The potential of NO⁺ and O₂^+• in switchable reagent ion Proton Transfer Reaction time-of-flight Mass Spectrometry

Selected ion flow tube mass spectrometry (SIFT-MS) and Proton Transfer Reaction mass spectrometry with switchable reagent ion capability (PTR+SRI-MS) are analytical techniques for real-time qualification and quantification of compounds in gas samples with trace level concentrations. In the detection process, neutral compounds—mainly volatile organic compounds—are ionized via chemical ionization with ionic reagent or primary ions. The most common reagent ions are H3O+, NO+ and O2 +•. While ionization with H3O+ occurs by means of proton transfer, the ionization via NO+ and O2 +• offers a larger variety on ionization pathways, as charge transfer, hydride abstraction etc. are possible. The distribution of the reactant into various reaction channels depends not only on the usage of either NO+ or O2 +•, but also on the class of analyte compounds. Furthermore, the choice of the reaction conditions as well as the choice of either SIFT-MS or PTR+SRI-MS might have a large impact on the resulting products. Therefore, an overview of both NO+ and O2 +• as reagent ions is given, showing differences between SIFT-MS and PTR+SRI-MS as used analytical methods revealing the potential how the knowledge obtained with H3O+ for different classes of compounds can be extended with the usage of NO+ and O2 +•

Oxygen Poisoning in Laboratory Testing of Iron‐Based Ammonia Synthesis Catalysts and its Potential Sources

The influence of oxygen poisoning on a state-of-the-art multipromoted iron-based industrial catalyst for ammonia synthesis as well as the effectivity of different gas purification methods to prevent oxygen poisoning for experiments on laboratory scale were studied in detail. Additionally, the observed results were compared to a common oxygen poisoning test from literature, which on the one hand confirmed its usability in a wide range of conditions, but on the other hand also demonstrated the limitations of this test

A Gas Generating System for Complex Gas Mixtures – Multifunctional Application in PTR Method Optimization and Downstream Methanol Synthesis

The multifunctional applicability of a gas mixing system is presented within the scope of Carbon2Chem® for the simulation of steel mill flue gases and their application in downstream processes. A special focus is set on the parallel operation of the gas mixing system to enable PTR-MS method optimization and methanol synthesis with simulated real gas matrices. Information is gathered for the design of downstream processes and their application, where methanol synthesis is chosen as a model reaction. A proof-of-principle study is presented where operation of a catalytic reactor setup in combination with the gas mixing system and a compressor generate reproducible results. The addition of potential trace components in methanol synthesis is exemplarily demonstrated using ammonia. With respect to the PTR-MS application, the dosing of two calibration gas standards, toluene and carbonyl sulfide, via the gas mixing system were analyzed in detail. The obtained results give insight into its applicability to simulate traces and enables the further development of analytical methods for the analysis of trace impurities in the ppb and ppt range in complex gas mixtures

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time-of-flight mass spectrometry under dry and humid conditions

A qualitative analysis was applied for the determination of trace compounds at the parts per trillion in volume (pptv) level in the mass spectra of nitrogen of different qualities (5.0 and 6.0) under dry and humid conditions. This qualitative analysis enabled the classification and discovery of hundreds of new ions (e.g., [Sx]H+ species) and artifacts such as parasitic ions and memory effects and their differentiation from real gas impurities. With this analysis, the humidity dependency of all kind of ions in the mass spectrum was determined. Apart from the inorganic artifacts previously discovered, many new organic ions were assigned as instrumental artifacts and new isobaric interferences could be elucidated. From 1140 peaks found in the mass range m/z 0–800, only 660 could be analyzed due to sufficient intensity, from which 463 corresponded to compounds. The number of peaks in nitrogen proton transfer reaction (PTR) spectra was similarly dominated by nonmetallic oxygenated organic compounds (23.5%) and hydrocarbons (24.1%) Regarding only gas impurities, hydrocarbons were the main compound class (50.2%). The highest contribution to the total ion signal for unfiltered nitrogen under dry and humid conditions was from nonmetallic oxygenated compounds. Under dry conditions, nitrogen-containing compounds exhibit the second highest contribution of 89% and 96% for nitrogen 5.0 and 6.0, respectively, whereas under humid conditions, hydrocarbons become the second dominant group with 69% and 86% for nitrogen 5.0 and 6.0, respectively. With the gathered information, a database can be built as a tool for the elucidation of instrumental and intrinsic gas matrix artifacts in PTR mass spectra and, especially in cases, where dilution with inert gases plays a significant role

The Carbon2Chem_® Laboratory in Oberhausen - A Workplace for Lab-Scale Setups within the Cross-Industrial Project

Within the Carbon2Chem® network, basic research is mandatory for a successful implementation and realization of sustainable technologies for CO2 emission reduction. For this purpose, the exchange of knowledge between the project partners in the individual subareas is as essential as obtaining precise data on the fundamental parameters on a laboratory scale in order to transfer them later to large-scale plants. Therefore, the Carbon2Chem® laboratory offers a platform to gain detailed insights into the individual sub-processes and to then apply these findings at the technical center in Duisburg

Deltoid, triceps, or both responses improve the success rate of the interscalene catheter surgical block compared with the biceps response

Background The influence of the muscular response elicited by neurostimulation on the success rate of interscalene block using a catheter (ISC) is unknown. In this investigation, we compared the success rate of ISC placement as indicated by biceps or deltoid, triceps, or both twitches. Methods Three hundred (ASA I-II) patients presenting for elective arthroscopic rotator cuff repair were prospectively randomized to assessment by biceps (Group B) or deltoid, triceps, or both twitches (Group DT). All ISCs were placed with the aid of neurostimulation. The tip of the stimulating needle was placed after disappearance of either biceps or deltoid, triceps, or both twitches at 0.3 mA. The catheter was advanced 2-3 cm past the tip of the needle and the block was performed using 40 ml ropivacaine 0.5%. Successful block was defined as sensory block of the supraclavicular nerve and sensory and motor block involving the axillary, radial, median, and musculocutaneous nerves within 30 min. Results Success rate was 98.6% in Group DT compared with 92.5% in Group B (95% confidence interval 0.01-0.11; P<0.02). Supplemental analgesics during handling of the posterior part of the shoulder capsule were needed in two patients in Group DT and seven patients in Group B. Three patients in Group B had an incomplete radial nerve distribution anaesthesia necessitating general anaesthesia. One patient in Group B had an incomplete posterior block extension of the supraclavicular nerve. No acute or late complications were observed. Conclusions Eliciting deltoid, triceps, or both twitches was associated with a higher success rate compared with eliciting biceps twitches during continuous interscalene bloc

Influence of Contaminants in Steel Mill Exhaust Gases on Cu/ZnO/Al₂O₃ Catalysts Applied in Methanol Synthesis

The influence of impurities in steel mill exhaust gases on ternary Cu/ZnO/Al2O3 catalysts was studied for conventional methanol synthesis, which is one of the central reactions within the cross‐industrial approach of Carbon2Chem®. A series of hydrocarbons was identified as inert spectators for methanol synthesis. Several catalyst poisons like N‐containing compounds or O2 show reversible characteristics at low pressure. However, by increasing the partial pressure of O2, poisoning becomes irreversible, indicating different poisoning mechanisms concerning the reversibility of deactivation