Determination of calcium in lithium salts

Two procedures are described for the determination of traces of calcium in lithium salts. In both procedures the calcium is titrated with very dilute EDTA and the end-point is determined fluorometrically with Calcein as indicator. This titration is carried out in the presence of the lithium salt in one procedure; in the other, a preliminary separation of the calcium is made on the chelating exchange resin, Dowex A-1.     

Determination of the water content of foods : Indirect determination of the water content

The indirect determination of the water content of foods is dealt witli on the basis of tlie following general considerations: A. The absolute vapour pressure of the water in the substance to be desiccated ; B. The absolute vapour pressure of the water in the surrounding air, C. Behaviour of the non-water components of the substance to be desicented , D. Special causes of errors, viz.: 1.. Retardation in the establishment of equihbrium; 2. Retardation due to title structure of the substancc to be desiccated, 3. Crust formation; 4. Analytical errors. E. Rate of desiccation: reference methods and rapid routine methods.We prefer to consider the problems relating to the indirect determination of the water content on the basis of absolute water vapour pressures. The advantages and disadvantages of this method of treatment have been indicated.     

Determination of water content by means of the Derivatograph

The determination of water content by means of the Derivatograph is treated in the paper. The determination of water in analytical precipitates, various pharmaceutical products, biological substances, the products of food industry is treated on the basis of some practical examples. The applicability of the Derivatograph for determining the adsorption capacity of industrial adsorbents, the hydration conditions of cement, the system Ca₃A-CaSO₄ · H₂O and the rehydrability of clay minerals is demonstrated. The aluminium oxide barrier layers were investigated on the basis of the water content of the aluminium hydroxide. For the characterization of the different strengths by which water is bound in strontium chloride hydrates the apparent activation energies are also presented.     

Determination of water content by means of the Derivatograph

The determination of water content by means of the Derivatograph is treated in the paper. The determination of water in analytical precipitates, various pharmaceutical products, biological substances, the products of food industry is treated on the basis of some practical examples. The applicability of the Derivatograph for determining the adsorption capacity of industrial adsorbents, the hydration conditions of cement, the system Ca₃A-CaSO₄ · H₂O and the rehydrability of clay minerals is demonstrated. The aluminium oxide barrier layers were investigated on the basis of the water content of the aluminium hydroxide. For the characterization of the different strengths by which water is bound in strontium chloride hydrates the apparent activation energies are also presented.

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Zusammenfassung Die Bestimmung von Wasser mit Hilfe des Derivatographen wurde besprochen. Es wurden die verschiedenen Anwendungsmöglichkeiten der Methode, wie die Bestimmung des Wassers in analytischen Niederschlägen, Arzeneimitteln, Lebensmittel, biologischen Substanzen an Beispielen besprochen. Die Anwendbarkeit des Derivatographen zur Bestimmung der Adsorptionskapazität von industriellen Adsorbenten, der Hydrationsverhältnisse von Zement, des Systems Ca₃A-CaSO₄ · H₂O und der Rehydration von Tonmineralien wurde erörtert. Aluminiumoxydgrenzschichten konnten auf Grund des Wassergehalts des Aluminiumhydroxyds geprüft werden. Zur Charakterisierung der verschiedenen wasserbindenden Kräfte werden die Werte der scheinbaren Aktivierungsenergien der Alkalierdchlorid-hydrate vorgelegt.

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Résumé L'article traite de la détermination de la teneur en eau à l'aide du Derivatograph. La méthode est exposée en se servant d'exemples pratiques comme les précipités analytiques, divers produits pharmaceutiques, alimentaires, des substances biologiques. On montre que le Derivatograph peut être utilisé pour déterminer la capacité d'adsorption des adsorbants industriels, pour examiner l'hydration du ciment, du' système Ca₃A-CaSO₄ · H₂O et la rehydration des minéraux argileux. Examination des couches interfaces d'oxyde d'aluminium sur Ja base de la teneur en eau du hydroxide d'aluminium. L'énergie d'activation apparente a été déterminée et utilisée pour caractériser les différentes forces de liaison de l'eau dans les chlorures alcalino-terreux hydratés.

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Lithium-ion conducting electrolyte salts for lithium batteries

This paper presents an overview of the various types of lithium salts used to conduct Li(+) ions in electrolyte solutions for lithium rechargeable batteries. More emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid-electrolyte interface (SEI) formation towards carbonaceous anodes and the effect of anions on the aluminium current collector. The physicochemical and functional parameters relevant to electrochemical properties, that is, electrochemical stabilities, are also presented. The new types of lithium salts, such as the bis(oxalato)borate (LiBOB), oxalyldifluoroborate (LiODFB) and fluoroalkylphosphate (LiFAP), are described in detail with their appropriate synthesis procedures, possible decomposition mechanism for SEI formation and prospect of using them in future generation lithium-ion batteries. Finally, the state-of-the-art of the system is given and some interesting strategies for the future developments are illustrated.     

Characterization of self-assembled monolayers from lithium dialkyldithiocarbamate salts

We report the formation of self-assembled monolayers (SAMs) onto gold substrates by exposure to lithium dialkyldithiocarbamate salts [(Li+(R2DTC-), where R = n-propyl, n-butyl, n-octyl, n-decyl, n-dodecyl, or n-octadecyl] in ethanol or methylene chloride. The crystallinity and composition of the monolayers were assessed by polarized modulation infrared reflection absorption spectroscopy (PM-IRRAS), wettability was characterized by contact angles of water and hexadecane, thickness was measured by spectroscopic ellipsometry, and barrier properties determined by electrochemical impedance spectroscopy. While the shorter R2DTC-s formed monolayers with liquid-like packing, monolayers prepared from the longest R2DTC- (where R = n-octadecyl) exhibit similar thickness, crystallinity, wettability, and capacitance as monolayers prepared from n-octadecanethiol. The hydrocarbon chains within the monolayers prepared from (C18)2DTC- are less canted on average than those prepared from n-octadecanethiol. Nonetheless, the (C18)2DTC- SAM exhibits an order of magnitude lower resistance against the penetration of redox probes, which is attributed to a higher density of pinhole defect sites.     

Solubilization of SEI lithium salts in alkylcarbonate solvents

The SEI (Solid Electrolyte Interphase) at the surface of electrodes in lithium-ion batteries is composed of various lithium compounds, organic or mineral, which have a direct impact on cycling performance. The main lithium species constituting the SEI and selected in this study are lithium fluoride LiF, lithium carbonate Li₂CO₃, lithium hydroxide LiOH, lithium oxide Li₂O, lithium methoxide LiOCH₃ and lithium ethoxide LiOC₂H₅. Their solubilities were determined in ethylene, propylene, dimethyl, diethyl and vinylene carbonates (EC, PC, DMC, DEC and VC) and in one of their mixtures commonly used in lithium-ion batteries (EC/PC/3DMC) by mean of atomic absorption spectroscopy (AAS). These solutions were also investigated by EIS (Electrochemical Impedance Spectroscopy) and conductimetry measurements. Results show that while solubilization properties differ between LiF and other lithium compounds considered, their association pattern in solution is identical and solutions are mainly constituted of quadrupolar aggregates.     

偏硼酸锂-四硼酸锂熔融-电感耦合等离子体原子发射光谱(ICP-AES)法测定石膏中多组分含量

石膏在我国储量丰富,应用广泛,快速准确分析其成分含量对石膏资源的综合利用具有重要意义。针对酸溶法无法测定SiO2,碱熔法无法测定K2O、Na2O的问题,本文建立一种偏硼酸锂-四硼酸锂熔融-电感耦合等离子体发射光谱法同时测定石膏中CaO、SO3、Al2O3、Fe2O3、MgO、TiO2、K2O、Na2O、SiO2含量。实验优化了熔剂用量、熔融温度,结果表明采用试样与偏硼酸锂-四硼酸锂混合熔剂质量比例1：5,在铂金坩埚中1000 ℃熔融10 min,在超声条件下,于50 mL 10 %盐酸中浸取熔融物,能够有效分解试样而浸取待测组分。向标准溶液系列中加入偏硼酸锂-四硼酸锂-盐酸基体溶液以消除基体对测试结果的影响。各待测组分的校准曲线的相关性系数均大于0.9990,方法检出限在3~292 μg/g范围内;采用实验方法分别对国家一级标准物质GBW03109a、GBW03110和实际样品进行测定,标准物质的5次平行测试的相对标准偏差在0.14 %~8.86 %之间,测定结果的相对误差在0.03~8.75 %之间,测试结果与标准值无显著性差异;实际样品中各成分测定值的RSD（n=5）为0.24~8.80 %。该方法操作简单、准确度高、精密度好、检出限低,可以同时测定石膏中的多组分含量,能够为石膏资源综合利用调查评价提供一定的技术支撑 。     

Quantitative analysis of the hydration of lithium salts in water using multivariate curve resolution of near-infrared spectra

The hydration process of lithium iodide, lithium bromide, lithium chloride and lithium nitrate in water was analyzed quantitatively by applying multivariate curve resolution alternating least squares (MCR-ALS) to their near infrared spectra recorded between 850 nm and 1100 nm. The experiments were carried out using solutions with a salt mass fraction between 0% and 72% for lithium bromide, between 0% and 67% for lithium nitrate and between 0% and 62% for lithium chloride and lithium iodide at 323.15 K, 333.15 K, 343.15 K and 353.15 K, respectively. Three factors were determined for lithium bromide and lithium iodide and two factors for the lithium chloride and lithium nitrate by singular value decomposition (SVD) of their spectral data matrices. These factors are associated with various chemical environments in which there are aqueous clusters containing the ions of the salts and non-coordinated water molecules. Spectra and concentration profiles of non-coordinated water and cluster aqueous were retrieved by MCR-ALS. The amount of water involved in the process of hydration of the various salts was quantified. The results show that the water absorption capacity increases in the following order LiI < LiBr < LiNO₃ < LiCl. The salt concentration at which there is no free water in the medium was calculated at each one of the temperatures considered. The values ranged between 62.6 and 65.1% for LiBr, 45.5–48.3% for LiCl, 60.4–61.2% for LiI and 60.3–63.7% for LiNO₃. These values are an initial approach to determining the concentration as from which crystal formation is favored.     

Electronic structure calculations on lithium battery electrolyte salts

New lithium salts for non-aqueous liquid, gel and polymeric electrolytes are crucial due to the limiting role of the electrolyte in modern lithium batteries. The solvation of any lithium salt to form an electrolyte solution ultimately depends on the strength of the cation-solvent vs. the cation-anion interaction. Here, the latter is probed via HF, B3LYP and G3 theory gas-phase calculations for the dissociation reaction: LiX <--> Li(+) + X(-). Furthermore, a continuum solvation method (C-PCM) has been applied to mimic solvent effects. Anion volumes were also calculated to facilitate a discussion on ion conductivities and cation transport numbers. Judging from the present results, synthesis efforts should target heterocyclic anions with a size of ca. 150 A(3) molecule(-1) to render new highly dissociative lithium salts that result in electrolytes with high cation transport numbers.     

A mild hydrolysis of esters mediated by lithium salts

When treated with amine bases such as triethylamine and various lithium salts in wet solvents, esters are efficiently hydrolyzed to the corresponding acids in good yields. Esters incorporating an α- or β-heteroatom with respect to the ester carbonyl group are hydrolyzed rapidly even at room temperature. To further demonstrate the usefulness of this method, one example is provided where hydrolysis of acetylated camphorsultam is mediated by LiBr.     

Determination of freezable water content of beef semimembranous muscle DSC study

The freezable water contents of samples obtained from previously chilled semimembranous muscle of middle-aged beef carcasses after a 24 h cooling period a room at in 5±1C were determined by differential scanning calorimetry (DSC) at –5, –10, –15, –20, –30, –40, –50 and –65C. This was accomplished by freezing the samples at the above-mentioned temperatures, followed by thawing to 35C, and measuring the melting peaks of freezable water. The areas of these peaks were determined by using the peak integration method programs through a computer linked to the DSC, and they were then used to determine the latent heat of melting (H _m) in kJ kg^–1 at each freezing temperature. The resultant latent heat of melting per sample was divided by the latent heat for pure water to determine the amount of freezable water present in these samples. This amount of freezable water was divided by the total water content of the meat sample to determine the percentage of freezable water in the sample. The percentage of freezable water was subtracted from 100 to determine the percentage of bound water present in the sample.     

Physicochemical and electrochemical properties of sulfolane solutions of lithium salts

The physicochemical and electrochemical properties (electrical conductivity, viscosity, density, and electrochemical stability) of sulfolane solutions of various lithium salts are studied. The nature of the anion considerably affects the physicochemical and electrochemical properties of the electrolyte systems considered. Sulfolane solutions of lithium salts have moderate electrical conductivity and high electrochemical stability, and can be used as electrolytes in lithium batteries.     

Phase behaviour of lithium and sodium salts of phenylstearic acid

Phenylstearic acid, prepared from oleic acid and benzene, using the Friedel-Crafts reaction, has been confirmed to be a reproducible mixture of twelve positional isomers. Lithium and sodium salts of this acid are semi-crystalline solids which behave in many ways like pure single substances. The thermotropic polymorphism of these soaps has been studied using DSC and polarizing microscopy (as well as X-ray diffraction and ⁷Li NMR spectroscopy for the former soap). Both soaps exhibit characteristic stepwise melting behaviour and form stable reversed hexagonal mesophases at elevated temperatures, in contrast to the lamellar phases exhibited by the unsubstituted soaps.     

单离子导体聚合硼酸锂盐的研究进展

目前商业化锂离子电池常用的锂盐LiPF6,对水极其敏感,热稳定性差,尤其是在高温条件下的应用存在着一定的安全隐患.种类多且环境友好的新型有机硼酸锂盐越来越受到人们的重视.本文综述了近年来几种锂盐的合成方法,电化学性能,各自存在的优点和不足以及本课题组在聚合硼酸锂盐方向取得的系列研究进展,并对锂盐和聚合物电解质的发展方向进行了展望.     

New family of lithium salts for highly conductive nonaqueous electrolytes

New lithium salts of weakly coordinating anions were prepared by treating lithium imidazolates or LiN(CH3)2 with 2 equiv of BF(3). They are LiIm(BF3)2, Li 2-MeIm(BF3)2, Li 4-MeIm(BF3)2, LiBenzIm(BF3)2, Li 2-iPrIm(BF3)2, and LiN(CH3)2(BF3)2 (Im=imidazolate, Me=methyl, iPr=isopropyl, BenzIm=benzoimidazolate). The salts were characterized by NMR spectroscopy and mass spectrometry. The structure of LiBenzIm(BF3)2 consists of a dimeric centrosymmetric unit with each lithium atom forming a bridge between the two anions through one fluorine contact to each anion. The structure of a hydrate of LiN(CH3)2(BF3)2 consists of an infinite chain in which each anion chelates two different lithium atoms through Li-F bonds. The conductivities of electrolyte solutions of these salts were measured and are discussed in terms of different ion-pairing modes determined from the solid-state structures, the anion's ability to distribute charge, and solution viscosity. Organic carbonate solutions of LiIm(BF3)2 partially disproportionate at 85 degrees C forming LiBF4, LiBF2[Im(BF3)]2, and Li[(BF3)ImBF2ImBF2Im(BF3)], reaching equilibrium by 3 months at 85 degrees C but not disproportionating at room temperature after 9 months. A mechanism for the formation of these disproportionation products is proposed. The lower conductivity of the 1 M LiIm(BF3)2 solution that has undergone disproportionation is attributed to the formation LiBF4, which is less conductive, and LiBF2[Im(BF3)]2 and Li[(BF3)ImBF2ImBF2Im(BF3)], which increase solution viscosity.     

Determination of lithium in sea water by atomic absorption and by flame emission spectrophotometry

Summary Comparison of two instrumental methods for the analysis of lithium in sea water showed that both atomic absorption and flame emission spectrophotometry can be used without pretreatment of the sample. The interference of the other constituents of sea water in the analysis has been studied. Calibrations using an artificial sea water or the standard addition method may be used.

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Zusammenfassung Ein Vergleich der beiden Methoden hat gezeigt, daß zur Analyse von Lithium im Meerwasser sowohl die Atomabsorptionsspektrophotometrie, als auch die Flammenspektrophotometrie ohne Vorbehandlung der Probe angewendet werden können. Der Einfluß der anderen Bestandteile des Meerwassers auf die Analyse wurde untersucht. Für die Eichung des Verfahrens wurde künstliches Meerwasser sowie die Methode des Standardzusatzes verwendet.

     

Organomercury compounds XX Reactions of lithium polyfluorobenzenesulphinates with mercuric salts

The lithium polyfluorobenzenesulphinates, Li O₂SR (R = C₆F₅, $\text{p}$-HC₆F₄, $\text{m}$-HC₆F₄, or $\text{o}$-HC₆F₄), and the dilithium tetrafluorobenzenedisulphinates, $\text{p}$- and $\text{o}$-(LiO₂S)₂C₆F₄, have been prepared by reaction of the appropriate polyfluoroaryllithium compounds with sulphur dioxide. All compounds were isolated as hydrates and gave the corresponding $\text{S}$-benzylthiouronium salts on treatment with $\text{S}$-benzylthiouronium chloride. From reactions of the lithium sulphinates with suitable mercuric salts in water, generally at room temperature, the derivatives RHgX (R = C₆F₅, X = Cl, Br, CH₃CO₂, or PhSO₂; R = $\text{p}$-HC₆F₄, X = Cl, Br, or CH₃CO₂; R = $\text{m}$-HC₆F₄, X = Cl or Br; R = $\text{o}$-HC₆F₄, X = Cl), $\text{p}$-(XHg)₂C₆F₄ (X = Cl, Br, or CH₃CO₂), and $\text{o}$-(XHg)₂C₆X₄ (X = Cl or Br) have been prepared. Similarly, the bispolyfluorophenylmercurials R₂Hg (R = C₆F₅, $\text{p}$-HC₆F₄, or $\text{m}$-HC₆F₄) have been prepared from the corresponding lithium sulphinates and either mercuric salts or polyfluorophenylmercuric halides in aqueous $\text{t}$-butanol. A possible mechanism for the sulphur dioxide elimination reactions is discussed.     

Electrochemical characteristics of the blended polymer electrolytes containing lithium salts

Blend-based polymer electrolytes composed of poly(ethylene oxide), poly(oligo[oxyethylene]oxysebacoyl), and lithium salts have been prepared. These polymer electrolytes have been investigated in terms of ionic conductivity, transport number, and interfacial characteristics of the lithium electrode in contact with the polymer electrolyte. The influences of the blend composition, the salt used, and its concentration on the electrochemical behavior were studied. © 1996 John Wiley & Sons, Inc.