Synergetic Catalysis of Copper and Iron in Oxidation of Reduced Keggin Heteropolytungstates by Dioxygen.

Polyoxometalates (POMs) and in particularly Keggin heteropolytungstates are much studied and commercially important catalysts for dioxygen-based oxidation processes. The rate-limiting step in many POM-catalyzed O2-based oxidations is reoxidation of the reduced POM by O2. We report here that this reoxidation process, as represented by the one-electron-reduced Keggin complexes POMred (α-PW12O404- and α-SiVW11O406-) reacting with O2, is efficiently catalyzed by a combination of copper and iron complexes. The reaction kinetics and mechanism have been comprehensively studied in sulfate and phosphate buffer at pH 1.8. The catalytic pathway includes a reversible reaction between Cu(II) and Fe(II), followed by a fast oxidation of POMred by Fe(III) and Cu(I) by O2 to regenerate Fe(II) and Cu(II). The proposed reaction mechanism quantitatively describes the experimental kinetic curves over a wide range of experimental conditions. Since the oxidized forms, α-PW12O403- and α-SiVW11O405-, are far better oxidants of organic substrates than the previously studied POMs, α-SiW12O404- and α-AlW12O405-, this synergistic Fe/Cu cocatalysis of reduced-POM reoxidation could well facilitate significant new O2/air-based processes.

Diffuser-incorporated transmission NIR measurement for reliable analysis of packed granular samples.

A diffuser-incorporated transmission near-infrared (NIR) scheme that enables direct spectral collection of packed granular samples with reliable sample representation and reproducibility has been demonstrated. The analytical utility of this method has been evaluated for the determination of polyethylene (PE) pellet density and the discrimination of the geographical origin of rice samples. Based on the preliminary observation of transmission spectral features acquired from spherical polyoxymethylene (POM) packings composed of different particle sizes as well as packing thickness, a portion of the radiation was propagated through the void space in the packing without fully interacting with the POM pellets. This type of radiation, so-called non-fully interacted radiation (NFIR), adversely affected the sample representation as well as the reproducibility of transmission measurements. To maximize the interaction of NIR radiation with granular samples, a polytetrafluoroethylene (PTFE) diffuser was positioned in front of the sample packing to introduce isotropically diffused radiation into the sample. This diffuser-incorporated scheme resulted in highly reproducible transmission spectra for both packed granular samples. Consequently, the density determination of PE pellets as well as discrimination of rice samples according to geographical origin was more accurate using the proposed scheme.

Enhancement of the spectral selectivity of complex samples by measuring them in a frozen state at low temperatures in order to improve accuracy for quantitative analysis. Part II. Determination of viscosity for lube base oils using Raman spectroscopy.

The use of selectivity-enhanced Raman spectra of lube base oil (LBO) samples achieved by the spectral collection under frozen conditions at low temperatures was effective for improving accuracy for the determination of the kinematic viscosity at 40 °C (KV@40). A collection of Raman spectra from samples cooled around -160 °C provided the most accurate measurement of KV@40. Components of the LBO samples were mainly long-chain hydrocarbons with molecular structures that were deformable when these were frozen, and the different structural deformabilities of the components enhanced spectral selectivity among the samples. To study the structural variation of components according to the change of sample temperature from cryogenic to ambient condition, n-heptadecane and pristane (2,6,10,14-tetramethylpentadecane) were selected as representative components of LBO samples, and their temperature-induced spectral features as well as the corresponding spectral loadings were investigated. A two-dimensional (2D) correlation analysis was also employed to explain the origin for the improved accuracy. The asynchronous 2D correlation pattern was simplest at the optimal temperature, indicating the occurrence of distinct and selective spectral variations, which enabled the variation of KV@40 of LBO samples to be more accurately assessed.

Use of temperature dependent Raman spectra to improve accuracy for analysis of complex oil-based samples: lube base oils and adulterated olive oils.

A simple and effective strategy to improve accuracy for Raman spectroscopic analysis of complex mixture samples by probing a measurement temperature yielding enhanced spectral selectivity has been demonstrated. For the evaluation, the determination of Kinematic Viscosity at 40 °C (KV@40) of lube base oil (LBO) samples was initially attempted. Partial least squares (PLS) was used to determine the KV@40 using Raman spectra of the samples collected at 8 different temperatures from 20 to 90 °C with 10 °C increments. Interestingly, the distinct temperature-induced spectral variation among the samples occurred at 50 °C, thereby resulting in the improved accuracy for determination of KV@40. Two-dimensional (2D) correlation analysis was also performed to find an additional supportive rationale for the improved accuracy. The strategy was further evaluated for the identification of soybean oil-adulterated olive oils using linear discriminant analysis (LDA). Similarly, the discrimination accuracy was improved around 80-90 °C due to the enhanced spectral selectivity between olive and soybean oils. In overall, these two results successfully demonstrate analytical effectiveness of the strategy.