rend. 103, 267 (1886). 1898VON von Stackelberg, EZ. Phys. Chem. 26, 533 (1898), 23MOLIGON Moles, B., Gonzales, P., Anales. Soe. Es- pan, Fis, Quim. 21, 204 (1923) SULAMIKEA — La Mer, V.K, Read, CL, J. Am, Chem, Soc. 52, 3098 (1930) 34KOLIGRI —Kolosovskii, N., Grishkun, E. V., Zh. Ob- sheh, Khim. 4, 1289 (1934). S4NEUIRIE Neuss, J.D, Rieman, W. II, J. Am. Chem, Soc. $6, 2238 (1934), 40PER Perreu, J. Compt. Rend, 211. 136 (1940). 4IPER Perreu, 1, Compt. Rend. 212, 442 (1941). SSTONKIN. Tong, J. Y., King, E. L., J. Am. Chem. Soc. 75, 6180 (1953). SMHER/LAU Herman, M. A., Lauryssens, M. G., Med, Koninkl. Viaam. Acad. Wetenschap. Belg. 16, 3 (1954), ESDAVIPRU —Devics, Wy Prey J. By Ths, Parlay Soc, 1, 1045 (1955). SSKAPISHI —Kapustinski, A. F, Shilovskii, A. A, le vesxt. Sektora Phatiny T Tinig” Rlagorod Metal, Inst. Obshchei I Neorg. Khim, Akad. Nauk $S.S.R. 30, 31 (1955). SOYATIVAS —Yatsimirsii, K.B., Vasi'eva, V. N., Zh Neorg. Khim. 1, 984 (1956). STMULIHEP —Muldrow, 0. N., Hepler, L. G., J. Am. Chem. Soc. 79, 495 (1957) STNEUMAR Neugebauer, C. A, MANBRIVe, J. La 4 Phys. Chem. 61, 1429 (1957). SHEP Hepler, L. G.,J. Am. Chem. Soc. 80, 6181 (1958), 6ONELIMOS Nelson, 7, Moss, C., Hepler, L. Gu J Phys. Chem, 64, 376 (1960). GISHVVAL —Shidlovskii, A.A. Valkina, K. V..Zh. Fiz. Khim. 38, 394 (1961). G4SHA/GER Shams EI Din, A. M., Gerges, A. A. A lectrochim. Acta 9, 613 (1964) 8. Cr,0,(cr) A. Selected Values, NBS Tables ‘The NBS tables have selected values for four (4) thermo- dynamic properties of crystalline chrominen (0) rile. ‘Tha thermodynamic functions and their selected values are AyFT,(298.15 K): 1139.7 kd-mot“! (2724 keal-mol~1) 4/G5298.15 KY: 1058.1 KI-mol™ (~252.9 keal-mol~!) Sq(298.15.K): 81.2 F-mol-K (194 cal-ma Cyn 298415 Ki) 118.74 Jemot!-K“! (28.38 cal-mol™-K™, J. Phys. Chom. Re. Data, Vol. 28, No. 6, 1999 DUANE R. KIRKLIN 1 was not clear upon which data the NBS selected value was deterined. However, based upon the notes around the combustion measurements of S4MAH, it appears tht the selected value came from this study. The selected NBS table value was ~1139.7 KI-mol”?. STAND measured the heat capacity of Cr,0s, the S{CHO3e)=81.2 Fmol and Cpa( C0500) = 118.74 J-mol"!.K~! came directly from their measure- tment data AyGy(CeOscr) was calculated using: A/G, A/Hlg-TAySm. The ApS, was calculated as_AyS” 81.3-2%(2371)-3/2x(304.999)]——F-mol”-K -~273.86 J-mol~'-K~" based upon the formation reaction, 2Hc0}+320,g)=Ce{0@). Therefor, AG m[-ing9.7=2983n(-0.2/380)) Kemol '=~ 1068 mot” B. Comments on NBS Selected Values SAMAH reported the enthalpy of formation as —1141.0 KJ-mol”' (~272.7 keal-mol”'), The value on the worksheets. ‘was —1140.6 kJ-mol' (—272.6 keal-mol”"), the difference apparently due to a diference in atomic weight of chro- tun The Value tabuated Was — 1139.7 ki-mOL ! (—2/28 ‘keal-mol”'), which is smaller than the value identified for ‘S4MAHL Other than the descriptions of otber measurements considered, found in Section D belo, no additional infor ‘ation a tothe origin ofthis value was avaiable. This is a ey quantity because the enthalpy of formation of Cr,0, is contained within the pedigrees of atleast the following sub- stances CO} (aq), CFO} (aq), HCrO, (aq), CrO;(cr), CrO5(aq), K,CrO,(cr), KyCr,0;(cr), Cr(OH),(cr), and all ‘Cx aq) species. C, Auxiliary Values Required for Data Pathway ChnlCH08) Cyon(One) S,(028) Su(Cee#) D. Other Thermodynamic Measurements Considered 29ROT/BEC also measured the enthalpy of combustion of chromium to form Cr,0s(ct) at 292.15 K. Conversion 10 298.15 K yielded a value of ~1208.8 KI-moI™. 39GRUIFLA measured the oxygen vapor pressure over Cr,0, at temperatures of 1168-1275 K. The reaction r,0}=2Cr+1.50; was assumed to occur. The enthalpy of Tormation Tor 298,19 k, calculated as an average trom these measurements, was 1118 KJ-mol"', with a range of 2 Kd-mot!PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT 40ROTAWOL measured the enthalpy of combustion of chromium to form Cr,Ox(cr) at 294.15 K. Conversion to 298.15 K yielded a value of ~1125.1 KJ-mol~! GIGOLITSZ measured the enthalpy of combustion at 298.15 K and obtained (—1137.67.5) kJ-mol SSROB/EN measured the enthalpy of the react €x,0,(c1)+2Al(er)=2Cr(c)}+ALO,(r) as —$40 KI-mol! Combination with the enthalpy of formation of Al,O,(ct), 1675.7 Ki-mol', gave AyH”=~11351-mol™ 2TVONIAOY measured the reduction equilibrium of C0 C0s(r)+Hilg)=28 Ce+H,0@) (1) at temperatures from 873 f0 1653 K. Their calculated value a1 298 K for Agi was ~1120.3 kS-mol™! S4AOYIKAN also measured the equilibrium of reaction (2) from 718 to 1409 K. Their calculated value at 298 K for Aji” was —11360 KS-mot-', 16 KF-mot-* alifferent from their earlier measurements (27VON/AOY).. 430KA also measured the equilibrium of reaction (2) fom 1212 t0 1583 K. Thelr calculated value at 298 K for AY was -11284 K-mol 46GRUMFLA also measured the equilibrium of reaction (2) ‘rom 1053 10 1373 K. Ther calculated at 298 K value for Ay was —11192 13-mol”™ 44KEL/BOR measured the enthalpy of the reaction (c1s0573C=2Cr+3CO t0 be 801.32 Kano!“ Combina- tion with the enthalpy of formation of CO(g), 110.52 Kd-mol, gave a Aff" ==1132.9KF-mol”! E, Additional Determinations of the ‘Thermodynamic Properties ‘SONOVILEN studied the reactioi beoween Hand C1305 at temperatures of 1220-1500°C from which was calculated the thermodynamic properties associated with the formation uf C05 avuunding die weauiant. 2044 1]0)~P-C130y AyGiz=270.180+ 0.06172XT( + 0.700) keal-mot™! and Po, =39453/T-8.994 were calculated for the reaction TAMALWEH. havo calculated A ij,= ~ L19.9+ 290.1 XT#146K)-mol! of crystalline Cr,05 as a function of| temperature inthe temperature region of 1150-1540 K from. ‘lootrochemical moasurements wing a Th, YO, volid clectrolyt. TIBRUICAN have made precise measurements ofthe heat cepacity of erystalline CxO, from 291 to 333 KE, F. Bibliography ‘yoo Wattnbeag, I, Aoyama, 8 2. Biche trochem, 33, 144 (1927), 2OROTIBEC Roth, W. A., Becker, G., Z. Phys. Chem 148. 461 (1929), 3MAOW/KAN Aoyama S., Kanda B., J. Chem. Soe. Jpn. 55, 1174 (1934) 1691 37ND Anderson, C.J. Am. Chem. Soe. 59, 488 (1937), S9GRUIFLA Grube, G, Fad, M,Z. Electrochem, 45, 835 (1938) 40ROTAWOL Roth, W.A., Wolf, U, Z, Elektrochem. 46, 45 (1040 #80KA kaka, S, Kogyo Kagaku Zasshi 46,324 (198). AMKELIROR Kelley, KK. Rowse, FS, Magee, ,, Huffman, E. H., and Banger, W. M. US, Bur, Mines Tech. Papers 662 (1944). 46GRUIFLA Grube, G., Fad, M., Z. Electochem, 48, 377 (1946). SHMAH Mah, A.D. J. Am. Chem, Soc. 76, 3363, (1954) SSROBITEN Robins, D. A, Jenkins, 1, Acta Metal. 3, 598 (1955). G1GOL/TSZ — Goluvin, Yu. M, Tsin’-Kui, 1, Zh. Phys him, 36, 129 (1961) OSNOVILEN —Novokivatski, LA., Lenev, L. M., Zh Neorg. Khim. 11, 2014 (1966) TAMAZPEH — Mazandarany, F.N.,Pehlke, RD, J Elec uochem, Soe. 124, 711 (1974). TIBRUICAN Broce, R. H., Cannell, D. S., Phys. Rev. 15, 4451 (1977) 9. Cr,0g'H,0 (cr) ‘A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (I) Auetnmalyuue nopeny of de exyotallite Muu (a) Jide monohydrate, The thermodynamic function and its se~ lected value is Apt y(2989 K):—1906. Eset * (S60, Keal-mot 29SIMIFIS measured pressure against temperature for hy- rated crystalline chromium (1m) oxide, Their measurements ‘were used to calculate the enthalpy of hydration for three (3) successive hydrations with one mole of water each. The monohydrate was formed according to the reaction €1,0,(62)FFLOKE)—CHOy MOK. The enuapy of nyu tion Was Ayeqfl” = 124.60 K-mol Ayif(CrOs140.) FY agll +A lal C03 0) * AH (H0.8) ~ 124.604 (1139.7) +(—241.82)] KI-mol™ 1506.1kJ-mol™', which was rounded to —1506.0 kJ-mol~' for the NBS se- ‘Comments on NDC Gelected Values None. 4. Phys. Chem. Ret. Data, Vol. 28, No.6, 10991602 DUANE R. . Auxiliary Values Required for Data Pathway AAT LCe205,0) ApHn(Ha0.2) . Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘Thermodynamic Properties None, F. Bibliography ‘Simon, A., Fischer, 0., Schmid, J, Z. An- org. Allgem. Chem. 185, 107 (1925). 29SIMIFIS 10. Cr,05-2H,0(er) A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (1) thermodynamic property ofthe crystalline chromium (it) ox- ide dihydrate. The thermodynamic function and its selocted value is: AYN (298.15 Ki) 1845, Kl-mot! (41, keal-mot™), 29SIMIFIS measured pressure against temperature for hy- rated crystalline chromium (tt) oxide, Their measurements were used to calculate the enthalpy of hydration for three (3) successive liyuralons wits oe table uf water eae, The de hydrate was formed according to the reaction, Cr,Os H,0(c1)+FH,0(@)=Cr,05-2H,0(cr). The enthalpy of hy- ration was A, Hq=—96.2 KJ-mot™? ApH (Cr0y-2H0.e1) Brat ApH (Ct.0s-H,0.60)+ 8 /H(H.0.8) = 962+ (—1506,)+(~241.82)] -mol™! 18443. Kd-mol ‘The NBS selected value is ~1845. kJ-mol™, Comments on NBS Selected Values None, C. Auxillary Values Required for Data Pathway Ay (C05 10.22) 4 fa(th0.8) 4. Phys. Chem. Ret. Data, Vol 28, No. 6, 1999 KIRKLIN D. Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘Thermodynamic Properties None. F. Bibliography mn, A., Fischer, O., Schmidt, J, Z. An- org. Allgem. Chem. 185, 107 (1928). 11. Cr,03-3H,0(cr) ‘A. Selected Values, NBS Tables 29SIMFIS ‘The NBS tables have a selected value for only one (1) thermodynamic property of the crystalline chromium (it) ox- ide trihydrate. The thermodynamic function and its selected value is aytFg(298.19 K).—21TL. Nin * 29SIM/FIS measured pressure against temperature for hy- rated crystalline chromium (tn) oxide, Their measurements ‘were used to calculate the enthalpy of Byaration forthe (3) successive hydrations with 1 mole of water each. The trihy- rate was formed according to the reaction, x04 211,0(61) #11,0(8)=Cr,0s Ole). The, enthalpy of hydration Was Aygly=—858 — K-mol”! ApH {Cr03H 0.01) B Fg + BH (Ct05°2H,0 02) +A, (H20.2)=[—85.8+ (— 1845) +(—241.82)] ki-mol”'==2172.7 Ki-mol ". The NBS selected value is 2071, WS-mol n°" (319, ean B. Comments on NBS Selected Values Nowe C. Auxiliary Values Required for Data Pathway Aylfy(Ce0s 2H,0.00) 3 (F0.8) D. Other Thermodynamic Measurements Considered None. E, Additional Determinations of the ‘Thermodynamic Properties None F. Bibliography 29SIMIFIS Simon, A., Fischer, O., Schmit, J, Z. Ane cg Allgem. Chem. 188, 107 (1929).PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT 12, Cr,0,(cr) A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (1) thermodynamic property of the crystalline mixed chromium (a) and chromium (ai) oxide, CrO-Cr,03. The thermody- namic function and its selected value is: A/H(298.15 K 1531. K-mol"! (~366. keal-mol™') ‘The Aff, of crystalline mixed chromium (1) and chro- rium i) oxie, CO-Cr0, was selected from the work of GIDANIMOR. An enthalpy’ of reaction of Aff ~ 550.6 ‘kJ-mol~! was measured for the following reaction at 100°C: CyOer +44 (@)=3Cr+4H 01). The Alf = S64 RET malt 91 25°C Ayta( COs) (Mente) +4, /H(H0.2) ~364.8++4(-241.82)]J-mol! 1531.41 -mol™ B. Comments on NBS Selected Values. None C. Auxiliary Values Required for Data Pathway Ayr (tO) D. Other Thermodynamic Measurements Considered None. E, Adaitional Determinations of the ‘Thermodynamic Properties None F. Bibliography GIDAN/MOR —Danilovich. Yu. A.. Moravov. A. N. Fir Khim. Osnovy Proizy. Stal, Akad. Nauk SSSR, Inst. Met, Tr, 6th Konf. Mos- ‘cow, 223 (1961). 13. CrO,(cr) A. Selected Values, NBS Tables ‘The NBS tables gives a selected value for only one (1) thermodynamic property ofthe crystalline chromium (tv) ox- id A Heya x!=— 598. KE-mol! (~143, keal mot) 1693, ‘The A/H,(CrO,,ct) was obtained as the average of two literature values, 6IKUB and SSARUSHC, 61KUB deter rmined the Ajef,=1100KF-mol* at a mean temperature of $00°C forthe decomposition of CrO;(cr) over the tem- perature range from 450 10 550°C according tothe following 1,0s(e}+ 120,68) wo A AC,=29 J-mol 1K"! was caleulated using an est mated ‘eat capacity for C1O3(c) of $23 J-mol!K"! The AC,=[118.7+429.4)—2(52.3)} J-mol-K"=29 Jemol-K"! The &z'y= 110.0 kI-mol reduces to 96.2 ‘r-mot"* when conected from 500 to 25 °C. Therefore, A pHa C102) =[~ (Mpc) + A pH ( C205 00) 2 —(96.2)+(— 139.7) 618.0 kI-mol™" 59, ARVSIIC determined Ayal 25°C for the following reaction: 2Cr0} (ct) +0.96H=Cr,0,(e8}+0.96H,0(0) 2) 2502 k-mol! at and AH, (C102): ~ (Briblg) +8sHy( C03 8) +096 XA (HOD =[-(-2502)+(=113927) ++096%(~285.83))2 =~582.0 KJ-mol™. 600.0 Ki-mol”!, The NBS selected value is —598 ky-mot™ (~143 Keal-mot™*). The NBS selected value was derived as —1434 keal-mel™ that was rounded to —143 kkcal-mol~! and when converted to KJ-mol”" produced the selected value of $98 kI-mol B. Comments on NBS Selected Values ‘The average of ~618.0 and ~$82.0 kI-mol”! (—147.7 and ~139.1-keal-mot') is ~600.0 KJ-mol~* (=143.4 kkcal-mol”). The NBS selected value is —598 kI-mol (143 Keal-mot-). The NBS selected value was derived fiom dhe souuded Keal-anol”* value sit dius de selection of ‘598 instead of 600 KI-mol™ ‘Auxiliary Values Required for Data Pathway ApH(Cr05,00) aytfgttOuug) D. Other Thermodynamic Measurements Considered None. 44 Phys. Chem. Ret. Data, Vol. 28, No. 6, 1999,1694 E. Additional Determinations of the Thermodynamic Properties None. F. Bibliography S3ARVSHC riya, S. M., Shchukarev, 8. A., Glushkova, V.B., Zh. Obshchei. Khim. 23, 1241 (1953). Kubota, B,J. Am. Ceram. Soe. 44, 230 (1961), 14. CrO,(cr) A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (1) thermodynamic property of the crystalline chromium (V1) ox ‘de. The thermodynamic function and its selected value is: A,IPO08 15K): 589.5 kS-mol! (-140.9 keal-mot~) STMULJHEP gave enthalpies for the two reactions: K,Cr,07()+20H (ag) =2K (aq) +2Cx0}>(aq)+H,0(0) 305 kdmol™! (-73 keal-mot!) siKUB Svat and (C10, (r)+20H"(aq)=CrOF (aq) +H,00) SyegHly=— 1172 K-mol- (280 keal-mol™ Subtraction of these two reactions gave K,Cr04(ct)+H,0()=2KOH(ag)+2Cr0, SyoqHly=2088 KF-mol™! (48.7 keal-mol™, which then Jed to. Aytty(CrOs(et)=—989.9 kd-mol* (140.9 Keal-mot™), using the AyH;, of crystalline K,Cr,0;, described under HCrO; (aq). B. Comments on NBS Selected Values The value of A/H(KsC1.0».cf) used in the ealetation 4id_not match that tabulated; see HCrO, (ag) Section B. C. Auxiliary Values Required for Data Pathway ASH (RC107 £2) ‘AjH;,(H0,)) Aj#,(KOH,9q) D. Other Thormedynamle Measurements Considered 29ROT/BEC measured the enthalpy change for the reac ton: 2CrOs(er)=Cr,0,(c8)+3220;(8) J. Phys. Chom. Ref. Data, Vo. 28, No 6, 1999 DUANE R. KIRKLIN 8 28.3 K/-mol™. Combination with the tabulated AH, for Cr0\(ct), -1139.7 Ki-mol, gave AyH, for CrOs(e), 384.5 KI-mot™! O8MIX measured the enthalpy changes for the reactions: (C10 s(c) +NajOe}=Na,CxO ler) and Cx(ct)+3Nag0y(c}=NayC10 (et) +2Na,0(ce) a5 ~322.2 KJ-mol” and ~6644 KJ-mol”?. Combination of the two reactions yields Cr+ 3N0,0,{e~ C0468) +3Na,O(e) with a calculated enthalpy change of ~342.2 KI-mol~!. This ‘was combined. with AHs for Na,O,(cr) and Na,O(er) of 3040 and 4139 Eimol 10 give yt (Cry) 608.4 KJ-mol”?, The AyH, used for Na,O(er) and Na,O,(cr) did not match the values tabulated: ~414.22 and 510.87 1d-mol"!, Use of thece valvea gives Aj Ffy(CrO,) 632.2 Ki-mol™! E. Additional Daterminatians af the Thermodynamie Properties S2HAR made an extensive study of the periodicity of chemical deumodysaunie fuuetious. A family of strsigh lines, based upon the periodic table grouping, was observed when the standard molar entropies were plotted against the log of the moleenlar weight Making use of all the curves, entropies were estimated for several oxides where data were missing. S2HAR estimated the entropy for CrOy to be 63.6 Semot 1-7" (15.2 cal: mol” !-K~), However, Table Lin the paper contains the value of 72.0 J-mol'-K™! (172 cal-mol-K™), F. Bibliography O8MIX Miter, W. G., Am. J. Sci, 26, 125 (1908). 29ROT/BEC Roth, W. A., Becker, G.,Z. Phys. Chem, 145, 461 (1929), S2HAR Hast, D., J. Phys, Chem. $6, 202 (1952). STMULIHEP Muldrow, O. N., Hepler, L. G., J. Am. Chem, Bux. 79, 4095 (1957). 15. CrO3-80H,0 A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (I) thermodynamic property of the chromium (v1) oxide in 80 mole of water. The thermodynamic function and its selected value is ApH (298.15 601.2 Ki-mol! (—143.7 keal-mol™) PRTICIPRI meseneed the enthalpy of soliton of crystal line chromium (vt) oxide in 80 mole of water as AyiuHy 103KJ-mol"! at 15°C that was calculated 0 WePROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT Ayeglli,= ~11.71d-mot™! at 25°C. An enthalpy of forma- tion of the crystalline substance of — A,H’, =—589.5kJ-mol™' was used from the work of STMUL/ ‘HEP. 1878MOR measured enthalpies of solution at several concentration using from 2 to 50 mole of HO. Therefore the NBS table has enties for te enhaipy of formation of aqueous chromium (v1) oxide with from 2 to 80 mole of #0. B. Comments on NBS Selected Values None. C. Auxiliary Values Required for Data Pathway ©, q( C030 C.m(C10300) Cy (HO) D. Other Thermodynamic Measurements Considered None. E, More Recent Determinations of the ‘Thermodynamic Properties, None. F. Bibliography 1878MOR —Morges, F, Compt. Rend. 86, 1443 (1878). IPBUCIPRI Buchner, E.B., Prins, Ay Z. Phys. Chew, 81, 113 (1912). STMULIHEP Muldrow, O. N., Hepler, L. G, J. Am. Chem, Soc. 79, 4095 (1957). 16. [Cr(H,0)g]2(SO,)3 (aq,violet) A. Selected Valuso, NBS Tabloo ‘The NBS tables have a selected value for only one (1) thermodynamic property of the aqueous chromium (a) sul- ‘te dodecanyarate. Ine thermodynamic function and iss Tected value is Ag,(298.15 K): 67174 kJ-mol-! (~1605.5 keal-mol~'), The Aff, of this hexshydated chromium sulfate com- plex, [Cr(H,0}¢](SO4)s, was determined as the average of ‘three (3) measurements reported in the literature. The first value was reported in OTOL as [cH O)g}[$0,h(0q)=—6714.1 IF mol\-1604.7 Keal ‘mol, This value was determined from the enthalpy ofthe following reaction [€xd1,0}4)£50, (9) +GHCI-1500H,0 =2[Cx{H;0),]CIy(aq)+3H,80,-1000 #0 (1) 1695 With AyayAly=35.6 K-mol'(+8.5. Keal-mot). AH, =[-35.6+3(—2501.2) +3( ~892.36)~6(—166.82)] kd-mol'=—6714.1 10-mol™(— 1604.7 keal-mol). A, eal-mol™') came from 1882THO. 1882THO had an en- thalpy of reaction of AyaqMy——186372 KI-aol™! (~44.544 keal-mol™) for the following reaction: [cH{H:0)<){S0,](aq)+6KOH =3K,S0,+2Cr(OH)(cr)+12H,0. @ ‘The A H{Cr(H,0)¢](S04)3.aq]=[186.372+ 3(— 1414.02) +2(—1064.0)+ 12(~ 285.830) -6¢- 482.37)] KJ-mol~! =~ 6719.5 KJ-mol”"(— 1606.0 keal-mot™'). The third value of AyH,=6719.1 KJ-mol”! (=1605.9 keal-mot™') also came from 1882THO. The traction 2CHOH)s+3H,$0,-400H,0 +6H,0=[CHH,0) L504 @) had an enthalpy of rection Of raqHy™ 2005 KI-mol * (493. keal-mol™). The A ffq{(Cr(H0))($0.)s, a9) ~206.3+2(~ 1064.0) +3(~$89.974),o9 +6 (=285.830)] 1 mot"!——6710.1 WS mol" (16059 Kcal-mol™"). The average of these three values, (6714.1 +67I95+6719.1) — Ki-mol} W-mol"! (16047 keal-mot™) value used le work of O7COL. The calcula tions used HCI-1500H,0 and H,SO,: 10000 while the re- ‘actions reported in O7COL used HCI-400H,O and H,$0,-400H,0 The correction to a lower degree of hydra tion only amounts to less than 2 KJ-mol™ and with the other ‘uncertainties involved, this quantity is negligible. C. Auxiliary Values Required for Data Pathway A {HCI 300.29) A/H{H,80,-1000H,0.2q] Ay HSU, 4WDH,0.q) A af (CAH0) ICs 29] 4 fal KOHAg) 4 Hal S04.) ALO) Other Thermodynamic Measurements. ‘Considered None. ‘J. Phys. Chom. Ret. Data, Vol. 28, No. 6, 19991696 E. Additional Determinations of the ‘Thermodynamic Properties None F. Bibliography 1882THO Thomsen, 1, Thermochemische Untersuchungen von Julius Thomsen (J. Barth Verlag, Leipzig, 1882-1886). Colson, A., Ann. Chim. Phys. 12, 433 (1907). o7coL 17, [Cra(H,0)6](SO,)s (aq, green) A. Solected Values, NBS Tables ‘The NBS tables have a selected value for only one (1) thermodynamic property of the aqueous chromium (11) sul- fate hexahydrate, The thermodynamic function and its se- Tected value is: A/Hf,(298.15 X): 4935.0 kJ-mol™! (—1179.5 keal-mol~'), ‘The Aji, of this hexahydated chromium sulfate com- plex, [Ch(HO}[S0.);, was determined trom the work of OTCOL. The following chemical reaction was used: [cx,11,0),K(S0.)3(0q) +6KOHaq) =2Cx{OH)+3K,S0,(aq)+6H,0() a with an enthalpy Araallg = ~ 1069.4 AH ({CrfH,0},1804).09) (A ag) +2 AF (CAOH) 560) “$34 HK$) + 6% 8H (H0,) 6 yt1g¢Othag) =[-(~ 1069.4) +2x(— 1064.0) +3x(~1414.0) bey (-288.83) 6 (=482.27)) Wma“! of reaction, 4935.0 Ki-mol"! (1179.5 keal-mot™. ‘Comments on NBS Selected values. None C. Auxiliary Values Required for Data Pathway Ay Miy( KOH ag) AHCHOM 3.2) Asda FS0y 00) Api HO) J. Phys. Chem, Ret, Data, Vol 28, No.6, 1900 DUANE R. KIRKLIN D. Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘Thermodynamic Properties Nowe F. Bibliography OTCOL Colson, A., Ann. Chim. Phys. 12, 433 (1907) 18. [Cr2(H20)q(SO,)2](SO,)(aq) A. Selected Values, NBS Tables ‘The NBS tables have a selected value for only one (1) thermodynamic property of the aqueous chromium (a1) sul- fate octahydrate. The thermodynamic function and its se- lected value is: AyHhy(29815 KY: ~ $521.6 Kd-mol™ (—1319.7 keal-mot“). The AH of this octahydrated chromiam sulfate com plex, (Cr(H;0}($0.);]80,, was determined from the work of O7COL. The following chemical reaction was used: {Cxs(H,0)(80,),180,(0q)+6KOH(G9) =2Cr(OH)+3K,S0q(aq)+8H,0(1) wo with an enthalpy of reaction, MyaqHfy=—241.0 Kimo“ ($576 keal-mol™"). The A Hy ((Cr(H30)(S0,):1804,a9) Bulg + 2X By Ho CA(OH) 8) +3% ly X80.) +08 fT HO)— OX tty KOHL) (—241.0)+2x(— 1064.0) +3x(— 1414.02) +8X(—285.830)—6%(—482.37)] ‘kJ-mol” S-mot! (1919.7 kkcal-mot™!). $521.6 B. Comments on NBS Selected Values None. ©. Auxillary Values Required for Data Pathway Aglf(KOH.s9) Apt (UH)s.c7) A jE K2804.09) Apt HU) D. Other Thermodynamic Measurements Considered None.PROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT E, Additional Determinations of the ‘Thermodynamic Properties None. F. Bibliography O7COL Colson, A., Ann. Chim. Phys. 12, 433 (1907). 19. [Cra(H20)19S04](SO4)2(2q) A. Selected Values, NBS Tables ‘The NBS bles have a selected value for only one (1) thermodynamic property of the aqueous chromium (it) sul fate decahydrate, The thermodynamic function and ested value i: ApH 298.5 K): = 6123.3 KI-mol™! (—1463.5 keal-mol~!) ‘The AyH 255454 of this decahydrated chromium sulfate complex, {Cia(H:0)pS0,]($0,), was determined from the work of O7COL. The following chemical reaction war uted: 2CH(OHy+3H,$0,(9) +4H1,0 =[Cr(H,0) 0S0,1S0.),(aa) oO) with an enthalpy of reaction, A_,H/(298.15 K)=—182.0 Kisinol™! (43.5. keal-mol™)."The AyH{y(298.15 K) (£Cr(H,0) 801504). 89)= Brent 2A 298.15 K) (COM) c0)+3XAMA2981S KY (HySOy aq) +4 XAyHg(298.15.K)(H0,))=[(-182.0)+2x(— 1064.0) +3%("889.98)+4X(~285.830)] WJ: mol"!=—6123.3 WW-mot™* (=1463.5 keal-mol™) B. Comments on NBS Selected Values None. cw ry Values Required for Data Pathway AYH(29815.K)(CHOHs £0) A/H,(298.15 ¥)(HS0,.0q) AyH,(298.15.K)(H0.)) D. Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘Thermodynamic Properties None, F. Bibliography (OTCOL Colson, A., Ann. Chim. Phys. 12, 433 (1907). 1697 20. CrCl(er) A. Gelected Values, NBS Tables ‘The NBS tables have selected values for six (6) thermo- dynamic properties ofthe crystalline chromium (n) chloride. ‘The thermodynamic functions and ther selected values ae: Agdf(0 K):—397.19 KI-mol™! (94.93 keal-mol™) ApHy(298.15.K):~395.4 KI-mol™? (—94.5 keal-mol™ ‘AyG;,(298.15.K):~356.0 ki-mol“! (~85.1 keal-mol™ H(298.15 K)-H,(0 ) 15094 kd-motl (4503 keal-mat™) $,(298.15 K): M831 F mol! KF 7.56 oal mol“! 1) Cn( 298.15 K 1S} TOL eat-mo RK), COSTOICHT measured the heat capacity of crystaline ‘CrCl between 11 and 300 K. Their measurement data were used to derive most ofthe selected thermodynamic proper- ties of crystalline CrCl, The hea capacity, entropy, and en- thalpy increment from 0 to 298 K came directly from their measurement data ‘The equilibrium data of 37DOE and that of 38SAN were also used to derive the standard molar enthalpy of formation, G2STOICHT recalculated the enthalpy ofthe reacuon studied by both 37D0E and 38SAN. A Myoyff)=210.87KI-mol! was obtained forthe reduction of CxCiy according to the following reaction: CxCL (cr) +H,(@)=Cr(er)+2HC(g) Ay gl CAC Bally 2% QA (CLE) (~210.87+2%(—92.307)] kJ-mol™! 395.48 Ki-mol™', wo ‘The ApH'(0 K) was calculated using A "(298 K) minus the [11208 K) —1°(0¥)] of CrClyy Cr, and Cl, based wpon reaction (2): ° Cx(er)+Ch(g)=CrCh (er) @ as Alo ~3955-[15.033-4058-9.176 K-mol™ The relation A Giy= Aly 1% AS was used Ww ease late A,Gi,. A/S, was calculated based upon reaction (2) a8 AySq=Sy(CrCh) ~ S3(Co)~S(Ch)=[11531= 23.77 =222 987) TrmolK-1a—141 At TemolK-L Then AyGu=[=395.4=298.15x(-0.131411)]—Ki-mol! = 356.1 kd-mol 397.19 J. Phys. Chem. Ret. Data, ol. 28, No 6, 19881698 B. Comments on NBS Selected Values ‘None C. Auxiliary Values Required for Data Pathway ApHn(HChg) [7298 K)-H'(0 K)\(Crex) [27298 K)~#"(0 KCC, g) S'(Crer) S(Che) D, Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘Thermodynamic Properties TOOREISHE valculated a Ayffy~ 396724030 1J-mol™ for crystalline CrCl, from emf measorements of solid electrolyte galvanic cells containing the Cr, C1Cl elec trode: The cell utilized was PICe,CrChBaCh|Fe.FeCh Pt cover the temperature range of 530-800 K. The emf measure rments produced a AjGy=(~380.210+ 0.104587) d-mol” for the formation of CrCl, according tothe reac tion: Cr(c)+Ch(g)=CrCh(c). The Avil, of exystaline CIC was Caculated NOME UE Ay, Me he RAO crystalline CrCly and tabulated standard entropies and heat capacities, F. Bibliography 37DOE Deemer, H. A., US. Bur. Mines. Tech. Pa- pots Nu. 277 (1937), 38SAN Sano, J. Chim. Soc. Jpn. 59, 937 (1938). ©2STOICHI Stout, J. W., Chisholm, R. C.J Chem. Phys. 136, 979 (1962), ‘TOGEEISHE Gee, R., Shelton, R. A. J, Trans, Inst. Min Metal. 85, 208 (1976). 21. CrCL(aq) A. Selected Values, NBS Tables ‘The NBS tables have selected values for one (1) thermo- dynamic propesty of aqueous chromium (1) chloride. The thermodynamic function and its selected value is: AjH,(298.15 K):—477.8 KI-mol”! (—1142 keal-mol™) 1886REC determined the enthalpy of solution of cxystal- Tina chenenine (0) chloride ‘The NRG tables valve for the enthalpy of formation of aqueous chromium (i) chloride was calculated as the sum of the enthalpies of formation and so- 4. Phys. Chem, Ret, Dats, Vol 28, No. 6, 1988 DUANE R. KIRKLIN lution of crystalline chromium (1) chloride, Therefore, SgH{C1C 9) = Bt ( CC 1) +B gl CHC) =[(—395.64)+(-77.8)] KJ-mol”'=—473.46 — kJ-mol~! (-113.16 keal-mol™!) which would round to —473.5 kd-mol' (113.2 keal-mol”'). The NBS tables selected a ‘value of —477.5 kJ-mol~' (—114.2 keal-mvl™') and aut the calculated value of —473.5 kJ-mol~! (—113.2 keal- mol’ 'B. Comments on NBS Selected Values The Ayf,(CeCh,cx)=~395.64Ki-mol“! (94.56 keal-mot ian earlier NBS value but the selected value that was derived from 62STOICHI and AyH,(CiCl, ct) 395.47 kJ-mol (94.52 kcal-mol”) should have been used, The result would be —473.29 Ki-mol"! (~113.12 Kcal-mol ") which would round off to ~473.3 kJ-mot ($113.1 keal-mot”). The NBS selected value of —477.8 Kx-mol~t (~114.2 keal-mol”) seems to have been a tran- scription eror that was discussed earlier under dhe sues Ce” species C. Auxillary Values Required tor Data Pathway Ayfh{CCh 0) D. Other Thermodynamic Measurements Considered None. E. Additional Determinations of the ‘nermoaynamic Properties None. F. Bibliography 1886REC_Recoura, A., Compt. Rend. 102, 865 (1886) S2STOICHE Sto.) CHIMHO, R.C., 2/ CHE PHYS 36, 979 (1962), 22, CrLlyZH,0 (Cr, lignt green) ‘A. Selected Values, NBS Tables ‘The NBS tables have selected values tor one (1) thermo- «dynamic property of crystalline chromium (t) chloride diby- 285.89)] 1 mot! 1608.3 kd-mot! (—384.4keal-mol™), In the second method, also from 1886REC, the messured enthalpy of reaction, Myr Hy= 69.5 KI-mol-! (-16.6 {kcal-mot™) was used based upon the following reaction: CxCIy (et) +4100) “CC 411,046). @ ApHf,(CrCh-4H,0.1) Sand t A Hig( CrCl 0g) +4%A (M20), =[--69.5 +(-395.4)44%(~285,830)] k-mol™? J Phys. Chem. Ret. Data, Vol. 28, No.6, 19081700 =~ 1608.3 KJ-mol“! (—384.4kcal-mol), ‘The two methods produced identical results B. Comments on NBS Selected Values The second calculation, which yielded the ~1608 u-mol”! (3844 keal-mol"), should have used the en- thalpy of formation for gaseous wate, ,Hi,=~241.84 Ki-mol"! (=57.80 Keal-mol™), and not the enthalpy of for. ration for liguid, water, A/H=—285.83. KI-mot! (68.315 kcal-mol™") and ths would have produced a dif ferent result C. Auxiliary Values Required for Data Pathway AsH,(CrCh*) Ay _(CCh a9) AH, (#101) D. Other Thermodynamic Measurements: Considered Nove. E. Additional Determinations of the ‘Thermodynamic Properties None F. Bibliography Recoura, A., Compt, Rend. 102, 865 (1886). 25. CrCl, (cr) A. Selected Values, NBS Tables ‘The NBS tables have selected values for six (6) thermo- ‘oye properties uf tie crystal cnutunt (4s) cionkle, ‘The thermodynamic functions and their elected values are Aytf (0. K):~$5630 KI-mol“! (—132.96 keal-mot™!) ApH, (298.15 K):—$56.5 kI-mol~' (—133.0 keal-mol~) 1886REC AG, (298.15 K):~486.1 KI-mot“t (1162 keal-mol“!) (298.15 K)-H(0 17.66 kI-mol“* (4.22 keal-mol™) Sq(298.15 K):123.0 F-mol" KF (294 eal-mol™ Cyn (29815 Ki): 91.80 Femol“/K-* (21.94 eal-mol" KY. ‘The values for [H,(298.15 K)—H;(0K)], Cand Ss, ‘same from SOHAN/GHU that sorta lvatvapily manure” rents from 15 to 300 K. This work expanded on the work in 37AND which contained measurements from 54 to 297 K. KY) 4 Phys. Chom. Ret. Data, Vol 28, No. 6, 1999) DUANE R. KIRKLIN AH, was determined by six (6) investigators. Most used «a seties of reactions fo ohain the enthalpy f reaction for one of two reactions: reaction (1): the oxidation of chromium (u) chloride with chlorine to obtain chromium (mt) chloride 2CrCI,fet)+C{g) ~2ErC,r) « ‘or reaction (2) the reduction of chromium (mt) chloride with Ihydrogen to produce chromium (a) chloride and hydrogen chloride, 2CICL (er) HL{a)=2CrCh(e+2HCU@). 2) 1887REC determined 4 AjagHy=— 164 8kI-mot"! per role of CrCl for the oxidation in reaction (1).NNo correction was used to comect the measured enthalpy to 25°C. A yHlg(CXCh 2) = Aygg Hl Tf CrCl ex) =[(—1648) +¥(~395.4)] kd -mot 560.2 K-mot 39SAN determined the Ky from partial pressures of HCL and Hy gases at several temperatures between 600 and 700°C forthe. reduction in reaction (2). His Arey, =93,01 -mol~ at 650°C from the slope of his fited data was calculated 10 be AyqHy=97.5KI-mol! at 25°C. The AC; » Was calculated 8 126 J-mol "-K * tor reaction ().‘therefore, A g(CrCls.62) =[~Ayeg hl +2% A Hg CrCl 1) +2 AsH(HClg) /2 ={[(-97.5)+2x(-3954) $2%(—92.307))2} KF-mot! =75364 Kl-mot"! 291ELIKOO determined a Ayaqff,=~280.121-mol“t {or the oxidation of reaction (I) at 736°K. This was comected 285.62 Wl-mol” of Cly at 298 K using a ee Jmol" SK"! This produced a Ada CrCly ot) = ~ 538.1 KF-mol™! 37DOE determined a A,.aff~=~307.9 k-mol~! of Cl, for the oxidation of reaction (1) at 298 K. This produced a Aydt (CeCy et) = ~ 5494 1-mol™ SBFLE/ING measured the electrode potential in two cells from 973 to 1173 K. The overall reaction was CrCh(ot)+ARCHCr) =CrChy(cr) HARE). The Apel 49.54 Ki-mol"' at 1073 K comected to nally ==4025 “Ki-mot' at 2K and yielded a ApH (CrCl) = ~ 568.6 K-mol™ -42MAT measured the vapor pressure of Cl for the reverse of reaction (1) 2CiC(er)=2CrCh(er)+C1,8). 6 The Apelfy294.60 I mol! ot 298 K yielded o AgCHCs 0) ‘The selected value was AjHy(CiCh et) =~3565 Jx-wot. The only way that this elected vale can be ob- tained from the above six (6) values is to se only the results of I887REC and 37DOE withthe former being given doublePROPERTIES OF CHROMIUM AND ITS COMPOUNDS IN THE ENVIRONMENT Weight. This would imply that the high value of ~568.6 K-mol~! and all values less than ~$44 KI-mot™ were re- jected, However, there is no evidence on the worksheets to support this hypothesis or to indicate how this value was obtained. "The Apllg= —$56:30 1-mol™ was calculated as Ally = Ay(298.15 K)— A (Haga x~ He x) for the formation re- action, CH{eN+LS ChE)=CICI CE. ® Therefore, A sHj=Ayf (298.15 K)—A (Hg x) ={-556.5-[17.66~4.058~1.5%9.176}} Kd-mol~!==556.30 kJ-mot™ The A,Gigg x= ~486.2 kI-mol“! was calculated from the relation of AG, A H,~TA,S,. The AS, was calculated from the formation reaction, reaction (4), a5 A,S,=A(S"). Therefore, 123.0~23.7~1.5%222.96) J-mol.K! 235.19 J-mol/-K"! Then NGise x $56.5 ~208.15%(~0.235 19)} kI-mol™! 486.2. KJ-mol B. Comments on NBS Selected Values ‘The actual method used to select the A (CsCl,er) was not clearly identified. Se the comments under Section A C. Auxiliary Values Required for Data Pathway A(CiClae) etl g(FHCLe) AyHfg(AgCher) Ulex Hi el( Crt) Uize Ho xl(Ch) [lee Hi e(CCh) Sa(Crer) Sq(Cho) Sq(CHClser) D. Other Thermodynamic Measurements Considered 37AND measured the heat capacity measurements from 54 t 297 K, however, the SSHAN/GRI data were more re- cent and were made from 15 to 300 K. 1701 42VON measured the enthalpy of solution of CrCl, in ‘aqueous HC and the enthalpy of formation of aqueous CrCl, by reacting Cr with IICL. These reactions were combined 1 obtain the enthalpy of formation of crystalline CxC, A. AjH= ~ 564.8 KF-mol™! was calculated. E. Additional Determinations of the ‘Thermodynamic Properties 68KOS made heat capacity measurements of anhydrous CrCl, from 2 to 4 K. The experimental data fit the equation C=0.051XT+7.1X10"XT°, where C was expressed in cal-mol "-K 1 TBKOS/LUK made heat capacity measurements of any- drous CrCh, from 4.5 to 20 K in magnetic fields of 0, 870, 5800, and 8100 H. At 7<12K, the heat capacity was inde- pendent of the magnetic fcld, At T= 10K, the experimental data fit the equation C=0.0535xT+5.11X10~"x7, wi © was cates i al-anut—-E~! ‘TSGEE/SHE used a mixture of crystalline CrCl, and CrCl, 4s a chlorine electrode to obtain the Gibbs energy of forma- tiv CxCty Uy the ef meta ef ~ 217.07 O.OITAT wad ‘obtained from 570 to 680 K for the cell: PYNi, NiChPbCHICrCL, CrC1|Pt. Tey calculated forthe cell r= setion: Nifer)+2C1C1 (ct)=NiCL (ex) +2CrCh(r) Avex Frx=(42,000-0,119%T) Kd-mol~ ‘The same authors, 7T6GEE/SHE, made other emf measure- ‘ments to determine Ay_,G%, for the formation of NiCl(ct) and CrCl; according 10 the reactions: Niler)+Cl{g)=NiCh(cr) AvaxGg=(~310.110+0.15685%7) KI-mol™ Cx(er)+Cl(@)=C1CL(e) ~380,210+0.104 58%) Kd-mol~ Addition and subtraction ofthe three reactions produced: Cr{et)+ ECh(e)=CrC (er) vanGiy=(~556.260%0.24238XT) KI-mol”!, A third law A/H},=~553.025.01-mol™! for CrCl(ct) Was calculated isifig tabulated standard entropies and heat capacities. However, the emf measurements were done at elevated temperatures and they may not be valid at 298.15 K. SOTIM/YUL chlorinated a heated Cr sample inside a bomb calorimeter. A A,Hy=~S44.42105 kJ-mol™! was determined for chromium’ (tt) chloride according to the following reaction: Cr(oncubie)+1.5Ch(g) =CiClycr hexagonal), F. Bibliography 1887REC —_Recoura, A., Ann. Chim. Phys. 10, 68 (1887), ‘4 Phys. Chem. Ret. Data, Vol. 28, No. ©, 1999