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A valuable aspect of the work from Marzilli's group23 and the present studies is that it draws attention to the rather common "insidious impurity problem": namely, that a trace impurity is causing problems in a reaction where one reagent is in large excess to the other reagents. Solvents are one common place where, for example, trace water or oxygen or other impurities can cause problems in reactions. Catalysis is a place where the substrate is in large excess vs the catalyst; the need to remove peroxides from olefins is a well know example.53 Autoxidations catalyzed by trace radical initiators or other reactions that can have large chain lengths are another example. Useful to note here are the general ways that one has to deal with this problem: (i) studies testing the reproducibility of a system using multiple batches of reagents from multiple suppliers, or different lots from the same supplier; (ii) studies using reagents purified by multiple methods; and (iii) studies examining a large change in the ratio of reagents with a careful examination of the resultant.23 Alternatively, (iv) the most powerful, but often most difficult, method of dealing with a trace impurity is to identify it directly, then either eliminate it, or alternatively to increase its concentration, that is, to decrease or increase its concentration and observe the effect.
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Tomasik, P.1
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82
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1942442905
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note
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a values cited should follow the same relative order in the alcohol solvent, ethylene glycol.
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85
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1942442904
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note
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a = 9.8 of adenine.82,83
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86
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0003836971
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Dawson, R. M. C., Elliot, D. C., Elliott, W. H., Jones, K. M., Eds.; Oxford University Press: Oxford
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Data for Biochemical Research, 2nd ed.; Dawson, R. M. C., Elliot, D. C., Elliott, W. H., Jones, K. M., Eds.; Oxford University Press: Oxford, 1969.
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88
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1942475057
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note
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90
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37049129569
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Forsythe, P.; Frampton, R.; Johnson, C. D.; Katritzky, A. R. J. Chem. Soc., Perkin Trans. 2 1972, 671.
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Forsythe, P.1
Frampton, R.2
Johnson, C.D.3
Katritzky, A.R.4
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Elliott, C. M.; Hershenhart, E.; Finke, R. G.; Smith, B. L. J. Am. Chem. Soc. 1981, 103, 5558.
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-1, which as Noyes aptly notes "does not obviously imply the stoichiometry of the transition-state of the rate-determining step". Noyes goes on to say: "Although this example provides a caveat against the uncritical equating of kinetics with transition state stoichiometry, a rather unusual combination of circumstances would be needed to create a situation where such difficulties would arise". The present example is perhaps a more common situation, one where a reagent in large, unchanging excess (e.g., solvent), as well as acid/base reactions, obscure the true rate law and make "clue #1" dangerous to apply. Note however and interestingly that if the [glycol] dependence of the rate law had been uncovered experimentally (i.e., in addition to the observed [bulky base] dependence), then interpretation of that resultant rate law via "clue #1" would have yielded the generally correct interpretation. Also meriting comment here is that it is very well-known that the empirical reaction order and the theoretical concept of molecularity are the same only for elementary steps.87e The above example, as well as common observation of, for example, fractional orders (e.g., in radical chain reactions), teaches that only by doing the math (the kinetics derivation) for a proposed mechanism can one reveal the predicted rate law and overall order for a given mechanism under a specific set of experimental conditions. Hence, this is the principle that the corresponding author teaches in his kinetics class, along with the useful heuristic device of "clue #1" which works in enough cases that Espenson also cites it in his textbook.87b
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95
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Lewis, E. S., Ed.; J. Wiley: New York (see pp 528-529)
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(d) Noyes, R. M. In Techniques of Chemistry, Vol 6, part 1; Lewis, E. S., Ed.; J. Wiley: New York, 1974; p 489 (see pp 528-529).
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Noyes, R.M.1
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(e) Steinfeld, J. I.; Francisco, J. S.; Hase, W. L. Chemcial Kinetics and Dynamics; Prentice Hall: Englewood Cliffs, NJ, 1989; see p 5.
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Steinfeld, J.I.1
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(a) Several early X-ray structures of hemoprotein CO adducts which claimed an Fe-C-O angle of 120-140° were the initial source of the bent Fe-C-O controversy: Collman, J. P.; Brauman, J. I.; Halbert, T. R.; Suslick, K. S. Proc. Natl. Acad. Sci. 1976, 73, 3333.
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0035110522
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Later structural work showed that the error bars on these angles is ≥±25° as discussed in: Spiro, T. G.; Kozlowski, P. W. Acc. Chem. Res. 2001, 34, 137.
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(b) See p 120 of: Lippard, S. J.; Berg, J. M. Principles of Bioinorganic Chemistry, University Science Books: Mill Valley CA, 1994. In this text, the perhaps obvious yet noteworthy point is made that "One lesson for the student of bioinorganic chemistry is that protein crystal structures should not be considered as credible as small-molecule X-ray structures".
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Lippard, S.J.1
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Finke, R. G.; Smith, B. L.; McKenna, W. A.; Christian, P. A. Inorg. Chem. 1981, 20, 687.
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Finke, R.G.1
Smith, B.L.2
McKenna, W.A.3
Christian, P.A.4
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101
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1942475056
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2-py.
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