There is a special reason for reviewing this book at this time: it is the 50th edition of a compendium that is known and used frequently in most chemical and physical laboratories in many parts of the world. Surely, a publication that has been published for 56 years, withstanding the vagaries of science in this century, must have had something to offer. There is another reason: while the book is a standard fixture in most chemical and physical laboratories, including those in medical centers, it is not as frequently seen in the laboratories of physician's offices (those either in solo or group practice). I believe that the Handbook can be useful in those laboratories. One of the reasons, among others, is that the various basic items of information it offers may be helpful in new tests, either physical or chemical, which are continuously being published. The basic information may relate

Handbook of Chemistry and Physics

Diastereoisomerism and diastereoselectivity in metal complexes.- Mechanistic aspects of the photochemical reactions of coordination compounds.- Complexation and activation of diazenes and diazo compounds by transition metals.

Theoretical inorganic chemistry

Kinetic investigations on the oxidation of l-asparagine (Asn) by alkaline permanganate have been carried out spectrophotometrically at a constant ionic strength and temperature. The reaction is first order with respect to [MnO4
 −] and less than unit order with respect to both [Asn] and [alkali]. The influence of pH indicated that the oxidation is base catalyzed. The reaction rate was found to increase with increasing ionic strength and temperature. The addition of alkali metal ion catalysts accelerates the oxidation rate. The proposed reaction mechanism involves the formation of a 1:1 intermediate complex between l-asparagine and an alkali-permanganate species in a pre-equilibrium step, which was confirmed by both spectral and kinetic evidence. The complex decomposes slowly in a rate determining step, resulting in the formation of a free radical. The latter reacts again with another alkali-permanganate species in a subsequent fast step to yield the final reaction products which were identified as aldehyde (α-formyl acetamide), ammonia, manganate(VI) and carbon dioxide. The appropriate rate laws are deduced. The reaction constants involved in the mechanism were evaluated. The activation and thermodynamic parameters were determined and discussed.

Base-catalyzed oxidation of l-asparagine by alkaline permanganate and the effect of alkali metal ion catalysts: a kinetic and mechanistic approach

Copper(II) catalysis for oxidation of l-tryptophan by hexacyanoferrate(III) in alkaline medium: A kinetic and mechanistic approach

Kinetics of ruthenium(III) catalyzed oxidation of L-proline by hexacyanoferrate(III)(HCF) in alkali was studied spectrophotometrically at 30 0 C. A reaction was found to be independent upon (L-proline). The reaction was occurred without intervening free radical. Since unit order each in (Ru(III)) and (HCF), the oxidation follows an outer-sphere mechanism. A suitable mechanism was proposed and rate law was derived as kobs = kK

/pdf/kinetics-and-mechanism-of-ruthenium-iii-catalyzed-oxidation-1awem2g7g1.pdf

Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of LProline by Hexacyanoferrate(III) in Aqueous Alkali

Kinetics of oxidation of l-proline by hexacyanoferrate(III) catalyzed by osmium(VIII) in alkaline medium was studied at 30 °C. A mechanism involving free radical path was proposed. Rate law of the reaction was derived as rate=kK1K2[HCF][L-proline][OH−][Os(VIII)]1+K1[OH−]+K1K2[L-proline][OH−] The rate constant k and equilibrium constants K1 and K2 were evaluated as 3.79 × 103 dm3 mol−1 s−1, 0.52 dm3 mol−1, and 3.78 × 103 dm3 mol−1, respectively. The main reactive species of the catalyst appears to be OsO5(OH)3−. The oxidative product of l-proline was identified as l-glutamic acid which is different from the earlier reports. The literature reveals that 4-amino butyric acid, 4-amino butaraldehyde and keto acids were the oxidative products. Activation parameters were evaluated as Ea = 33.5 ± 2 kJ mol−1, ΔH⧧ = 31.0 ± 0.2 kJ mol−1, ΔS⧧ = −24 ± 1.5 J K−1 mol−1, ΔG⧧ = 38.0 ± 2 kJ mol−1.

Osmium(VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in l-Proline by Hexacyanoferrate(III) in Alkaline Media

The diperiodatocuprate(III) (DPC) oxidation of DL-methionine, a sulfur containing amino acid, was studied spectrophotometrically in alkaline solution. The reaction rate was first order in the concentration of DPC and fractional order in the concentration of DL-methionine. Increasing the OH− concentration decreased the rate of reaction, whereas adding IO
 4
 −
 enhanced the rate. The reaction was preceded by a small initiation period of about 0.8 minutes. This initiation time decreased when the concentration of IO
 4
 −
 or DPC increased. Adding the reaction products did not alter the rate of reaction. A mechanism including the intervention of a DL-methionine free radical is proposed and the corresponding rate law is derived. The reaction rate constants are evaluated as well as the activation parameters.

Periodate Influencing Diperiodatocuprate(III) Oxidation of Sulfur Containing Amino Acid in Aqueous Alkaline Medium

Kinetics and mechanism of oxidation of DL-methionine by hexacyanoferrate(III) in aqueous alkaline medium

The kinetics of oxidation of L-valine by a copper(III) periodate complex was studied spectrophotometrically. The inverse second-order dependency on [OH−] was due to the formation of the protonated diperiodatocuprate(III) complex ([Cu(H3IO6)2]−) from [Cu(H2IO6)2]3−. The retarding effect of initially added periodate suggests that the dissociation of copper(III) periodate complex occurs in a pre-equilibrium step in which it loses one periodate ligand. Among the various forms of copper(III) periodate complex occurring in alkaline solutions, the monoperiodatocuprate(III) appears to be the active form of copper(III) periodate complex. The observed second-order dependency of [L-valine] on the rate of reaction appears to result from formation of a complex with monoperiodatocuprate(III) followed by oxidation in a slow step. A suitable mechanism consistent with experimental results was proposed. The rate law was derived as: $$- \frac{\mathrm{d}[\mathrm{DPC}]}{\mathrm{d}t} =\frac{kK_{1}K_{2}K_{3}[\mathrm{Cu}(\mathrm{H}_{2}\mathrm{IO}_{6})_{2}]_{\mathrm{f}}^{3-} [\mathrm{L} -\mathrm{Val}]_{\mathrm{f}}^{2}}{[\mathrm{H}_{3}\mathrm{IO}_{6}^{2 -}]_{\mathrm{f}}[\mathrm{OH}^{ -} ]_{\mathrm{f}}^{2}}.$$
 The temperature effect on the rate of reaction was also studied. The activation parameters of the reaction E
 a, ΔH
 #, ΔS
 #, ΔG
 #, and log10
 A are 49±2 kJ⋅mol−1, 47.5±2 kJ⋅mol−1, −49±2 J⋅K−1⋅mol−1, 62±3 kJ⋅mol−1 and 6.0±0.1, respectively.

K. Sharanabasamma

Papers

Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of LProline by Hexacyanoferrate(III) in Aqueous Alkali

Osmium(VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in l-Proline by Hexacyanoferrate(III) in Alkaline Media

Periodate Influencing Diperiodatocuprate(III) Oxidation of Sulfur Containing Amino Acid in Aqueous Alkaline Medium

Kinetics and mechanism of oxidation of DL-methionine by hexacyanoferrate(III) in aqueous alkaline medium

Kinetics of Oxidation of L-Valine by a Copper(III) Periodate Complex in Alkaline Medium