Vibrational Spectrometry Strategies for Quality Control of Procymidone in Pesticide Formulations

Abstract

Two vibrational spectrometry–based methodologies were developed for procymidone determination in wettable powdered pesticide formulations. The Fourier‐transform infrared (FTIR) procedure was based on the selective extraction of procymidone by chloroform and determination by peak area measurement between 1451 and 1441 cm^?1, using a baseline correction established between 1490 and 1410 cm^?1, and a precision of 0.4% and a limit of detection of 0.01% w/w procymidone for a sample mass of 25 mg were obtained. For FT‐Raman determination, the selected conditions were peak area measurement between 1005 and 995 cm^?1 Raman shift, with a baseline correction fixed between 1030 and 947 cm^?1, and a relative standard deviation of 1% and a limit of detection of 0.8% procymidone in the original sample were obtained. The sample frequency for FTIR determination was 30 hr^?1, lower than that for Raman with 40 hr^?1. FT‐Raman reduces to the minimum the reagent consumption and waste generation, also avoiding the sample handling and contact of the operator with the pesticide. It can be concluded that the proposed methods are appropriate for quality control in commercial pesticide formulations.     

The order of addition of corn starch/lithium perchlorate/glycerol affects the optical,mechanical, and electrical properties of a solid polymer electrolyte

Optical, mechanical, and electric properties of solid polymer electrolyte (SPE) were affected by the order of addition of corn starch (S), lithium perchlorate (Li), and glycerol (G) during the preparation process. Four formulations were made based on whether Li was added prior to S gelatinization (simultaneous formulations SGLi and SLi+G) or whether it was added after S was gelatinized (sequential formulations SG+Li and S+LiG). Simultaneous formulations produced films with smaller elongation-at-break response (60–75%) relative to their sequential counterparts (75–82%). The simultaneous formulations exhibited higher electrical conductivity (～0.7 mS cm^?1) and capacitance (～0.017 F cm^?2) and electrochemical stability than the sequential formulations (～0.9 mS cm^?1 and ～0.012 F cm^?2) at room temperature. Results from FTIR and DSC analyses indicated that starch re-crystallization in casting phase could lead to variations on electrical properties for the different SPE formulations. It was postulated that Li cations replace hydrogen ions inside starch molecules, retarding the re-crystallization of starch molecules.     

A New FTIR Method for the Analysis of Low Levels of FFA in Refined Edible Oils

Abstract

This paper summarizes the application of stoichiometric analytical approaches to quantitative IR analysis and describes the development of a rapid and sensitive Fourier transform infrared (FTIR) method using such an approach for the determination of low levels (<0.005%) of free fatty acids (FFA) in refined edible oils. The method simply involves mixing the sample with methanol containing 2 g /L sodium carbodiimide (NaHNCN) on a vortex mixer for 30 s to convert the FFA to their salts, centrifuging the sample to separate the methanol phase containing the FFA salts from the oil, recording the FTIR spectrum of the upper methanol layer in a 100‐µm CaF₂ transmission flow cell, and ratioing this spectrum against that of the NaHNCN/methanol solution. The concentration of FFA salts is determined from the resulting differential spectrum by measurement of the v(COO^?) absorbance at 1573 cm^?1 relative to a reference wavelength of 1820 cm^?1. A calibration spanning the range 0–0.1% FFA (expressed as oleic acid) was devised by gravimetric addition of a defined, pure fatty acid to an acid‐free oil. Validation of the method by standard addition of palmitic acid to a variety of oils yielded an overall standard error of <±0.001% FFA. Comparison of triplicate FTIR and IUPAC titrimetric analyses of oils spiked with palmitic acid demonstrated that this FTIR method was more sensitive, accurate, and reproducible than the titration procedure, the latter having a significant positive bias of ～0.02%. Solvent/oil consumption in the FTIR method is 2 mL/10 g versus 150 mL/20 g for the titrimetric procedure. The FTIR method developed is particularly well suited for the determination of the low levels of FFA in refined oils but can readily be adapted with a simple adjustment of the oil/methanol ratio to cover FFA levels of up to 4.0%.     

Influence of nano-sized fumed silica on physicochemical and electrochemical properties of cellulose derivatives-ionic liquid biopolymer electrolytes

Nanocomposite biopolymer electrolyte was prepared by solution-casting technique. Carboxymethyl cellulose from kenaf bast fibre, ammonium acetate, (1-butyl)trimethyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquid and silica nanofiller was used to prepare the biopolymer electrolyte samples. The films were characterized by Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, scanning electron microscopy, transference number measurement and linear sweep voltammetry. The interactions of doping salt, ionic liquid and inorganic nanofiller with the host biopolymer were confirmed by FTIR study. The highest conductivity achieved was 8.63 × 10^?3 S cm^?1 by the incorporation of 1 wt% of SiO₂ at ambient temperature. The electrochemical stability of the highest conducting sample was stable up to 3.4 V, and the ion transference number in the film was 0.99.     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

FTIR spectroscopic studies of the matrix photoionization and photolysis products of methylene halides

Matrix photoionization of methylene bromide produced absorptions at 1019, 897, and 788 cm^?1 identified previously as CBr₂⁺, CHBr₂⁺, and CHBr₂. High-resolution FTIR spectra revealed overlapping 1/2/1 triplets for natural bromine isotopes with individual linewidths near 0.2 cm^?1. New absorptions at 3121, 2897, and 1345 cm^?1 are assigned to the (CH₂Br⁺)Br cation complex which yields CHBr₂⁺ on photolysis. A substantially increased yield of the CHCl₂⁺ species made possible observation of the CH stretching mode at 3033 cm^?1 and the symmetric CCl₂ stretching mode at 845 cm^?1 along with the previously observed stronger 1291- and 1044-cm^?1 fundamentals. The high resolution and enhanced signal-to-noise capability of the FTIR are clearly demonstrated in this investigation.     

Study on the effect of PEG in ionic transport for CMC-NH<Subscript>4</Subscript>Br-based solid polymer electrolyte

The present study investigates the ion transport properties and structural analysis of plasticized solid polymer electrolytes (SPEs) based on carboxymethyl cellulose (CMC)-NH₄Br-PEG. The SPE system was successfully prepared via solution casting and has been characterized by using electrical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) spectroscopy, and x-ray diffraction (XRD) technique. The highest conductivity of the SPE system at ambient temperature (303 K) was found to be 1.12?×?10^?4 S/cm for un-plasticized sample and 2.48?×?10^?3 S cm^?1 when the sample is plasticized with 8 wt% PEG. Based on FTIR analysis, it shows that interaction had occurred at O–H, C=O, and C–O moiety from CMC when PEG content was added. The ionic conductivity tabulation of SPE system was found to be influenced by transport properties and amorphous characteristics as revealed by IR deconvolution method and XRD analysis.     

Synthesis of thiol-functionalized MCM-41 mesoporous silicas and its application in Cu(II), Pb(II), Ag(I), and Cr(III) removal

Thiol-functionalized MCM-41 mesoporous silicas were synthesized via evaporation-induced self-assembly. The mesoporous silicas obtained were characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption analysis, Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The products were used as adsorbents to remove heavy metal ions from water. The mesoporous silicas (adsorbent A) with high pore diameter (centered at 5.27 nm) exhibited the largest adsorption capacity, with a BET surface area of 421.9 m² g^?1 and pore volume of 0.556 cm³ g^?1. Different anions influenced the adsorption of Cu(II) in the order NO₃ ^? < OAc^? < SO₄ ^2? < CO₃ ^2? < Cit^? < Cl^?. Analysis of adsorption isotherms showed that Cu²⁺, Pb²⁺, Ag⁺, and Cr³⁺ adsorption fit the Redlich–Peterson nonlinear model. The mesoporous silicas synthesized in the work can be used as adsorbents to remove heavy metal ions from water effectively. The removal rate was high, and the adsorbent could be regenerated by acid treatment without changing its properties.     

Effect of variation of different nanofillers on structural,electrical, dielectric,and transport properties of blend polymer nanocomposites

In the present work, the effect of various nanofillers with different particle sizes and dielectric constants (BaTiO₃, CeO₂, Er₂O₃, or TiO₂) on blend solid polymer electrolyte comprising PEO and PVC complexed with bulky LiPF₆ has been explored. The XRD analysis confirms the polymer nanocomposite formation. FTIR provides evidence of interaction among the functional groups of the polymer with the ions and the nanofiller in terms of shifting and change of the peak profile. The highest ionic conductivity is ~?2.3?×?10^?5 S cm^?1 with a wide electrochemical stability window of ~?3.5 V for 10 wt% Er₂O₃. The real and imaginary parts of dielectric permittivity follow the identical trend of the decreasing value of dielectric permittivity and dielectric loss with increase in the frequency. The particle size and the dielectric constant show an abnormal trend with different nanofillers. The AC conductivity follows the universal Jonscher power law, and an effective mechanism has been proposed to understand the nanofiller interaction with cation coordinated polymer.     

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe, Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca, Fe, Na)₂(Sb, Ti)₂O₆(O, OH)₇, an antimony-bearing mineral, has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals, including bindheimite, stibiconite, and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm^?1 with a shoulder at 507 cm^?1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356, and 400 cm^?1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm^?1, with a distinct shoulder at 3542 cm^?1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200–3500 cm^?1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as (Ca, Fe²⁺, Na)₂(Sb, Ti)₂(O, OH)₇ xH₂O.     

The effect of LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript> on the complexation with potato starch-chitosan blend polymer electrolytes

This work examines the effect of lithium trifluoromethanesulfonate (LiCF₃SO₃) and glycerol on the conductivity and dielectric properties of potato starch-chitosan blend-based electrolytes. The electrolytes are prepared via solution cast technique. From X-ray diffraction (XRD) analysis, the blend of 50 wt.% starch and 50 wt.% chitosan is found to be the most amorphous blend. Fourier transform infrared (FTIR) spectroscopy studies show the interaction between the electrolyte materials. The room temperature conductivity of pure starch-chitosan film is found to be (2.85 ± 1.31) × 10^?10 S cm^?1. The incorporation of 45 wt.% LiCF₃SO₃ increases the conductivity to (7.65 ± 2.27) × 10^?5 S cm^?1. Further conductivity enhancement up to (1.32 ± 0.35) × 10^?3 S cm^?1 has been observed on addition of 30 wt.% glycerol. This trend in conductivity is verified by XRD and dielectric analysis. The temperature dependence of conductivity of all electrolytes are Arrhenian.     

The intercalation/deintercalation kinetic studies on the structure-integrated cathode material 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2

A cathode material, 0.5Li₂MnO₃ 0.5LiNi_0.5Mn_0.5O₂, was prepared by citric acid-assisted sol–gel method and its electrochemical performance was investigated. It delivered a charge capacity of 270 mAh g^?1 and a discharge capacity of 189 mAh g^?1 in the first cycle. With the increase of current density from 14 to 28 mA g^?1, the discharge capacity dropped severely to 130 mA g^?1. Obviously, the rate capability of the material was inferior to most of the oxide cathode materials. The diffusion coefficient of this material was calculated to be 6.04?×?10^?12 cm² s^?1 from the results of cyclic voltammetry measurements. Moreover, diffusion coefficients between 3.13?×?10^?12 and 1.22?×?10^?10 cm² s^?1 in the voltage range of 3.8–4.7 V were obtained by capacity intermittent titration technique. This, together with the localized Li₂MnO₃ domains in the crystal structure, may validate the poor rate capability.     

EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate

X-band electron paramagnetic resonance (EPR) study of Cr³⁺-doped dipotassium tetrachloropalladate single crystal is done at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters have been evaluated by employing hyperfine resonance lines observed in EPR spectra for different orientations of crystal in externally applied magnetic field. The values of spin-Hamiltonian and zero-field splitting (ZFS) parameters of Cr³⁺ ion-doped DTP for site I are: g _x  = 2.096 ± 0.002, g _y  = 2.167 ± 0.002, g _z  = 2.220 ± 0.002, D = (89 ± 2) × 10^?4 cm^?1, E = (16 ± 2) × 10^?4 cm^?1. EPR study indicates that Cr³⁺ ion enters the host lattice substitutionally replacing K⁺ ion and local site symmetry reduces to orthorhombic. Optical absorption spectra are recorded at room temperature. From the optical absorption study, the Racah parameters (B = 521 cm^?1, C = 2,861 cm^?1), cubic crystal field splitting parameter (Dq = 1,851 cm^?1) and nephelauxetic parameters (h = 2.06, k = 0.21) are determined. These parameters together with EPR data are used to discuss the nature of bonding in the crystal.     

The Translation Mechanism of Smectite to Illite: An Infrared Spectroscopic Study of Ordered Mixed-Layer Illite/Smecite

The infrared spectral characteristics of ordered mixed-layer illite/smectite interstratified clay mineral with different mixed-layer ratios (S% = 5%, 10%, 15%, 20%, 25%, and 30%, where S% is mixed-layer ratio) from the Shihezi Formation of Late Permian in the Hanxing mining area, Hebei province of China, were studied by infrared spectroscopy. The results show that three infrared regions (3625 cm^?1±, 1200–1000 cm^?1, 850–700 cm^?1) changed with S%'s variation. The characteristic absorption bands of smectite at 3640 cm^?1, 1030 cm^?1, and 825 cm^?1 disappeared gradually with the decrease of S%, and the intensity of characteristic absorption bands of illite at 3625 cm^?1, 1100 cm^?1, 1024 cm^?1, 796 cm^?1, and 777 cm^?1 increased. These changes indicated that the illitization of smectite was realized by partial substitution of aluminum iron (Al³⁺) for silicon iron (Si⁴⁺) in silico-oxygen (Si–O) tetrahedron.     

Biopolymeric electrolyte based on glycerolized methyl cellulose with NH<Subscript>4</Subscript>Br as proton source and potential application in EDLC

In the present work, biopolymer electrolyte films based on MC doped with NH₄Br salt and plasticized with glycerol were prepared by solution casting method. Fourier transform infrared (FTIR) spectroscopy analysis confirms the interaction between MC, NH₄Br, and glycerol. X-ray diffraction (XRD) explains that the enhancement of conductivity is affected by the degree of crystallinity. This result is verified by field emission scanning electron microscopy (FESEM). For unplasticized system, sample containing 25 wt% of NH₄Br possesses the highest ionic conductivity of (1.89 ± 0.05) × 10^?4 S cm^?1. The addition of 30 wt% glycerol increases the conductivity value up to (1.67 ± 0.04) × 10^?3 S cm^?1. The conduction mechanism was best presented by the correlated barrier hopping (CBH) model. The linear sweep voltammetry (LSV) and cyclic voltammetry (CV) result confirms the suitability of the highest conducting electrolyte to be employed in the fabrication of electrochemical double layer capacitor (EDLC).     

The development of Li<Superscript>+</Superscript> conducting polymer electrolyte based on potato starch/graphene oxide blend

Solid polymer electrolytes based on potato starch (PS) and graphene oxide (GO) have been developed in this study. Blending GO with PS has improved the ionic conductivity and mechanical properties of the electrolytes. In this work, series of polymer blend consisting of PS and GO as co-host polymer were prepared using solution cast method. The most amorphous PS-GO blend was obtained using 80 wt% of PS and 20 wt% of GO as recorded by X-ray diffraction (XRD). Incorporation of 40 wt% lithium trifluoromethanesulfonate (LiCF₃SO₃) into the PS-GO blend increases the conductivity to (1.48 ± 0.35) × 10^?5 S cm^?1. Further enhancement of conductivity was made using 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). The highest conductivity at room temperature is obtained for the electrolyte containing 30 wt% of [Bmim][Cl] with conductivity value of (4.8?0 ± 0.69) × 10^?4 S cm^?1. Analysis of the Fourier transform infrared spectroscopy (FTIR) spectra confirmed the interaction between LiCF₃SO₃, [Bmim][Cl], and PS-GO blend. The variation of the dielectric constant and modulus studies versus frequency indicates that system of PS-GO-LiCF₃SO₃-[Bmim][Cl] obeys non-Debye behavior.     

Proton-conducting polymer electrolyte based on PVA-PAN blend doped with ammonium thiocyanate

Blending of polymers is one of the most useful methods for modulating the conductivity of solid polymer electrolytes. Blend polymer electrolytes have been prepared with polyvinyl alcohol (PVA)-polyacrylonitrile (PAN) blend doped with ammonium thiocyanate with different concentrations by solution casting technique, using dimethyl formamide (DMF) as the solvent. The prepared electrolytes are characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), ultraviolet (UV), and ac impedance measurement techniques. The increase in amorphous nature of the blend polymer electrolyte by the addition of salt is confirmed by XRD analysis. The complex formation between the polymers and the salt has been confirmed by FTIR analysis. The thermal behavior has been examined using DSC and TGA. The maximum conductivity has been found to be 2.4?×?10^?3 S cm^?1 for 92.5PVA/7.5PAN/25 % NH₄SCN sample at room temperature. The temperature dependence of conductivity has been studied with the help of Arrhenius plot, and the activation energies are calculated. The proton conductivity is confirmed by dc polarization measurement technique. ¹H NMR studies reveal the presence of protons in the sample. A proton battery is constructed with the highest conducting sample, and its open circuit voltage is measured to be 1.2 V     

Raman Spectroscopic Analysis of Perovskite-Structured Alkali Metal Fluorides Containing Nickel and Copper Ions

ABSTRACT

The mixed metal fluorides containing alkali metals have a range of important applications in optical and electronic devices. Raman spectrums of two such fluorides were examined. Raman spectrum of KCuF₃ at 300 K exhibited bands at 261, 295, 363, 468, 519, and 549 cm^?1, indicating site symmetry (orthorhombic) lower than the tetragonal symmetry as observed from the powder X-ray diffraction pattern. Cubic KNiF₃ showed bands at 410, 468, and 657 cm^?1. The first two bands were attributed to the second-order phonon scattering, and the band at 657 cm^?1 was assigned to two-magnon peak.     

Synthesis of Ge-Sn at high pressure and high temperature in a laser-heated diamond anvil cell

Ge–Sn compound is predicted to be a direct band gap semiconductor with a tunable band gap. However, the bulk synthesis of this material by conventional methods at ambient pressure is unsuccessful due to the poor solubility of Sn in Ge. We report the successful synthesis of Ge–Sn in a laser-heated diamond anvil cell (LHDAC) at ~7.6 GPa &; ~2000 K. In situ Raman spectroscopy of the sample showed, apart from the characteristic Raman modes of Ge TO (Г) and β-Sn TO (Г), two additional Raman modes at ~225 cm^?1 (named Ge–Sn₁) and ~133 cm^?1 (named Ge–Sn₂). When the sample was quenched, the Ge–Sn₁ mode remained stable at ~215 cm^?1, whereas the Ge–Sn₂ mode had diminished in intensity. Comparing the Ge–Sn Raman mode at ~225 cm^?1 with the one observed in thin film studies, we interpret that the observed phonon mode may be formed due to Sn-rich Ge–Sn system. The additional Raman mode seen at ~133 cm^?1 suggested the formation of low symmetry phase under high P–T conditions. The results are compared with Ge–Si binary system.     

EPR and Optical Absorption Study of VO2+-Doped Lithium Hydroxylammonium Sulphate

ABSTRACT

Single-crystal and powder EPR studies of VO²⁺-doped lithium hydroxylammonium sulphate (LiNH₃OHSO₄) were carried out at room temperature. The results indicate the presence of two magnetically inequivalent VO²⁺ sites. The VO²⁺ ion takes up a substitutional position in the host lattice. The angular variation of EPR spectra in three mutually perpendicular planes were used to determine the spin Hamiltonian parameters, and the values obtained were the following: For Site 1, g_x = 2.0249 ± 0.0002, g_y = 1.9698 ± 0.0002, g_z = 1.9552 ± 0.0002, A_x = (51 ± 2) × 10^?4 cm^?1, A_y = (93 ± 2) × 10^?4 cm^?1, and A_z = (165 ± 2) × 10^?4 cm^?1; and for Site 2, g_x = 2.0267 ± 0.0002, g_y = 1.9743 ± 0.0002, g_z = 1.9213 ± 0.0002, A_x = (40 ± 2) × 10^?4 cm^?1, A_y = (80 ± 2) × 10^?4 cm^?1, and A_z = (155 ± 2) × 10^?4 cm^?1. The optical absorption spectrum recorded at room temperature shows four bands. From the optical and EPR data, various molecular coefficients are evaluated, and the nature of bonding in the crystal is discussed.