High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are usually operated at an absolute pressure of 20 mbar reaching high reduced electric field strengths of up to 125 Td for controlled reaction kinetics. This significantly increases the linear range and limits chemical cross sensitivities. Furthermore, HiKE-IMS enables the ionization of compounds normally not detectable in ambient pressure IMS, such as benzene, due to new reaction pathways and the inhibition of clustering reactions. In addition, HiKE-IMS allows the observation of additional orthogonal parameters related to an increased ion temperature such as fragmentation and field-dependent ion mobility, which may help to separate compounds that have similar ion mobility under low field conditions.Aiming for a hand-held HiKE-IMS to carry its benefits into field applications, reducing size and power consumption of the vacuum system is necessary. In this work, we present a novel HiKE-IMS design entirely manufactured from standard printed circuit boards (PCB) and experimentally investigate the analytical performance in dependence of the operating pressure between 20 mbar and 40 mbar. Hereby, the limit of detection (LoD) for benzene in purified, dry air (1.4 ppmV water) improved from 7 ppbV at 20 mbar down to 1.8 ppbV at 40 mbar. Furthermore, adding 0.9 ppmV toluene the signal of the benzene B + peak decreases by only 2 % at 40 mbar. Even in the presence of high relative humidity in the sample gas above 90 % or toluene concentrations of up to 20 ppmV, the LoD for benzene just increases to 9 ppbV at 40 mbar.

Classical ion mobility spectrometers (IMS) operated at ambient pressure, often use atmospheric pressure chemical ionization (APCI) sources to ionize organic compounds. In APCI, reactant ions ionize neutral analyte molecules via gas-phase ion–molecule reactions. The positively charged reactant ions in purified, dry air are H3O+, NO+, and O2 +•. However, the hydration of reactant ions in classical IMS operated at ambient pressure renders ionization of certain analytes difficult. In contrast to classical IMS operated at ambient pressure, High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are operated at a decreased pressure of 10–40 mbar, allowing operation at high reduced electric field strengths of up to 120 Td. At such high reduced field strengths, ions reach high effective temperatures causing collision-induced cluster dissociation of the hydrated gas-phase ions, allowing ionization of nonpolar and low proton affinity analytes. The reactant ion population, consisting of H3O+(H2O) n , NO+(H2O) m , and O2 +•(H2O) p with an individual abundance that strongly depends on the reduced field strength, differs from the reactant ion population in IMS operated at ambient pressure, which affects the ionization of analyte molecules. In this work, we investigate the influence of reduced field strength on the product ion formation of aromatic hydrocarbons used as model substances. A HiKE-IMS-MS coupling was used to identify the detected ion species. The results show that the analytes form parent cations via charge transfer with NO+(H2O) m and O2 +•(H2O) p depending on ionization energy and protonated parent molecules via proton transfer and ligand switching with H3O+(H2O) n mainly depending on proton affinity.

Rationale: Ion mobility spectrometry (IMS) instruments are typically equipped with atmospheric pressure chemical ionization (APCI) sources operated at ambient pressure. However, classical APCI-IMS suffers from a limited ionization yield for nonpolar substances with low proton affinity (PA). This is mainly due to ion clustering processes, especially those that involve water molecules, inhibiting the ionization of these substances. Methods: High Kinetic Energy (HiKE)-IMS instruments are operated at decreased pressures and high reduced electric field strengths. As most clustering reactions are inhibited under these conditions, the ionization yield for nonpolar substances with low PA in HiKE-IMS should differ from that in classical APCI-IMS. To gain first insights into the ionization capabilities and limitations of HiKE-IMS, we investigated the ionization of four model substances with low PA in HiKE-IMS using HiKE-IMS-MS as a function of the reduced electric field strength. Results: The four model substances all have proton affinities between those of H 2 O and (H 2 O) 2 but exhibit different ionization energies, dipole moments, and polarizabilities. As expected, the results show that the ionization yield for these substances differs considerably at low reduced electric field strengths due to ion cluster formation. In contrast, at high reduced electric field strengths, all substances can be ionized via charge and/or proton transfer in HiKE-IMS. Conclusions: Considering the detection of polar substances with high PAs, classical ambient pressure IMS should reach better detection limits than HiKE-IMS. However, considering the detection of nonpolar substances with low PA that are not detected, or only difficult to detect, at ambient pressure, HiKE-IMS would be beneficial. 1 | INTRODUCTION Due to their high sensitivity, fast response times, and compact design, ion mobility spectrometers are commonly used in safety and security applications such as the detection of chemical warfare agents, 1,2 toxic industrial chemicals, 3,4 drugs, 5,6 and explosives. 7-9 Basically, ion mobility spectrometry (IMS) instruments can be divided by their principle of ion separation. In this work, a drift tube (DT) ion mobility spectrometer is used. In DT-IMS, ions are separated by their motion along the axis of a drift tube driven by a homogeneous static electric field. To initiate the measurement, an ion packet is injected into the drift tube. During their motion, the ions are separated based on the absolute value of their ion mobility in the present drift gas. At the end of the drift tube, the ions are captured by a detector that converts

Due to their high sensitivity and compact design, ion mobility spectrometers are widely used to detect toxic industrial chemicals (TICs) in air. However, when analyzing complex gas mixtures, classical ion mobility spectrometry (IMS) suffers from false-positive rates due to limited resolving power or false-negative rates caused by competitive ion−molecule reactions and the resulting suppression of certain analyte ions. To overcome these limitations, high-kinetic energy IMS (HiKE-IMS) was introduced some years ago. In contrast to classical IMS, HiKE-IMS is operated at decreased pressures of 20•••60 mbar and high reduced electric field strengths E/N of up to 120 Td. Under these conditions, the influence of competitive ion−molecule reactions on the prevailing ion population should be less pronounced, thus reducing false negatives. Additionally, effects such as fragmentation and field-dependent ion mobility may help to reduce false positives. In this work, the capabilities and limitations of HiKE-IMS in the field of on-site detection of the volatile TICs NH 3 , HCN, H 2 S, HCl, NO 2 , Cl 2 , and SO 2 are evaluated for the first time. Based on the limits of detection and the extent of spectral and chemical cross-sensitivities in gas mixtures, the results obtained for HiKE-IMS are compared with those obtained for classical IMS. It is shown that HiKE-IMS is less sensitive in comparison to classical IMS. However, when used for TIC detection, the reduced sensitivity of HiKE-IMS is not a major drawback. With values around 1 ppm v , the achievable limits of detection for almost all TICs are below the AEGL-2 (4h) levels. Furthermore, in comparison to classical IMS, it is still striking that HiKE-IMS shows significantly less spectral and chemical cross-sensitivities and thus exhibits considerably lower false-positive and false-negative rates. Overall, it thus turns out that HiKE-IMS is a promising alternative to classical IMS in the field of on-site detection of TICs.

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) chemically ionize gaseous samples via reactant ions and separate the generated ions by their motion in a neutral gas under the influence of an electric field. Operation at reduced pressures of 10–40 mbar allows for reaching high reduced electric field strengths (E/N) of up to 120 Td. At these high E/N, the generated ions gain the namesake high kinetic energies, leading to a decrease in cluster size of the reactant ions by increasing the reaction rate of collision-induced cluster dissociation of hydrates. In positive ion polarity and in purified air, H3O+(H2O) n , NO+(H2O) n , and O2 +•(H2O) p are the most abundant reactant ions. In this work, we investigate the effect of varying sample gas humidity on product ion formation for several model substances. Results show that increasing the sample gas humidity at high E/N of 120 Td shifts product ion formation from a charge transfer dominated reaction system to a proton transfer dominated reaction system. For HiKE-IMS operated at high E/N, the reduction in cluster size of reactant ions allows ionization of analytes with low proton affinity even at high relative humidity in the sample gas of RH = 75% at 303.15 K and 1013.25 hPa. In contrast to conventional IMS, where increasing the sample gas humidity inhibits ionization for various analytes, increasing sample gas humidity in HiKE-IMS operated at 120 Td is actually beneficial for ionization yield of most analytes investigated in this work as it increases the number of H3O+(H2O)n.