Oxygen uptake method

Figure C4.2.2 summarizes anticipated results from the use of Basic Protocol 1 (oxygen uptake method) compared with the Alternate Protocol (UV method). Figure C4.2.2 shows hypothetical responses obtained with an equal concentration of LOX and substrate by the two methods.

We have reviewed briefly the many different methods to evaluate antioxidants indicating advantages or limitations where appropriate. It is emphasized again that in order to determine the antioxidant activity, one must control the rate of free radical initiation. A preferred way to do this is by using azo initiators which decompose to form peroxyl radicals at a known, controlled rate. The advantages of the simple oxygen uptake method... 

Table III. The evaluation of ABS thermal oxidative stability by the chemiluminescence, DSC and oxygen uptake methods...

It is known that ABS exhibits dramatic loss of impact resistance when aged in an air oven even at 130 C. The DSC and oxygen uptake methods are probably useful in estimating the high temperature performance but not necessarily directly applicable to predict life times at service temperatures (18). Thus the ability of chemiluminescence to be applied for evaluation of ABS thermal oxidative stability at 150°C and even lower temperatures seem to be important. 

For this work they chose several types of base stocks—some were raffinates from solvent extraction and therefore contained different percentages of aromatics and some were blends of white oils (of near-zero aromatic content) with added quantities of aromatic fractions separated from bright stocks. Oxidations were performed at a number of temperatures with and without added metals (metallic iron and copper to simulate wear metals) and were followed by the oxygen uptake method. Their overall conclusion was that aromatics did indeed inhibit oxidation, whether metals were present or not, and that the effect with their samples exhibited a maximum at about 5% aromatics content. Figure 5.4 illustrates this phenomenon, with measurements of the time for uptake of 1800 ml of oxygen per 100 ml of sample. It can be seen that the reaction rate at zero and 8% aromatics is twice as fast as at 5% (times vary by a factor of two). It was clear that aromatics contained these naturally occurring inhibitors, but this work was unable to shine any light on just what these inhibitors were. 

This concept of optimum aromaticity and the role of sulfur compounds as inhibitors were further established by a study by Bum and Greig (British Petroleum) of the oxidation of solvent extracted base stocks.18 They chose samples from a North African (Sahara) and three Middle East (Iran, Abu Dhabi, and Kuwait) crudes. The aromatic + heterocyclic (A + II) and paraffin + naphthene (P + N) components were separated by alumina chromatography from each base stock (Table 5.9 includes their composition and sulfur contents) and recombined in several ratios and the resistance of the blends to oxidation measured by the oxygen uptake method. 

The first step in the complete biodegradation of primary alcohol sulfates seems to be the hydrolysis to yield alcohol. Sulfatases are able to hydrolyze primary alcohol sulfates. Different authors have isolated and used several sulfia-tase enzymes belonging to Pseudomonas species. The alcohol obtained as a result of the hydrolysis, provided that dehydrogenases have been removed to avoid the oxidation of the alcohol, was identified by chromatography and other methods [388-394]. The absence of oxygen uptake in the splitting of different primary alcohol sulfates also confirms the hydrolysis instead of oxidation [395, 396]. The hydrolysis may acidify the medium and stop the bacterial growth in the absence of pH control [397-399]. 

Thermal reduction at 623 K by means of CO is a common method of producing reduced and catalytically active chromium centers. In this case the induction period in the successive ethylene polymerization is replaced by a very short delay consistent with initial adsorption of ethylene on reduce chromium centers and formation of active precursors. In the CO-reduced catalyst, CO2 in the gas phase is the only product and chromium is found to have an average oxidation number just above 2 [4,7,44,65,66], comprised of mainly Cr(II) and very small amount of Cr(III) species (presumably as Q -Cr203 [66]). Fubini et al. [47] reported that reduction in CO at 623 K of a diluted Cr(VI)/Si02 sample (1 wt. % Cr) yields 98% of the silica-supported chromium in the +2 oxidation state, as determined from oxygen uptake measurements. The remaining 2 wt. % of the metal was proposed to be clustered in a-chromia-like particles. As the oxidation product (CO2) is not adsorbed on the surface and CO is fully desorbed from Cr(II) at 623 K (reduction temperature), the resulting catalyst acquires a model character in fact, the siliceous part of the surface is the same of pure silica treated at the same temperature and the anchored chromium is all in the divalent state. 

In OIT determinations, the test samples are flushed continuously with oxygen during the course of the measurement [1], This is in contrast to oxygen-uptake measurements that are mostly undertaken in a static oxygen atmosphere (see below). Effects such as dynamic removal of volatile antioxidants in the OIT method can lead to these two methods yielding very different assessments of a polymer formulation s stability [1]. 

Comparison of chemiluminescence isothermal runs with oxygen uptake and DSC measurements has been at the centre of interest since practical industrial applications of the chemiluminescence method were attempted. It is a fact that the best comparison may be achieved when studying polymers that give a distinct induction time of oxidation typical for autoaccelerating curves of a stepwise developing oxidation. This is the particular case of polyolefins, polydienes and polyamides. The theoretical justification for the search of a mutual relationship between the oxidation runs found by the various methods follows directly from the kinetic analysis of the Bolland-Gee scheme of polymer oxidation. 

Reaction (12) is under control of G-6-PDH, reaction (13) is catalyzed by MHbR and provides the limiting rate, while reaction (14) is nonenzymatic and indicates the measurable oxygen uptake. The blank in this method contains no dye and the unit of MHbR system is defined as the increase of 02 uptake of one micromole per hour after the addition of an excess of toluidine blue (L7). The determination of MHbR activity in hemolyzates demands the further addition of G-6-P, G-6-PDH, and NADP to the system (W3), the enzyme activity being thus assayed independently from the physiological function of G-6-PDH system. 

Andre et al. [8] discuss the determination of adenosine-5 -triphosphate by luciferin-luciferase assay. This method was applied to the determination of adenosine-5 -triphosphate in bacterial colonies filtered from samples of polluted water after incubation for different periods. The adenosine-5 -triphosphate was extracted from the residue in the filter and the amount compared with the biochemical oxygen demand of the filtered water. The oxygen uptake rate and the rate of formation of adenosine-5 -triphosphate were then plotted against time, the two curves being similar in up to three to four days incubation, after which adenosine-5 -triphosphate production declined markedly, although oxygen uptake continued to increase. 

Off-gas analysis is widely used in many industrial fermentation plants to determine the cellular activity of growing cultures by monitoring respiration. One can measure oxygen uptake and CO2 production rates and thus measure metabolic activity/9 In addition, off-gas analysis is also used for monitoring other volatiles, the synthesis of which are strongly dependent on cultivation conditions 10 and product formation. 11 Off-gas estimation and control therefore serves as an indirect method for process analysis and control. 

Direct measurement of oxygen uptake can be performed with O2 sensors in the headspace of a closed system and organic deposition by measuring the weight changes with a quartz microbalance. This method was applied to investigate the dependence of jet fuel autoxidation on temperature and the presence of antioxidants . 

The correlation between the TEARS assay and MDA dnring oxidation of edible oils may be complicated by the presence of tocopherols (e.g. Vitamin E, 21) . An evaluation was carried of MDA, determined by an independent method , and TEARS as indices for direct oxygen uptake of edible oils and unsatnrated fatty acids. The linear increase of MDA and TEARS with oxygen consumption of soybean oil, in a closed vessel at 170 °C, stops when the latter value reaches 500 p.molL, when both MDA and TEARS start to decrease on further O2 consumption. The same process carried out at 40 °C, using 2,2 -azobis(2,4-dimethylvaleronitrile) (171) as initiator, shows linearity up to 1500 p,molL O2 consumption . A similar behavior is observed for nnsatnrated fatty acids snch as oleic, linoleic and linolenic acids . On the other hand, depletion of Vitamin E (a-tocopherol, 21) and its analogs y- and 5-tocopherol (172, 173) present in the oil show a linear dependence on O2 consumption of the oil, np to 1800 p,molL . This points to the consumption of these antioxidants, and especially 21, as a good index for the O2 uptake in oils at high temperature. The determination of the tocopherols is carried ont by HPLC-FLD (Xex = 295 nm, Ah = 325 nm) . ... 

Monolayer coverage of vanadium oxide on tin oxide support was determined by a simple method of low temperature oxygen chemisorption and was supported by solid-state NMR and ESR techniques. These results clearly indicate the completion of a monolayer formation at about 3.2 wt.% V2O5 on tin oxide support (30 m g" surface area). The oxygen uptake capacity of the catalysts directly correlates with their catalytic activity for the partial oxidation of methanol confirming that the sites responsible for oxygen chemisorption and oxidation activity are one and the same. The monolayer catalysts are the best partial oxidation catalysts. 

The liquid-phase oxidation of acrolein (AL), the reaction products, their routes of formation, reaction in the absence or presence of catalysts such as acetylacetonates (acac) and naphthenates (nap) of transition metals and the influence of reaction factors were discussed in an earlier paper (22). The coordinating state of cobalt acetylacetonate in the earlier stage of the reaction depends on the method of addition to the reaction system (25, 26). The catalyst, Co(acac)2-H20-acrolein, which was synthesized by mixing a solution of Co(acac)2 in benzene with a saturated aqueous solution, decreases the induction period of oxygen uptake and increases the rate of oxygen absorption. The acrolein of the catalyst coordinated with its cobalt through the lone pair of electrons of the aldehyde oxygen. Therefore, it is believed that the coordination of acrolein with a catalyst is necessary to initiate the oxidation reaction (10). 

X 10 g. at. of oxygen/g. of oxide can be readily obtained. By this method Krauss measured the rate of oxygen uptake by nickel oxide (35) and a number of other oxides (36) at 300°C., as well as the amount of oxygen taken up at that temperature after 2 hr., when apparent saturation is reached. For the rate he found a parabolic law ... 

---