Negative Ion Mobility Research Articles

Measurement of negative ion mobility in O2 at high pressures using a point plate gap as an ion detector

This paper describes the experimental results for negative ion mobility in O2 at 0.5–2.0 atm. The ion mobility is observed using a high-pressure ion drift tube with a positive corona gap (Geiger counter), which is constructed from a point plate gap and acts as a negative ion detector. The variation of waveforms in the burst pulse is observed by varying the voltage applied to the ion detector to find the optimum voltage that must be applied across the ion detector in O2. This is investigated carefully to ensure the precise determination of mobility. The distortion of the electric field near the mesh electrode, which operates as the cathode of the ion detector and as the anode of the ion drift gap, is then examined to determine the optimum applied voltage to suppress its effect on the measurement of mobility. The mobility is subsequently measured at a reduced electric field intensity of 2.83 × 10−3 to 2.83. The observed mobility of 2.31 ± 0.03 cm2 V−1 s−1 in O2 is concluded to be that of . This value is also obtained in experiments over a wide range of gas pressures (0.5–2.0 atm) and drift lengths (1.00–9.00 cm). The mobilities of and O− are also obtained experimentally.

Simultaneous Determination of Nitrite and Nitrate in Potato and Water Samples Using Negative Electrospray Ionization Ion Mobility Spectrometry

Nowadays, nitrite and nitrate ions are analyzed in biological samples using laborious and expensive methods; such as HPLC, CE, MS-MS. In this work, the simultaneous analysis of nitrite and nitrate ions was conducted by electrospray ionization-ion mobility spectrometry (ESI-IMS), without using any complicated or laborious derivitization step. Ion mobility spectrometry with low cost, inexpensive maintenance and very fast analysis makes an attractive technique for the simultaneous determination of these ions in foodstuff and drinking water samples. The analyte interference was systematically investigated for binary mixture analysis. The obtained results provided detection limits of 3.8 and 4.7 µg/L for nitrite and nitrate, respectively. A linear dynamic range of about 2 orders of magnitude, and relative standard deviations below 5% were obtained by the proposed method for the analysis of both ions. Also, the proposed method was used to analyze various real samples of potato and drinking water samples, and the obtained results confirmed the capability of negative ESI-IMS for the simultaneous detection of nitrite and nitrate.

Rate constants of electron attachment to chlorobenzenes measured by atmospheric pressure nitrogen corona discharge electron attachment ion mobility spectrometry

Using atmospheric pressure nitrogen corona discharge electron attachment ion mobility spectrometry (APNCD-EA-IMS), the rate constants of electron attachment to 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene and α,α,α-trichlorotoluene have been determined at ambient temperature as a function of the average electron energy in the range from 0.35 to 0.65 eV based on the experimental measurements of the negative ion mobility spectra. The rate constants are in the order of magnitude of ∼10 −9 cm 3 molecule −1 s −1. The ability of the dichlorobenzene isomers to capture the electrons has been found to decrease following the order of 1,2-chlorobenzene, 1,3-chlorobenzene and 1,4-chlorobenzene, which is different from previously reported results in the literature. For electron attachment to 1,2,4-trichlorobenzene and α,α,α-trichlorotoluene, the experimental measurements show that α,α,α-trichlorotoluene has a higher rate constant than 1,2,4-trichlorobenzene.

Comparison of the Mobilities of Negative and Positive Ions in Nonpolar Solutions

The mobilities of organic radical ions of different molecular volumes have been determined in squalane and hexane solutions to study the influence of the ion charge sign on the ionic mobility in a weakly polar liquid. The relative mobility of geminate radical ions was measured using the method of time-resolved electric field effect in the recombination fluorescence. To determine the mobility of cations and anions separately, a trend in the value of the relative mobility was analyzed by varying the mobility of one of the geminate partners. The ratios between the mobilities of the anion and the cation of the same molecules were found to be about 1.1. It was shown that in liquid alkanes, the solvent electrostriction was the main factor determining a decrease in the mobility of an ion as compared to the parent neutral molecule. The strong dependence of the electrostrictive effect on the radius of the ionic solvation shell allows the observed difference between negative and positive charge carriers by a small but systematic difference in the effective radii of the ions to be explained.

Selective Method Based on Negative Electrospray Ionization Ion Mobility Spectrometry for Direct Analysis of Salivary Thiocyanate

This study describes a novel technique for direct analysis of thiocyanate in human saliva using negative electrospray-ion mobility spectrometry (ESI-IMS) and without any considerable sample pretreatment. The ESI-IMS system with nearly complete desolvation cannot be useful for salivary thiocyanate analysis because complete overlapping occurs between the format peak of the solvent and the thiocyanate peak. In addition, the chloride ions existing in saliva produce a very broad peak, which has a drastically interfering effect on SCN(-) determination. In this study, with a little change in the operation conditions of the apparatus (lowering the flow rate of the drift gas), it was possible to overcome these problems. The desolvation process was decreased in the lower flow of drift gas, and this caused the SCN(-) peak to be separated completely from other interference peaks such as chloride ions. The results obtained in this proposed methodology provide the detection limit of 0.003 microg/mL and the linear dynamic range from 0.01 to 1.00 microg/mL for the thiocyanate. Several human saliva samples were analyzed with the proposed negative ESI-IMS, and the satisfactory results confirm the capability of the method for direct analysis of salivary thiocyanate.

Relaxation effects in ionic mobility and cluster formation: negative ions in SF6 at high pressures

The relaxation effects of the ionic mobility and the formation of negative-ion clusters in SF6 are studied in this work. For this purpose, we have measured the mobility of negative ions in SF6 over the pressure range 100–800 Torr at a fixed value of density-normalized electric field, E/N, of 20 Td (1 Townsend = 10−17 V cm2). The data obtained show a clear dependence of the negative-ion drift velocity on drift distance. It is observed that the drift velocity (mobility) reaches a steady-state value only for drift distances above 2 cm, over the studied pressure range. In addition to this, we have observed that the ionic mobility depends strongly on the gas pressure. An explanation of this dependence of the ionic mobility on gas pressure is given in terms of a negative-ion clustering formation process. It was found that the assumption of a linear dependence of the cluster ion mass on pressure provides a satisfactory explanation for the observed mobilities.

The Mobility of Negative Ions in $\hbox{CF}_{3} \hbox{I}$, $\hbox{CF}_{3}\hbox{I}{-}\hbox{N}_{2}$ , $\hbox{CF}_{3}\hbox{I}{-}\hbox{Ar}$, $\hbox{CF}_{3}\hbox{I}{-}\hbox{Xe}$, $\hbox{C}_{2}\hbox{F}_{6}$, and $\hbox{CHF}_{3}$, and of Positive Ions in $\hbox{C}_{2} \hbox{F}_{4}$ and $\hbox{c-C}_{4}\hbox{F}_{8}$

Using a pulsed Townsend technique, the drift velocity and the mobility of positive ions in C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> and C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">8</sub> and those of negative ions in C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> , CHF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> , and CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I and its mixtures with N <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> , Ar, and Xe are reported. The overall range of the density-normalized electric field is 4-600 times10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-17</sup> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">V</sup> ldrcm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> . Ion identification is provided by means of previous studies on partial ionization and electron attachment. Thus, it is suggested that the predominant drifting ion in the discharge is C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> for C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> and c-C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">8</sub> , F <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> for C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> F <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> and CHF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> , and I <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> for CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I. The use of more comprehensive theories of ion motion considering the influence of a permanent dipole moment (CHF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> and CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I) has provided reasonable agreement between low-field measured and calculated mobilities. The mobility of negative ions in CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I-N <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> , CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I-Ar, and CF <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> I-Xe mixtures agrees reasonably well with the predicted values by Blanc's law.

Sterically hindered phenols in negative ion mobility spectrometry–mass spectrometry

Negative corona discharge atmospheric pressure chemical ionization (APCI) was used to investigate phenols with varying numbers of tert-butyl groups using ion mobility spectrometry-mass spectrometry (IMS-MS). The main characteristic ion observed for all the phenolic compounds was the deprotonated molecule [M-H](-). 2-tert-Butylphenol showed one main mobility peak in the mass-selected mobility spectrum of the [M-H](-) ion measured under nitrogen atmosphere. When air was used as a nebulizer gas an oxygen addition ion was seen in the mass spectrum and, interestingly, this new species [M-H+O](-) had a shorter drift time than the lighter [M-H](-) ion. Other phenolic compounds primarily produced two IMS peaks in the mass-selected mobility spectra measured using the [M-H](-) ion. It was also observed that two isomeric compounds, 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol, could be separated with IMS. In addition, mobilities of various characteristic ions of 2,4,6-trinitrotoluene were measured, since this compound was previously used as a mobility standard. The possibility of using phenolic compounds as mobility standards is also discussed.

Interaction of negative ions with the surface of inert liquids

The interaction potential of negative ions (electron bubbles) with the surface of liquid 4He, 3He, and Ne has been found. In addition to the electrostatic repulsion, the contribution of the long-range Van der Waals attraction of the electron bubble to the liquid surface has been also taken into account. Competition of these repulsion and attraction forces results in the formation of a potential barrier that prevents the motion of a negative ion from the liquid to the vacuum. The temperature and electric-field dependences of the lifetime of the bubble have been determined. The theory has been compared with the experiments with negative ions in liquid 4He. In contrast to the conventional idea based on the hypothesis of the quantum tunneling of an electron from a bubble to a vacuum, our theory is based on the Kramers’ diffusion model of the classical escape of the bubble over the potential barrier. In this model, a low-dynamic-friction approximation is applicable to liquid 4He owing to a high mobility of negative ions in the superfluid.

Cross sections and transport properties of negative ions in rare gases

We have used a combination of a simple semi-analytic theory - Momentum Transfer Theory (MTT) and exact Monte Carlo (MC) simulations to develop momentum transfer cross sections of negative ions in collisions with noble gases based on the available data for reduced mobility at 300K as a function of E/N. At very low energies, we extrapolated obtained cross sections using Langevin's cross section and supplemented it by the total detachment cross section that was used from the threshold around 6 eV up to 100 eV. Other possible reactive processes have not been taken into account. A good agreement for the mean energy and diffusion coefficients is an independent proof of the validity of the cross sections that were derived for the negative ion mobility data.

Results of the first air ion spectrometer calibration and intercomparison workshop

Abstract. The Air Ion Spectrometer (AIS) measures mobility and size distributions of atmospheric ions. The Neutral cluster and Air Ion Spectrometer (NAIS) can additionally measure neutral particles. The number of the (N)AIS instruments in the world is only 11. Nevertheless, they are already widely used in atmospheric ion studies, particularly related to the initial steps of new particle formation. There is no standard method applicable for calibrating the ion spectrometers in the sub-3 nm ion range. However, recent development of high resolution DMAs has enabled the size separation of small ions with good mobility resolution. For the first time, the ion spectrometers were intercompared and calibrated in a workshop, held in January–February 2008 in Helsinki, Finland. The overall goal was to experimentally determine the (N)AIS transfer functions. Monomobile mobility standards, 241-Am charger ions and silver particles were generated and used as calibration aerosols. High resolution DMAs were used to size-separate the smaller (1–10 nm) ions, while at bigger diameters (4–40 nm) the size was selected with a HAUKE-type DMA. Negative ion mobilities were detected by (N)AISs with slightly better accuracy than positive, nonetheless, both were somewhat overestimated. A linear fit of slope of one to the whole dataset of mobilities suggested that (N)AISs measured the negative mobilities 1.36±0.16 times larger compared with the reference instruments. Similarly, positive mobilities were measured 1.39±0.15 times larger compared with the reference instruments. The completely monomobile mobility standards were measured with the best accuracy. The (N)AIS concentrations were compared with an aerosol electrometer (AE) and a condensation particle counter (CPC). At sizes below 1.5 nm (positive) and 3 nm (negative) the ion spectrometers detected higher concentrations while at bigger sizes they showed similar concentrations as the reference instruments. The total particle concentrations measured by the NAISs were within ±50% of the reference CPC concentration at 4–40 nm sizes. The lowest cut-off size of the NAIS in neutral particle measurements was determined to be between 1.5 and 3 nm, depending on the measurement conditions and the polarity.

Electrical Mobilities of C60 Negative Ions in Noble Gases

We precisely measured the electrical mobilities of C60 negative ions (1.0 nm in outer diameter) using a differential mobility analyzer in helium, neon, argon, and krypton at pressures ranging from 1.07×104 to 4.40×104 Pa. The measured inverse mobilities were larger than those calculated from the hard-sphere collision model. We proposed a formula describing the relation between the electrical mobilities and the diameter of C60 ions in such noble gases, which compensates for the deviation from the hard-sphere collision model.

Negative ions in non-polar liquids

The structure and mobility of positive and negative ions in non-polar liquids are analyzed. The possibility of clusters and bubbles creation around ions of both signs is discussed. It is demonstrated that complexes formed around negative metal and halogen ions in superfluid helium have qualitatively different structures, although the measured values of the mobility were similar. In the case of Ba−and Ga− ions, which have low electron affinities, a bubble is formed around the ion; this bubble is similar to an electron bubble. In the case of Cl−, F−, and I− ions, which have high electron affinities, a cluster is formed near the ion; this cluster is similar to the well-studied cluster at the He+ ion.

Discriminant Analysis of Fused Positive and Negative Ion Mobility Spectra Using Multivariate Self-Modeling Mixture Analysis and Neural Networks

A new method coupling multivariate self-modeling mixture analysis and pattern recognition has been developed to identify toxic industrial chemicals using fused positive and negative ion mobility spectra (dual scan spectra). A Smiths lightweight chemical detector (LCD), which can measure positive and negative ion mobility spectra simultaneously, was used to acquire the data. Simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) was used to separate the analytical peaks in the ion mobility spectra from the background reactant ion peaks (RIP). The SIMPLSIMA analytical components of the positive and negative ion peaks were combined together in a butterfly representation (i.e., negative spectra are reported with negative drift times and reflected with respect to the ordinate and juxtaposed with the positive ion mobility spectra). Temperature constrained cascade-correlation neural network (TCCCN) models were built to classify the toxic industrial chemicals. Seven common toxic industrial chemicals were used in this project to evaluate the performance of the algorithm. Ten bootstrapped Latin partitions demonstrated that the classification of neural networks using the SIMPLISMA components was statistically better than neural network models trained with fused ion mobility spectra (IMS).

Leader effects on femtosecond-laser-filament-triggered discharges

Dynamics of laser filaments in strong nonuniform electric fields is studied with high temporal and spatial resolution. Considerable reduction of the breakdown potential is found and is attributed to a filament-induced leader. Two breakdown modes, fast and slow, are found in 0.4MV positive dc-voltage discharges activated by filaments that are induced by 65fs, 170mJ laser pulses. In the fast mode with duration order of a few microseconds, the filament may acquire the electrode potential and temporarily maintain it, becoming a leader. This gives rise to an average electric field over the attachment instability threshold between a leader head and cathode. Ionization waves precede the breakdown with maximal voltage reduction up to 40% for this mode. The slow mode with its duration order of 1ms appears with a considerably smaller voltage reduction when the leader decays before the secondary streamer; the breakdown delay depends on negative and positive ion mobilities in this case.

Relaxation Times of an Electrolytic Cell Subject to an External Electric Field: Role of Ambipolar and Free Diffusion Phenomena

We evaluate the relaxation times for an electrolytic cell subject to a step-like external voltage, in the case in which the mobility of negative ions is different from that of positive ions. The electrodes of the cell, in the shape of a slab, are supposed to be perfectly blocking. The theoretical analysis is performed by assuming that the applied voltage is so small that the fundamental equations of the problem can be linearized. In this framework, the eigenvalues equations defining all relaxation times of the problem are deduced. In the numerical analysis, we solve the complete set of equations describing the time evolution of the system under the action of the external voltage. Two relaxation processes, connected with the ambipolar and free diffusion phenomena, are sufficient to describe the dynamics of the system, when the diffusion coefficients are of the same order of magnitude.

Differential Mobility Analysis of C60 Negative Ion in He, Ne, and Ar

An anomalous behavior was found in the electrical mobilities of C60 negative ions in He, Ne, and Ar gas measured using a differential mobility analyzer (DMA). The measured inverse mobilities were larger than those calculated with a hard-sphere collision model. We suggested that this anomalous behavior could be ascribed to the potential force of interactions between the C60 negative ion and the gas molecule. Additionally, a method of ab initio calculation of potential energies between the C60 negative ion and the sheath gas molecule was developed, to quantitatively understand the anomalous behavior.

Detection of Aqueous Phase Chemical Warfare Agent Degradation Products by Negative Mode Ion Mobility Time-of-Flight Mass Spectrometry [IM(tof)MS

The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K(o) values, and signal intensities for each of the CWA degradation products are reported.

Influence of ionic transport on deformations of homeotropic nematic layers with positive flexoelectric coefficients

Electric field‐induced deformations of homeotropic nematic liquid crystal layers were studied numerically. A positive sum of the flexoelectric coefficients and a small negative dielectric anisotropy of the nematic material were adopted. Finite surface anchoring strength was assumed. The flow of ionic current was taken into account, the weak electrolyte model being used for description of the electric properties. The director orientation, the electric potential and the ion concentrations were calculated as functions of the coordinate normal to the layer. Calculations show that the threshold for deformation depends on the distributions of the ions (which are influenced by their mobilities), by the ion generation constant and by the properties of the electrodes. When the electrodes have pronounced blocking character and the ion concentration is large, a high and non‐uniform electric field is created by the subelectrode ion space charges. This causes drastic decrease of the threshold voltage, much below the value U f valid for an insulating nematic. At moderate concentrations, the electric field gradient arises in the bulk due to the difference between the mobilities of positive and negative ions. It favours deformation, therefore the threshold is reduced below U f. When the electrodes are well conducting, there are no significant space charges and the threshold voltage remains close to U f. The same value occurs when the space charges are negligible at very low ion contents.

Characteristics of Aerosol Charge Distribution by Surface-Discharge Microplasma Aerosol Charger (SMAC)

The surface discharge on a dielectric barrier induced by dc pulses was successfully utilized as a stable bipolar ion source for neutralizing submicron aerosol particles where the concentration of positive and negative ions could be adjusted independently (a surface-discharge microplasma aerosol charger: SMAC; Kwon et al., 2005). The aim of this study was to determine the charge distribution obtained by the SMAC, which has been qualitatively presented in our previous study, and to investigate the effect of unequal bipolar ion concentration on the charge distribution. For this purpose, we performed quantitative analysis of the charge distribution of monodisperse particles in the size range of 30–200 nm acquired by the SMAC and compared the charge distributions with calculated charge fractions obtained from the diffusion charging theory. The ion parameters were calculated by measuring the ion mobility of positive and negative ions and they were used to obtain the analytic solutions of charge distribution. Th...