Reference Label Details
Jessup 1938R. S. Jessup, J. Res. Nat. Bur. Stand. 21, 475-490 (1938)
Heats of Combustion of Diamond and of Graphite
Rossini 1938F. D. Rossini and R. S. Jessup, J. Res. Nat. Bur. Stand. 21, 491-513 (1938)
Heat and Free Energy of Formation of Carbon Dioxide, and of the Transition between Graphite and Diamond
note CO2aJessup 1938 reports the heats of combustion, -DeltaU, in int. kJ/mol, for solid carbon to form 1 mole of CO2 (44.010 g) at 30° C and pressure of 1 atm, as follows: Ceylon nat. graphite #1 393.402 +- 0.019; Ceylon nat. graphite #2 393.394 +- 0.026; Ceylon nat. graphite 3#3 393.324 +- 0.032; Buckingham nat. graphite 393.310 +- 0.016; Artificial Graphite #1 393.449 +- 0.020;Artificial Graphite # 2 393.438 +- 0.025. Further correction for heat capacities at constant volume is 1.5 J/mol/K, for a total of 7.5 J/mol to transform the results to 298.15 K. Jessup 1938 takes the correction for external work (p DeltaV) as -11 J/mol. This was later recalculated by Hawtin 1966 to be -12 J/mol. Also, Prosen 1944a find that the data of Jessup 1938 have to be increased by 0.0071% in order to compensate for slight errors. Finally, the result has to be corrected for the changed molecular weight of CO2. Hawtin 1966 make the corrections, but apparently do not take into account all that is needed. They use the equation -DeltaHstd298(correct,cal/mol) = 0.2390681[-DeltaH298(int.J/mol)-32]. Their factor 0.2390681 = 44.011/44.010*1.000071/4.1833. The reduction by 32 int. J/mol is the sum of (-33 +1). However,it is not quite clear how they get -DeltaH298 from -DeltaU303. Other than increasing the -DeltaU values by 11 int. J/mol, it seems that no correction for difference in temperature has been taken, or it amounts to decreasing the values by 1 int. J/mol. (There is also a typo involving the Ceylon nat. graphite #1, which makes the reconstruction of what has been done there difficult.) The temperature correction (-7.5 int. J/mol) used by Jessup 1938 may be too high. He usess Cv of 8.78, 20.82, and 28.08 J/mol for graphite, O2, and CO2. This gives -1.52 int. J/mol/K, or for 5 K -7.6 int. J/mol. Using more current values for Cp reduced by R for the two gases to get Cv: 303.15 K, 8.699, 21.089, 29.049, for a difference of -0.739 J/mol/K or -3.7 J/mol for 5 K; at 298.15 K 8.528, 21.064, 28.821, for a difference of -0.771 J/mol/K or -3.8 J/mol for 5 K; using the average temperature gives -3.8 J/mol for 5 K. (Note that using Cv or Cp in this case leads to the same result, since the amount of gas is the same on both sides of the equation.) Indeed, the enthalpy increment [H303.15-H298.15] for the reaction C + O2 -> CO2 is -0.004 kJ/mol. Hence, we will leave out the correction from 30 deg C to 25 deg C and give the result at 303.15 K. The weighted average (average) of -DeltaU303 of Jessup 1938 is 393.381 - 0.064 int. kJ/mol. With corrections of +12 - 33 int. J/mol and with the additional factor of 1.000071 as per Prosen 1944a, this produces 393.388 +- 0.064 (393.393) int. kJ/mol or 393.451 +- 0.064 (393.456) abs. J/mol for 44.010 g CO2. For comparison, this is equivalent to 94.0393 +- 0.0153 (94.0404) kcal/mol for 44.011 g CO2, to be compared to the similar reinterpretaion of this data by Hawtin 1966 resulting in 94040.6 +- 13.1 kcal/mol, but then taken by them to be at 298 K). For 44.0095 g CO2, the enthalpy of combustion at 303.15 K is then 393.447 +- 0.064 (393.452) kJ/mol. At 298.15 K the value would be 0.004 kJ/mol higher, 393.451 (393.455) kJ/mol. Note that CODATA Key Vals quotes this result as 393.40 +- 0.06 kJ/mol at 298.15 K, and Cox 1970 quote it as 94037 +- 13 cal/mol = 393451 +- 54 J/mol. In addition, from Jessup 1938, Prosen 1944a finds that the enthalpy of combustion of diamond relates to the enthalpy of combustion of graphite via a factor of 1.004820 +- 0.000216. Taking our interpretation for graphite, 393.447 +- 0.064 J/mol, this produces for diamond the value 395.343 +- 0.182 J/mol at 303.15 K. Note that Cox 1970 quote the diamond result as 94505 +- 23 cal/mol = 395409 +- 96 J/mol at 298.15 K.
note CO2cRossini 1938 re-evaluates the data of Jessup 1938 and Dewey 1938 and arrives at the weighted average enthalpy of combustion of graphite at 298.15 K to form 44.010 g of CO2 of -393355 +- 46 int. J/mol. Rossini 1940 restates the exact same result. This corresponds to -393418 +- 46 abs. J/mol, or for 44.0095 g of CO2 to 393.413 +- 46 abs. kJ/mol. This is slightly lower than our reinterpretation, see note CO2 and note CO2a, which produces a weighted average of 393.473 kJ/mol. Rossini also similarly analyses the combustion of diamond, arriving at -395254 - 115 int. J/mol. From these he derives the enthalpy for C -> C of 1899 +- 124 int. J/mol. Correcting this for the change in molecular weight of CO2 from 44.010 to 44.0095 and converting to abs. J/mol produces 1899.3 +- 124.0 abs. J/mol.