Application of the generalized internal reference method for the characterization of parameters causing drift in inductively-coupled plasma emission spectrometry

Drift in signals limits the performance of inductively-coupled plasma (i.c.p.) emission spectrometry. The generalized internal reference method was applied to deconvolute the drift of an i.c.p. system. The plasma parameters were correlated to the drift components and the error boundary for the method was found. In the system studied, it was found that fluctuations in the nebulizer uptake rate were responsible for short-term signal changes. Long-term signal drift was caused mainly by flow variations of both cooling gas and aerosol carrier gas. The incident power to the plasma was found to be stable compared to other sources of drift. The method was found to be adequate for evaluating the origins of i.c.p. drift.     

On the reactivity-selectivity relationship in the solvolysis of several reactive alkyl halides

In contrast to previous reports, the selectivities of four carbenium ions R⁺ towards N₃^? and H₂O (log(K_N3^?/K_H2O)) change more than the solvolytic reactivities (log K_solv) of their rather reactive precursors RCl.     

Enols of 2‐nitro‐ and related 2‐substituted malonamides

The structures of 2‐substituted malonamides, YCH(CONR¹R²)CONR³R⁴ (Y = Br, SO₂Me, CONH₂, COMe, and NO₂) were investigated. When Y = Br, R¹R² = R³R⁴ = HEt; Y = SO₂Me, R¹–R⁴ = H and for Y = CONH₂ or CONHPh, R¹–R⁴ = Me, the structure in solution is that of the amide tautomer. X‐ray crystallography shows solid‐state amide structures for Y = SO₂Me or CONH₂, R¹–R⁴ = H. Nitromalonamide displays an enol structure in the solid state with a strong hydrogen bond (O^…O distance = 2.3730 Å at 100 K) and d(OH) ≠ d(O^…H). An apparently symmetric enol was observed in solution, even in appreciable percentages in highly polar solvents such as DMSO‐d₆, but K_enol values decrease on increasing the solvent polarity. The N,N′‐dimethyl derivative is less enolic. Acetylmalonamides display a mixture of enol on the acetyl group and amide in non‐polar solvents, and only the amide in DMSO‐d₆. DFT calculations gave the following order of pK_enol values for Y: H > CONH₂ > COMe ≥ COMe (on acetyl) ≥ MeSO₂ > CN > NO₂ in the gas phase, CHCl₃, and DMSO. The enol on the C?O group is preferred to the aci‐nitro compound, and the N? O? H^…O?C is less favored than the C?O? H^…O?C hydrogen bond. Copyright © 2009 John Wiley & Sons, Ltd.