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Lithium chloride

Lithium chloride (LiCl) is an inorganic ionic compound consisting of cations and anions, appearing as a white, crystalline, deliquescent solid with a saline taste. It is highly hygroscopic and exhibits high in (approximately 1 g per 1.3 mL of cold water), as well as solubility in polar solvents like , acetone, and , but is insoluble in nonpolar solvents such as . The compound has a molecular weight of 42.39 g/mol, a of 605 °C, and a of 1382 °C at standard pressure. Lithium chloride is primarily produced from lithium-rich brines through solar evaporation processes, which concentrate and precipitate the compound from saline solutions, often in salt flats or geothermal sources. Alternatively, it can be synthesized by reacting (Li₂CO₃) or (LiOH) with (HCl), yielding LiCl along with byproducts like and . This production is critical for the global lithium supply chain, as lithium chloride serves as a key intermediate in extracting high-purity for various industries. The most significant application of lithium chloride is in the electrolytic production of lithium metal, where it is fused with (KCl) to form a at around 450 °C, enabling the reduction of Li⁺ ions at the . Beyond this, it functions as a in drying systems due to its strong moisture-absorbing properties, as a brazing and flux for aluminum and magnesium alloys, and in to produce red flames from emissions. In and , lithium chloride solutions are used in absorption systems for dehumidification. Additionally, as a lithium salt, it has roles in pharmaceutical contexts, including as an antimanic agent for treatment and in biochemical research as an NMR reference. Due to its and potential to cause gastrointestinal distress or neurological effects upon , handling requires precautions.

Background

History

The element was discovered in 1817 by Swedish chemist Johan August Arfwedson while analyzing the mineral from a mine on the island of Utö, , with confirmation assistance from . Arfwedson identified an component in the mineral that differed from known elements like sodium and , leading to the naming of after the Greek word "lithos" for stone. Around 1818, Arfwedson prepared the first samples of lithium salts—derived from —confirming the new element's chemical properties through various salt formations. In the early , lithium salts, including lithium chloride, found initial medical applications in treating conditions like and , based on their ability to dissolve deposits; British physician Alfred Baring Garrod notably advocated their use in 1859, following his 1847 detection of elevated uric acid in gout patients' blood. Commercial production of lithium metal began in 1923 when Germany's AG pioneered of molten mixed with , marking the shift from laboratory-scale isolation to industrial viability. During the 1940s in the United States, was marketed as a low-sodium for patients on restricted diets, but reports of severe toxicity, including fatalities from and renal failure, prompted the to ban its over-the-counter sale in 1948. Following these incidents, lithium chloride's medical use declined sharply due to safety concerns, leading to a post-1950s pivot toward safer compounds like for psychiatric treatments, particularly after Australian psychiatrist John Cade's 1949 demonstration of its efficacy in , which spurred controlled trials and eventual approvals.

Natural occurrence

Lithium chloride does not occur in nature as a discrete pure compound, but lithium ions (⁺) are present in trace amounts within various s and as dissolved salts, including lithium chloride, in natural s. In forms, is primarily hosted in silicate structures such as (LiAlSi₂O₆) and (K(,Al)₃(Al,Si,Rb)₄O₁₀(F,OH)₂), which are found in deposits formed from late-stage magmatic fluids in granitic rocks. Additionally, associates with clay s like hectorite, a clay (Na₀.₃(Mg,)₃Si₄O₁₀(F,OH)₂), in sedimentary environments linked to volcanic activity. These occurrences represent hard-rock sources of , contrasting with more soluble deposits. The most significant natural sources of lithium chloride are concentrated brines in closed-basin salt lakes, where evaporation in arid regions enriches alongside ions. Notable examples include the Dead Sea in the , with lithium concentrations averaging 30–40 mg/L; the in , , where levels range from 3–60 mg/L depending on lake arm and seasonal variations; in , , at about 10 mg/L; and Clayton Valley in , , with brines typically at 150–200 mg/L. These hypersaline environments, often in tectonic basins, accumulate through from surrounding rocks and evaporative concentration over geological timescales. Lithium also occurs in trace amounts in global water bodies, including at approximately 0.17 ppm and sources varying from 0.001 to 0.2 ppm, influencing minor environmental cycling and human exposure through . Overall, global lithium resources exceed 98 million tons as of 2024 (with 2025 estimates ranging from 96 to 115 million tons), with deposits accounting for the majority—estimated at around 58%—highlighting their dominance in natural lithium distribution. and clay-associated reserves complement these, but brines represent the most economically viable natural concentrations for lithium chloride precursors.

Properties

Physical properties

Lithium chloride appears as a white, odorless, cubic crystalline solid that is highly hygroscopic and deliquescent, readily absorbing moisture from the air to form a corrosive . The form has a molecular weight of 42.39 g/ and a of 2.068 g/cm³ at 25 °C. It exhibits a of 605 °C and a of 1382 °C. The specific heat capacity is 48.0 J/·K at 298.15 K, and the is 1 mm at 547 °C. Lithium chloride is highly soluble in , with a solubility of 83.2 g/100 mL at 20 °C, and also dissolves in polar organic solvents such as (approximately 2.5 g/100 g at 25 °C), acetone (0.83 g/100 g at 25 °C), and , but it is insoluble in nonpolar solvents like and . The compound has a sharp, saline taste.

Chemical properties

Lithium chloride (LiCl) is primarily an ionic compound, consisting of Li⁺ and Cl⁻ ions, but it exhibits partial covalent character owing to the high polarizing power of the small Li⁺ cation, which has an of 76 for sixfold coordination. This polarization of the larger Cl⁻ anion aligns with , which predict increased covalency in bonds involving small, highly charged cations. In terms of reactivity, aqueous solutions of LiCl serve as a source of ions, reacting with to form a white precipitate of according to the equation LiCl + AgNO₃ → AgCl ↓ + LiNO₃. Additionally, anhydrous LiCl readily absorbs gas, forming ammoniate complexes such as Li(NH₃)₄Cl, with up to four equivalents of NH₃ per of LiCl. LiCl is stable under normal conditions and non-flammable, though it emits toxic fumes upon heating to decomposition. Its strong hygroscopic nature leads to deliquescence in humid environments, where it absorbs atmospheric to form a hydrated solution. The behavior of LiCl is dominated by the Li⁺/Li standard of -3.04 V, making an exceptionally strong . This property is exploited industrially in the of molten LiCl (often as a LiCl-KCl eutectic) to produce metal at the , with gas evolving at the .

Structure

Crystal structure

Anhydrous adopts the rock salt (NaCl-type) structure, a common arrangement for ionic halides, featuring a face-centered cubic (FCC) with the Fm\overline{3}m (No. 225). In this structure, lithium cations and chloride anions alternate along each edge of the cubic , forming a three-dimensional stabilized by electrostatic interactions. The conventional unit cell contains four formula units of LiCl (Z = 4). The lattice parameter for this cubic phase is a = 5.14 at 25 °C, as determined from measurements. Within the structure, each ion is octahedrally coordinated to six nearest-neighbor Cl⁻ ions, with a Li–Cl interatomic distance of 2.57 (equivalent to a/2), while each Cl⁻ ion is similarly surrounded by six ions in an octahedral geometry. This symmetric coordination reflects the high ionic character of the compound, contributing to its stability under ambient conditions. Anhydrous LiCl does not exhibit polymorphism at ambient pressures and temperatures, existing solely in this ; theoretical studies predict potential high-pressure or hypothetical polymorphs, but none have been observed experimentally under conditions. At elevated temperatures, the structure remains cubic without transitioning to other polymorphs. The powder diffraction () pattern is diagnostic of the rock salt .

Hydrates and solvates

Lithium chloride forms several crystalline hydrates due to its strong affinity for , including the monohydrate (LiCl·H₂O), dihydrate (LiCl·2H₂O), trihydrate (LiCl·3H₂O), and pentahydrate (LiCl·5H₂O). The dihydrate is less stable than the others. The stability regions of these hydrates vary with temperature in the LiCl-H₂O system. The monohydrate is stable in contact with aqueous solutions from approximately 19 °C up to 93.5 °C, beyond which to the form occurs under dry conditions above 120 °C. The dihydrate forms at lower temperatures, remaining stable up to about 8.5 °C. The trihydrate is stable between 1 °C and -56 °C, while the pentahydrate persists from -56 °C down to the eutectic point at approximately -77 °C, below which coexists with the pentahydrate and saturated solution. In all known hydrates, the Li⁺ cation adopts octahedral coordination, typically involving 3 to 6 molecules and anions to complete the . For instance, the monohydrate features a structure derived from a distorted type with the formula Cl(H₂O)Li□₂ (where □ denotes a vacancy), forming layers linked by bonds between water oxygen atoms and ions. The di- and trihydrates crystallize in structures analogous to NaCl·2H₂O or LiClO₄·3H₂O types, with hydrogen-bonded networks stabilizing the assembly; notably, in the tri- and pentahydrates, one molecule per Li⁺ remains uncoordinated. Lithium chloride also forms solvates with non-aqueous solvents, such as , yielding ammoniates like LiCl·4NH₃ (or Li(NH₃)₄Cl). In these complexes, Li⁺ maintains octahedral coordination by four ammonia molecules, with additional stabilization from chloride ions, enabling stepwise deammoniation upon heating.

Production

Laboratory preparation

Lithium chloride is typically prepared in the laboratory by reacting lithium carbonate with hydrochloric acid in aqueous solution. The balanced equation for this reaction is: \ce{Li2CO3 + 2HCl -> 2LiCl + H2O + CO2 (g)} Lithium carbonate is dissolved in distilled water to form a slurry, and concentrated hydrochloric acid is added dropwise with stirring until carbon dioxide evolution ceases, indicating complete reaction. The resulting solution is filtered to remove any insoluble impurities and then evaporated under reduced pressure or gentle heating to yield hydrated lithium chloride crystals. An alternative route involves the neutralization of with : \ce{LiOH + HCl -> LiCl + H2O} In this method, an of lithium hydroxide is titrated with dilute hydrochloric acid while monitoring the to reach neutrality (approximately 7), followed by to isolate the product. This approach allows precise control and is suitable for smaller scales. To obtain lithium chloride, the hydrated form is dehydrated by heating in a stream of gas at 200–300 °C, which prevents to lithium or hydroxide. This process is conducted in a specialized or tube setup to ensure a dry, inert atmosphere. Purification of the crude product is achieved through recrystallization from hot or acetone, where the lithium chloride dissolves readily and impurities remain insoluble or less soluble. The solution is cooled slowly to promote formation, followed by filtration and drying, typically yielding 90–95% recovery of high-purity material. Lithium starting materials are often sourced from natural mineral deposits such as . All laboratory preparations involving hydrochloric acid must be performed in a well-ventilated fume hood to avoid exposure to corrosive HCl fumes and ensure safe handling.

Industrial production

Lithium chloride is primarily produced on an industrial scale from lithium-rich brines, which account for the majority of global lithium supply. The process begins with solar evaporation in large ponds to concentrate lithium ions while precipitating out impurities such as sodium, potassium, and magnesium salts. The resulting lithium concentrate is then treated with hydrochloric acid to form a lithium chloride solution, which undergoes further processing to yield technical-grade LiCl. Key production sites include the Salar de Atacama in Chile, where brine extraction supports a significant portion of worldwide output. For lithium derived from ores, such as , the production involves high-temperature roasting of the ore at around 1000 °C with to convert it into , followed by and purification to produce . This intermediate is then reacted with to generate lithium chloride: Li₂CO₃ + 2HCl → 2LiCl + CO₂ + H₂O. This route is prominent in hard-rock mining operations, particularly in , where spodumene processing contributes substantially to lithium chemical supply. High-purity grades of lithium chloride, required for advanced applications, are obtained through additional purification steps including , solvent extraction, and membrane separation to remove residual impurities like calcium, magnesium, and . A notable advancement in extraction technology is the 2023 direct lithium extraction (DLE) method developed at , which uses porous polymer strings to selectively capture and crystallize lithium chloride from brines via and , reducing land requirements by over 90% compared to conventional solar evaporation. Anhydrous lithium chloride is produced by dehydrating the hydrated form through gentle heating under a atmosphere, which prevents and ensures high purity. Global lithium production, including chloride forms, reached approximately 180,000 metric tons of lithium content in 2023, with growth driven by demand; lithium chloride specifically supports this expansion as a key intermediate.

Applications

Industrial applications

Lithium chloride serves as an effective in and applications, particularly for aluminum and its alloys in automotive and other processes, by lowering the and aiding in removal. It is typically incorporated into flux compositions at concentrations of 30-45%, often in combination with and other salts to form low-melting eutectics. Due to its hygroscopic nature and low , lithium chloride is widely used as a liquid in systems and industrial processes, where aqueous solutions effectively absorb moisture from air streams. Solutions with 30-45% lithium chloride concentration exhibit strong capabilities, making them suitable for dehumidification in humid climates. The of molten chloride is the primary method for industrial lithium metal production, utilizing a eutectic of 45 wt% LiCl and 55 wt% KCl at around 450 °C to achieve high efficiency and metal purity up to 99.9%. In , chloride imparts a characteristic crimson-red color to flames in and flares through excitation of its . Lithium chloride contributes to the ceramics and sector through its role in fluxing and enhancement, as well as in synthesis as a or in reactions like processes. It also supports the of lithium-based lubricating greases, providing high-temperature stability in industrial applications.

Specialized applications

Lithium chloride serves as a selective precipitant in biochemical applications, particularly for isolating from DNA and proteins in protocols. Solutions of 2 M lithium chloride are commonly employed to precipitate following in vitro transcription or extraction from biological samples, as the salt efficiently recovers while leaving contaminants in solution. This method is integrated into commercial kits for purification, offering a rapid alternative to due to its specificity for larger molecules over short or tRNA. In pharmaceutical contexts, lithium chloride has historical use as an antimanic agent but was discontinued due to ; it is now explored in research for geroprotective effects, potentially extending lifespan through mechanisms like kinase-3 inhibition, though direct clinical use remains limited to other lithium salts such as . In materials synthesis, lithium chloride functions as an additive to accelerate the Stille coupling reaction, a -catalyzed cross-coupling of organotin s with organic halides to form carbon-carbon bonds in . The chloride anion stabilizes the (0) and enhances the rate of , particularly for aryl chlorides, enabling efficient synthesis of pharmaceuticals and materials. Additionally, molten lithium chloride serves as a medium for producing carbon nanostructures; electrochemical reduction in LiCl melts yields carbon nanotubes and sheets by templating graphitic carbon deposition from CO2 or precursors. For crystals, used in and electro-optics, lithium chloride provides a lithium source in flux-growth methods, lowering the and promoting single-crystal formation from mixtures. In , lithium chloride is applied as an to control mites in colonies, addressing a major threat to apiculture. Low-concentration solutions (0.1–1%, equivalent to 0.025–0.25 M) are administered orally via sugar syrup, achieving high mite mortality through systemic uptake by bees while minimizing impact on brood and adults at optimized doses. Field studies demonstrate up to 90% mite reduction in treated hives, positioning it as an alternative to synthetic miticides. Lithium chloride finds utility in research as a reference for (NMR) spectroscopy, where a 1 M solution in oxide (D₂O) is standardized at 0 ppm for ⁷Li NMR, aiding in of lithium-containing compounds. As of 2025, it is emerging in electrolytes, where chloride-based formulations like LiCl-Li₂TiF₆ composites enhance ionic conductivity and mechanical stability, enabling all-solid-state lithium-metal batteries with improved and safety over liquid electrolytes. In , lithium chloride hydrates offer high gravimetric capacity of approximately 1250 Wh/kg, suitable for seasonal heat and cold storage in sorption systems, though challenges like deliquescence require composite encapsulation for practical deployment. Other specialized uses include sensing in hygrometers, where lithium chloride's hygroscopic properties alter electrical in response to relative , enabling precise measurement in devices. Thin films of lithium chloride on conductive substrates form the basis of resistive hygrometers, responding within minutes to vapor changes for applications in cleanrooms and .

Safety and environmental aspects

Health hazards and precautions

Lithium chloride exhibits moderate upon oral exposure, with a reported (LD50) of 526 mg/kg body weight in rats. Ingestion can cause gastrointestinal symptoms including , , profuse , and , as well as central nervous system effects such as tremors, , confusion, and in severe cases, convulsions or . These neurological symptoms typically manifest when serum lithium concentrations exceed 1.5 mEq/L, reflecting the compound's dissociation into lithium ions that affect neuronal function. Chronic exposure to lithium chloride may lead to dysfunction, including , as well as kidney damage and neuromuscular disorders such as and . In the , lithium chloride was briefly marketed as a for individuals with , but this practice resulted in several fatalities due to lithium accumulation and toxicity, prompting the U.S. to issue warnings and prohibit its use in foods in 1949. The primary routes of exposure to lithium chloride are , , and dermal . of dust or aerosols irritates the , potentially causing and pulmonary effects. may result in irritation or burns, while eye exposure leads to serious irritation or corneal damage. poses a particular risk due to its salty taste, which can lead to accidental overconsumption and subsequent ion accumulation in the body. Safe handling of lithium chloride requires the use of , including chemical-resistant gloves, safety goggles, and protective clothing to prevent skin and eye contact. It should be stored in a cool, dry place to avoid moisture absorption, and work areas must provide adequate to minimize inhalation. Although no specific OSHA exists for lithium chloride, general limits apply, such as 15 mg/m³ for total , and workers handling the compound should undergo regular medical monitoring for levels and organ function. Regulatory measures reflect lithium chloride's health risks; the U.S. FDA banned its use as a following the incidents. In the European Union, it is classified as a reproductive category 1A under the , indicating known human hazard for and developmental based on harmonized labeling agreed upon by the .

Environmental impact

The production of lithium chloride through brine evaporation in arid regions, such as the in , consumes approximately 500,000 liters of water per ton of , leading to significant depletion and reduced water availability for local ecosystems and communities. This process exacerbates in already dry areas, altering hydrological balances and impacting in surrounding wetlands and rivers. Due to its high , lithium chloride readily disperses into environments, posing risks to and freshwater . The median lethal concentration (LC50) for is around 120 mg/L, indicating moderate . A 2025 study demonstrated that environmental concentrations of 1–10 mg/L impair reproduction and mitotic processes, potentially disrupting in contaminated waters. Ore processing for lithium chloride generates tailings that contaminate soils with and associated , such as and , reducing and microbial activity. These contaminants can bioaccumulate in plants, with species like absorbing over 300 mg/kg of from mine , raising concerns for terrestrial food chains. Handling and production of lithium chloride release dust particles into the air, contributing to respiratory issues in nearby ecosystems, while the energy-intensive of the process emits 10–20 kg of CO₂ per kg of lithium chloride, amplifying . Mitigation efforts include emerging technologies in 2025 that recover up to 95% of , reducing the need for new , and direct lithium extraction (DLE) methods that cut usage by approximately 70% compared to traditional .

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