WHAT HAPPENS AFTER GRAD SCHOOL
I. Graphite/Chromium trioxide
Our first publication showed that grahite/chromium trioxide prepared by the Croft method was NOT an intercalation compound of graphite but rather a physical mixture of graphite and Cr3O8. X-ray diffraction was definitive on the point, but other lines of proof appeared in the paper. Ten years elapsed without much commentary on the point, until a certain worker in Poland claimed there was an intercalation compound prepared by the Croft method. Various papers appeared at this point.
B. Science issue
Inability of reviewers to understand the significance of a Cu K-beta peak in x-ray radiation in a diffraction experiment performed with filters rather than a monochromator.
C. Relevant papers
L.B. Ebert, R.A. Huggins, J.I. Brauman, The nature of the chromium trioxide intercalation in graphite, Carbon, Volume 12, Issue 2, April 1974, Pages 199-208
J.G. Hooley, Monica Reimer, The chromium trioxide-graphite system, Carbon, Volume 13, Issue 5, 1975, Pages 401-404
W. Metz, H. Meyer-Spasche, Reactions in the system graphite-CrO3-acetic acid I. , Synthetic Metals, Volume 1, Issue 1, October 1979, Pages 53-61
L.B. Ebert, L. Matty Jr., Intercalation compounds of graphite: Chemical identity and reactivity, Synthetic Metals, Volume 4, Issue 4, May 1982, Pages 345-361
J.O. Besenhard et al, Characteristics of molybdenum oxide and chromium oxide cathodes in primary and secondary organic electrolyte lithium batteries. Part II. Transport properties , Solid State Ionics
Volume 8, Issue 1, February 1983, Pages 61-71
J.M. Skowroński, The dilute intercalation compounds of graphite with chromium trioxide, Carbon, Volume 24, Issue 2, 1986, Pages 185-194,
L.B. Ebert, J.C. Scanlon, X-ray diffraction of Croft's graphite/chromium trioxide material, Carbon, Volume 25, Issue 3, 1987, Pages 437-439
J. M. Skowro ski, The influence of a CrO3---graphite intercalation compound on the discharge characteristics of an MnO2 cathode in alkaline electrolyte, Journal of Power Sources, Volume 25, Issue 2, February 1989, Pages 133-140
J.M. Skowroński, New evidence for intercalation of graphite with CrO3 , Carbon
Volume 27, Issue 4, 1989, Pages 537-548 [Some of the reasons for difficulties in interpretation of the X-ray results are considered in relation to graphite intercalation compounds with CrO3 (CrO3-GICs) prepared by the dry method. This paper presents the changes in the X-ray diffraction patterns resulting from the preparation conditions, an insufficient purification of CrO3-GICs and their thermal treatment. The usefulness of indirect methods of examining the compounds with unclear X-ray data is discussed.
L.B. Ebert, J.C. Scanlon, Does chromium trioxide form an intercalation compound with graphite at 200°C?, Carbon, Volume 28, Issue 1, 1990, Pages 253-255
J.M. Skowroński, K. Jurewicz, Anodic oxidation of CrO3-graphite intercalation compounds in sulfuric acid, Synthetic Metals, Volume 40, Issue 2, 1 April 1991, Pages 161-172
J. M. Skowro ski, Distribution of intercalates in CrO3---H2SO4-graphite and CrO3---HClO4-graphite bi-intercalation compounds, Synthetic Metals, Volume 95, Issue 2, 15 June 1998, Pages 135-142
E. Fr ckowiak, J. M. Skowro ski, Passivation of zinc in alkaline solution effected by chromates and CrO3–graphite system, Journal of Power Sources, Volume 73, Issue 2, 15 June 1998, Pages 175-181
Jianyong Liu, Zhaoxiang Wang, Hong Li, Xuejie Huang, Synthesis and characterization of Cr8O21 as cathode material for rechargeable lithium batteries, Solid State Ionics, Volume 177, Issues 26-32, 31 October 2006, Pages 2675-2678
Shih-Fong Lee, Yung-Ping Chang, Li-Ying Lee, Enhancement of field emission from carbon nanotubes by post-treatment with a chromium trioxide solution, New Carbon Materials, Volume 23, Issue 2, June 2008, Pages 104-110
II. Poly (carbon monofluoride
At Stanford, second moment calculations on the F-19 NMR absorption of CF were used to show carbon monofuoride had a boat conformaton, rather than the previously reported chair conformation and the results were published in J. Am.Chem Soc. Although the second moment was calculated using double integration techniques, a later paper, (appearing after I left Stanford) also published in J.Am.Chem.Soc, suggested our result was wrong, because we used only single integration. I (naively) thought it would be an easy matter to correct the factually incorrect assertion about the single integration.
But no, J. Am. Chem. Soc. had an editorial policy not allowing third party commentary on published articles, and as to the second J.Am.Chem.Soc paper, I was a third party. J.Am.Chem.Soc. would not allow correction of an error about what the Stanford work did. Years went by, but I finally had a chance to state the issue, and correct the misstatement in the second J.Am.Chem.Soc. article, curiously in a symposium proceedings of a symposium I did not attend. But the story did not end there.
I was appointed to the “Ethics Task Force” of the American Chemical Society, where I had a chance to bring up the issue of journals issuing corrections. As a lawyer, I participated in a litigation wherein an uncorrected error in J.Am.Chem.Soc. produced a multi-million dollar patent case.  Nevertheless, even with this example, the ACS (and JACS) would not alter the policy. Mistakes last forever. Legal publications suffer the same problem. 
B. Science issue
The inability of a journal to correct a mistake in a published paper leads to later workers overlooking key issues, here the large second moment of the F-19 NMR absorption, which cannot be reconciled with the chair model.
From L.B. Ebert, INTERSECTION OF SCIENCE AND LAW at SSI-11:
In my own experience, I came across one episode which illustrated the inability of the scientific
community to deal with each side of the coin. In a paper by D. L. Wertz and M. Bissell, Energy &
Fuels, 1994, 8, 613-617 on the diffraction of the graphene layer ["(002)"] peak in bituminous coals, the
authors stated that the diffraction peak was "far too intense to be caused by amorphous scattering and far
too broad to be caused by conventional diffraction." The authors cited three papers to justify this
assertion. Of three papers relied upon to prove the statement, which was the key assumption in the
paper, one was non-existent, one was irrelevant and one supported a contrary position. Following use of
the key assumption, the authors utilized an undefined short range interference function to manipulate the
x-ray diffraction data of the paper. The modified data led to a remarkable conclusion: that analysis of a
peak related to interference between aromatic entities (sp2 hybridized carbon) could predict the amount
of aliphatic carbon (sp3 hybridized carbon). Pertinent prior work on diffraction of "poorly crystalline"
carbonaceous systems with sp2 and sp3 carbon was ignored.
I contacted the editor of the journal. Of the non-citation and mis-citation issues, nothing was
done, and in fact the mis-citation was repeated in a later paper.
From L.B. Ebert, A Tale of Conflicting Models;
THE COMING SKIRMISH ON THE IP FRONTIER, Intellectual Property Today, p. 20 July, 2001
The Journal of the American Chemical Society has a policy of not allowing mistake correction by third parties, and the present author has direct experience with this policy. This author wrote a paper on the calculation of the second moment of the fluorine nuclear magnetic resonance (NMR) of solid poly (carbon monofluoride), which led to the conclusion that the structure contained an infinite array of cyclohexane boats, rather than the expected chairs, J. Am. Chem. Soc., 1974, 96, 7841, which boat structure was reproduced in the Cotton and Wilkinson, 4th edition. Five years later, different workers, who also published in JACS, criticized the calculation, on the basis that it involved a single integration, rather than a double integration. Although the allegation had no basis in the text of the 1974 paper, and was untrue, the journal (which did not dispute the truth of what this author said) would not allow a comment to be published. Five years later, this author did publish a comment, which appeared in the Proceedings of the Workshop on Electrochemistry of Carbon, pp. 595-607, Electrochemical Society Proceedings Series, Volume 84 No. 5 (1984). (Poly(carbon monofluoride) is a useful cathode for high energy density lithium batteries.)
C. Relevant papers
L. B. Ebert, J. I. Brauman and R. A. Huggins, J. Am. Chem. Soc., 1974,
Y. Kita, N. Watanabe and Y. Fujii, J. Am. Chem. Soc., 1979, 101,
L.B. Ebert, Electrochemistry of intercalation compounds of graphite, Proc. - Electrochem. Soc.; (United States); Journal Volume: 84-5; Conference: Workshop on the electrochemistry of carbon, Cleveland, OH, USA, 17 Aug 1983, pp. 595-607
Peter Kamarchik Jr., John L. Margrave, Poly(carbon monofluoride): a solid, layered fluorocarbon, Acc. Chem. Res., 1978, 11 (8), pp 296–300
Thomas R. Krawietz and James F. Haw, Characterization of poly(carbon monofluoride) by 19F and 19F to 13C cross polarization MAS NMR spectroscopy, Chem. Commun., 1998 2151 [One such study concluded that (CFx)n is an array
of cis-trans-linked boats, with all fluorine in axial positions. A
more recent student used similar methods to support a transtrans-
linked chair structure, and that conclusion is supported by
the available X-ray data. (…)samples of (CF0.87)n
and (CF1.12)n The most
intense peak in both spectra, at 187 ppm, is assigned by
comparison to the fluorines on C9 and C10 of either trans- or
cis-perfluorodecalin, each at 186 ppm. Therefore, the 187
ppm resonance in Fig. 1 is confidently assigned to C–F
P. Lam (Caltech-CNRS) and R. Yazami, Physical characteristics and rate performance of (CFx)n (0.33 < x < 0.66) in lithium batteries, Journal of Power Sources, Volume 153, Issue 2, 28 February 2006, Pages 354-359
Jérôme Giraudet (Université Blaise Pascal ) et al. Comparative performances for primary lithium batteries of some covalent and semi-covalent graphite fluorides Journal of Power Sources, Volume 158, Issue 2, 25 August 2006, Pages 1365-1372
Special issue including selected papers from the 6th International Conference on Lead-Acid Batteries (LABAT 2005, Varna, Bulgaria) and the 11th Asian Battery Conference (11 ABC, Ho Chi Minh City, Vietnam) together with regular papers.
Jérôme Giraudet (Université Libre de Bruxelles), Solid state NMR studies of covalent graphite fluorides (CF)n and (C2F)n, ,Journal of Physics and Chemistry of Solids, Volume 67, Issues 5-6, May-June 2006, Pages 1100-1105 [See also J. Phys. Chem. B, 2006, 110 (24), pp 11800–11808]
Proceedings of the 13th International Symposium on Intercalation Compounds, Clermont-Frerrand, France, 6-9 June, 2005
H. Fujimoto, Structure analysis of graphite fluoride by the Rietveld method, Carbon Volume 35, Issue 8, 1997, Pages 1061-1065
Lawrence B. Ebert , Robert A. Huggins and John I. Brauman, Reaction of antimony pentafluoride with poly (carbon monofluoride) , Materials Research Bulletin, Volume 11, Issue 6, June 1976, Pages 615-619
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III. The problem of ignoring the literature
In parts I. and II., examples were given wherein there was an engaged debate of relevant science issues, although the dialog was imperfect, either through the inability of reviewers to recognize basic science facts or through the unwillingness of scientific editors to correct errors.
A different pathology arises when authors/reviewers/editors simply choose to ignore relevant published papers.
B. Science issues
When authors/reviewers/editors ignore relevant published papers, great waste occurs.
C. Relevant published papers
For example, see J. M. McBride, The hexaphenylethane riddle, Tetrahedron
Volume 30, Issue 14, 1974, Pages 2009-2022.
The correct quinoid structure for the dimer of triphenylmethyl radicals was proposed in 1904. By 1906 there existed three independent lines of evidence which support this structure: acid-catalyzed aromatization, para-halogen lability, and radical chain autoxidation. Despite this evidence, and the skill and insight of the numerous chemists who studied the system,the incorrect hexaphenylethane structure was assigned to the dimer until 1968. This paper attempts to explain how this could have happened by tracing the evolution of triphenylmethyl theory and of attitudes toward the evidence from 1900 until 1968.
Hot off the press: the paper by Cecil D. Quillen, Jr. and Ogden H. Webster, Continuing Patent Applications and
Performance of the U.S. Patent and Trademark Oﬃce—One More Time, The Federal Circuit Bar Journal, 379 (2009)
which begins: This Article is the fourth by the authors reporting the eﬀect of continuing
patent applications on performance of the United States Patent and Trademark
Oﬃce (“USPTO”) and updates our earlier studies through the USPTO’s 2008
ﬁscal year (“FY”) and through 2007 for the European and Japanese Patent
Oﬃces (“EPO” and “JPO,” respectively).1
manages not to cite the variety of papers criticizing the first three papers in the series.
For example, PATENT GRANT RATES AT THE UNITED STATES PATENT AND
TRADEMARK OFFICE , 4 CHI.-KENT J. INTELL. PROP. 108 (2004):
In recent proposals for patent reform made by the Federal Trade Commission and by the National Academy
of Sciences, there has been discussion of the possibility that the grant rate of patents by the United States
Patent and Trademark Office [USPTO] is high compared to that of other industrialized countries, including
that of Japan and those of Europe. This discussion began with papers of Quillen and Webster that
suggested that the grant rate might be as high as 97% and more reasonably is at least 85%. Although the
actual grant rate at the USPTO is typically in the range 62% to 68%, Quillen and Webster suggested the
higher numbers based on an analysis of continuing applications (including continuations, divisionals, and
continuations-in-part). The present paper suggests that the analysis of Quillen and Webster is flawed both
legally and methodologically, and that recent work by Clarke, which places the corrected grant rate at less
than 75%, is more accurate.
The need to be "up to date" in Shepardizing cases is well recognized within the legal community.14 In the
present situation pertaining to patent grant rates, the impact of the first paper by Quillen and Webster,
which asserted a 97% patent grant rate, extended later in time than the second paper by Quillen and
Webster which withdrew the 97% patent grant rate and posited (among other numbers) an 85% patent grant
rate. Thus, the Harvard Law Review15and the chief patent counsel of Intel16 referred to the conclusions of
the first Quillen and Webster paper in the year 2003, after the conclusions had been modified in 2002.17
The patent grant rate studies of Quillen and Webster are flawed and the published grant rate numbers
should not be relied upon in making arguments about patent reform. The models of Quillen and Webster
erroneously assume that all continuing applications are repeated attempts to patent the invention of the
parent application. The methodology of Quillen and Webster, even as modified in 2002, involves double
counting of patents and artificially inflates the patent grant rate. The approximations of Clarke are more
reliable than those of Quillen and Webster.
See also 4 CHI.-KENT J. INTELL. PROP. 186
While Quillen and Webster based grant rate on applications
"allowed," Clarke based his studies on applications "issued." In this paper, we use data
from the USPTO to show that the difference between "allowed" and "issued" applications
is not the reason for the divergence in grant rates. Instead, we suggest that Quillen and
Webster's elevated grant rates arise from a flawed numerical approach.
John R. Allison and Emerson H. Tiller, The Business Method Patent Myth, 18 Berkeley Tech. L.J. 987,
at footnote 139 of QWII: "adjusting assumptions from previous study to correct a probable flaw, but still
producing an estimated allowance rate much higher than reported, and higher than in Japan and Germany."
In a different area, in the context of the plagiarism issue involving Professor Laurence Tribe
of Harvard Law School,20 Professor Allan Dershowitz suggested there was a “cultural
difference” between sourcing in the legal profession and other academic disciplines.21
One would hope that there is no cultural between law and other academic disciplines as
to the correction of published text which is indisputably wrong.22
**Of non-citation of work of a PRIOR researcher see
"Trolls on top?" or how not to cite relevant work?