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Potassium bitartrate

Potassium bitartrate, also known as potassium acid tartrate or cream of tartar, is the potassium acid salt of L-(+)-, a naturally occurring found in grapes and other fruits. It has the chemical formula C₄H₅KO₆, a molecular weight of 188.18 g/mol, and the CAS number 868-14-4. This compound typically appears as a white crystalline or granulated powder, with a slightly acidic of approximately 3.4 to 3.6 in , and it is soluble in (about 6% at 100°C) but insoluble in . As a byproduct of , potassium bitartrate forms naturally during the process from in lees, sediment, or press cake, and is extracted through without chemical alteration, yielding a purity of over 99.5%. In the , it is affirmed as (GRAS) by the U.S. (FDA) under 21 CFR 184.1077 and serves as a versatile additive for control, stabilization, action, and as a in baking powders and products. Its inclusion on the National List of the USDA's National Organic Program allows its use in certified organic processed foods, with typical daily intake estimated at around 30 mg per person in the U.S. Beyond culinary applications, functions as a in , such as producing , , silver, and nanoparticles from their respective salts. It also acts as a in dyeing and metal processing, and has historical and modern uses in laxatives and even as an ingredient in certain contraceptive formulations like Phexxi, where it is FDA-approved. Safety assessments indicate low toxicity, with no significant hazards at typical levels, though excessive could lead to potassium overload. Internationally, it is permitted by regulatory bodies such as and the for similar food and industrial purposes.

Chemical Properties and Structure

Molecular Formula and Structure

Potassium bitartrate has the molecular formula \ce{KC4H5O6}, consisting of a cation (\ce{K+}) and a anion (\ce{HC4H4O6^-}). The anion derives from L-tartaric acid (\ce{C4H6O6}) through monodeprotonation, retaining one group (\ce{-COOH}) and converting the other to a (\ce{-COO-}), with two hydroxyl groups attached to the central chiral carbons. This structure imparts the compound's acidic character and properties relevant to its applications. The IUPAC name for potassium bitartrate is (2R,3R)-2,3,4-trihydroxy-4-oxobutanoate, reflecting the specific at the C2 and C3 positions of the backbone. It is also known by synonyms such as and, in culinary use, cream of tartar. In its solid state, potassium bitartrate forms colorless crystals in the orthorhombic system with P2_12_12_1 (Z = 4) and dimensions a = 7.6065(5) , b = 7.7599(5) , c = 10.6054(7) . The anion adopts a conformation where the four-carbon chain is nearly extended, with the two hydroxyl groups in antiperiplanar orientation and the carboxylic groups positioned for intermolecular interactions. Strong O–H···O bonds link the proton of one anion to a oxygen of an adjacent anion, forming infinite zigzag chains along the c-axis; additional weaker bonds involve the hydroxyl groups, stabilizing layered arrangements. Each cation is coordinated to eight oxygen atoms from six anions, bridging the chains into a three-dimensional network. The molecular structure can be visualized as a linear chain: \ce{^{-}OOC-CH(OH)-CH(OH)-COOH}, where the and termini enable the characteristic hydrogen-bonded chains, and the vicinal segment contributes to the compound's and rigidity.

Physical Characteristics

Potassium bitartrate is a white crystalline powder that is odorless and exhibits a slight acidic . It exists as a solid at . The compound has a molecular weight of 188.18 g/mol and a of 1.984 g/cm³. Upon heating, it decomposes at approximately 267 °C without a distinct . In commercial forms, particularly for applications, it is supplied as a fine powder to ensure uniform distribution and ease of use.

Solubility and Stability

Potassium bitartrate exhibits limited in , with approximately 0.57 g dissolving in 100 mL at 20°C, increasing to about 6.1 g per 100 mL in boiling . It is practically insoluble in and , which contributes to its precipitation in alcoholic solutions like wine. The solubility product constant (Ksp) for the dissociation KHC₄H₄O₆ ⇌ K⁺ + HC₄H₄O₆⁻ is on the order of 10^{-3} at 25°C, reflecting its sparingly soluble nature in aqueous media. In solution, potassium bitartrate forms acidic conditions due to the partial ionization of the hydrogen tartrate ion, with values derived from at 3.04 (first dissociation) and 4.37 (second dissociation) at 25°C. This acidity influences its behavior in buffered systems, maintaining a typically around 3.5 in saturated aqueous solutions. Potassium bitartrate is thermally stable up to about 200°C, beyond which it decomposes, releasing carbon oxides and other products. It shows slight hygroscopicity, absorbing moisture from the air which can lead to caking if not stored properly, though it remains stable for extended periods under dry conditions. For optimal shelf life, it should be kept in a cool, dry environment in sealed containers to prevent moisture-induced clumping.

History and Discovery

Early Uses in

Potassium bitartrate, commonly referred to as cream of tartar or wine diamonds, naturally precipitates as crystals during the process, particularly after when temperatures drop, leading to potential or formation in the wine if left unaddressed. This compound arises from the present in grapes, combining with ions to form insoluble crystals that can adhere to bottle walls or float in the liquid, affecting clarity and appearance. Archaeological analyses of ancient jars, such as those from Abydos dating to around 3150 BCE and Tutankhamun's tomb (circa 1323 BCE), reveal residues of s (such as calcium ), indicating the early production of grape-based wine where potassium bitartrate forms as a byproduct. In these prehistoric and ancient practices, winemakers observed the formation of during storage and in large clay amphorae, recognizing it as an undesirable deposit that clouded the beverage. techniques focused on basic separation methods, with wine often left to settle naturally before being racked—transferred via siphons or pouring from one jar to another—to leave the heavy dregs behind, thereby improving clarity without advanced chemical intervention. By the Roman era (circa 500 BCE to 500 CE), these observations evolved into more systematic approaches, as documented by agronomist Lucius Junius Moderatus Columella in his De Re Rustica (circa 65 CE), where he describes the sediment as "lees" and recommends fining with roasted salt or seawater to coagulate and precipitate impurities, including tartrate crystals, facilitating easier removal. Racking remained a core pre-industrial method, involving multiple transfers between dolia (large earthenware vessels) to decant clear wine from the accumulated bitartrate sediment at the bottom, a practice that enhanced stability and prevented haze during aging or transport across the empire. These techniques, though rudimentary, laid the foundation for tartrate management, prioritizing practical sedimentation over scientific understanding of the compound.

Isolation and Naming

Potassium bitartrate, long observed as a deposit in , underwent formal scientific isolation and characterization in the late . Swedish chemist first isolated from the substance in 1769 by boiling cream of tartar with to form insoluble calcium , which was then treated with to liberate the free acid; this process established cream of tartar as the potassium salt of . 's experimental results were detailed in a 1770 publication by Anders Jahan Retzius in the proceedings of the , marking the compound's entry into systematic chemical study. Antoine Lavoisier advanced this understanding in his 1789 treatise Elements of Chemistry, where he classified as one of eighteen simple acids and integrated it into his oxygen-based theory of acidity, emphasizing empirical analysis over phlogiston concepts. Lavoisier's work on and purification techniques for acids, including derived from the salt, helped solidify its place in the emerging framework of modern chemistry. The naming of the compound reflects its origins and gradual scientific refinement. The vernacular term "cream of tartar" arose from the crème de tartre, describing the creamy-white, encrusted sediment that forms on the interior of wine vats during and is scraped away for purification into a . The word "" traces to tartarum, denoting the dregs or hard deposit from wine or other fermented liquids, a usage to the 14th century. This practical name persisted through the 18th century due to the compound's appearance and source in grape residues. In the , systematic supplanted common names, with playing a pivotal role in recognizing potassium bitartrate as the of during his studies of organic compounds in the . Berzelius introduced the elemental symbol K for in 1814 and advocated for empirical formulas, representing the compound as KC₄H₅O₆; his electrochemical dualistic theory and precise analytical methods confirmed its composition as a hydrogen tartrate . This led to the adoption of the formal names potassium bitartrate and potassium hydrogen tartrate, aligning with the era's emphasis on stoichiometric precision. Early synthesis attempts, beginning around the , involved neutralizing with or to form the , enabling production independent of natural sources.

Natural Occurrence and Sources

In Grapes and Wine

Potassium bitartrate, also known as cream of tartar, primarily originates in grapes through the biosynthesis of tartaric acid during berry ripening, where it combines with potassium ions absorbed from the soil by the vine roots. In grapevines (Vitis vinifera), tartaric acid is synthesized from L-ascorbic acid via the Smirnoff-Wheeler pathway in the cytosol of leaf and berry cells, involving key enzymes such as L-idonate dehydrogenase (L-IDH) that convert intermediates like 2-keto-L-gulonate and L-idonate into tartaric acid. This process peaks in immature berries, with tartaric acid then stored in vacuoles as the stable potassium bitartrate salt to prevent its degradation during maturation. Potassium uptake occurs primarily through the roots via xylem and phloem transport, accumulating in berry mesocarp cells where it exchanges with protons on tartaric acid molecules, facilitating salt formation. In , concentrations typically range from 4 to 8 g/L at harvest, primarily in the form of its , potassium bitartrate, which contributes to the juice's acidity and of 2.9–3.8. During , and cooling can lead to , as the of potassium bitartrate decreases at lower temperatures (approximately 5.5 g/L at 20°C but much lower near freezing), prompting the formation of visible crystals. These crystals, often appearing as harmless "wine diamonds," can affect wine clarity and stability if not managed, influencing sensory qualities like freshness and microbial resistance. To ensure wine stability, the cold stabilization process is employed, where wine is chilled to around -4°C for several days to induce controlled precipitation of potassium bitartrate crystals, which are then removed by racking or filtration. This step is crucial for preventing post-bottling crystallization, particularly in high-acid wines. Varietal differences influence potassium bitartrate levels, with white wine varieties like exhibiting higher concentrations of (up to 10 g/L in some cases) compared to reds like , due to genetic factors and quantitative trait loci on chromosomes LG7 and LG4. This results in greater risk in wines, necessitating more rigorous stabilization.

Other Natural Deposits

Potassium bitartrate, also known as potassium hydrogen tartrate, occurs naturally in trace amounts in certain fruits beyond grapes, particularly in the pulp of tamarind (Tamarindus indica), where it constitutes approximately 8% of the dry weight alongside tartaric acid and other organic acids. This presence arises from the fruit's biochemical composition, which includes potassium ions binding with tartaric acid during maturation. Similar trace occurrences have been noted in other fruits rich in tartaric acid, such as bananas and avocados, though at much lower concentrations and typically not in the precipitated bitartrate form. In fermented products from non-grape sources, such as tamarind-based beverages or other fruit ferments containing precursors, potassium bitartrate can form as a minor precipitate under conditions of , mirroring processes in biological systems. These occurrences are generally limited to organic matrices and do not constitute significant deposits. Although historically referred to as "tartrite" in obsolete for salts of , potassium bitartrate is rare as a distinct and is not commonly associated with geological formations like evaporites or volcanic soils. No verified records exist of commercial mining for natural tartar deposits, including in regions like , which are better known for other potassium-bearing minerals. Modern detection of potassium bitartrate in natural samples relies on spectroscopic techniques, such as (IR) spectroscopy, which identifies characteristic absorption bands for the group, or Fourier-transform (FTIR) analysis for confirmation in fruit pulps and organic residues. These methods enable precise quantification in trace amounts without destructive sampling.

Production Methods

Industrial Extraction from Wine

Potassium bitartrate, commonly known as cream of tartar, is industrially extracted as a valuable from operations, primarily from wine lees (sediment consisting of dead , pulp, and seeds) and argol (crude crystalline deposits formed on the sides of wine barrels and vats during and aging). These materials contain significant amounts of potassium bitartrate, typically 20-50% in lees and up to 80-90% in argol, making them ideal feedstocks for large-scale recovery. The process leverages the temperature-dependent of potassium bitartrate—highly soluble in hot (about 6.1 g/100 mL at 100°C) but sparingly so in cold conditions—to achieve efficient separation without the need for chemical reagents or solvents. The extraction begins with preprocessing: wine lees are dried and ground to facilitate handling, while argol is mechanically scraped and collected. The raw material is then mixed with hot potable (70-100°C) in large dissolvers or extraction tanks, where stirring at 700-1000 rpm dissolves the potassium bitartrate over 10-30 minutes. Insoluble residues, such as skins and debris, are removed via hot filtration using cartridge filters (e.g., 5 μm pore size with or carbon aids for clarity). The resulting clear solution is transferred to cooling crystallizers, where it is rapidly cooled to 10-20°C over several hours, often monitored by sensors to detect formation. To induce and accelerate , the solution is seeded with pre-formed potassium bitartrate s (typically 1-5% by weight), promoting and growth for uniform crystal size. The precipitated crystals are separated using centrifuges or rotary vacuum filters, washed to remove impurities, and dried at 105°C to yield crude potassium bitartrate. Further purification refines the crude product—often referred to as —into high-purity potassium bitartrate suitable for , pharmaceutical, and industrial applications. This involves redissolving the crystals in hot water, treating with for decolorization if needed, and subjecting the solution to ion-exchange resins to eliminate residual ions like sulfates. The purified solution is then concentrated under vacuum and recrystallized through controlled cooling, again with to ensure consistency. Modern facilities employ centrifuges for efficient solid-liquid separation and jacketed cooling tanks equipped with coils (e.g., 1-2 kW capacity) for precise temperature control, enabling batch sizes up to several tons. Yields from this process typically reach 80-90% of available potassium bitartrate from the raw material, with final purity exceeding 99.5% after recrystallization, meeting food-grade standards such as those set by the FDA (21 CFR 184.1077). Global production of potassium bitartrate is closely tied to the wine industry, with major output originating from leading grape-producing nations like , , and , where annual wine volumes exceed 40 million hectoliters combined. These countries account for over 60% of worldwide supply, processing millions of tons of lees and argol annually to generate an estimated 20,000-30,000 tons of refined product, supporting a market valued at approximately USD 200-300 million. This extraction not only valorizes waste but also complies with environmental regulations by reducing landfill disposal of organic byproducts.

Synthetic Synthesis

Potassium bitartrate can be synthesized through chemical routes that avoid natural sources, beginning with the production of precursors followed by neutralization and . The first synthetic routes to emerged in the early , driven by the need for consistent supply independent of agricultural variability; for instance, chemical oxidation methods using as a starting material were investigated as early as the 1920s to produce racemic . These developments allowed for scalable , with refining the approach for commercial viability. Synthetic , the key precursor, is primarily obtained via oxidation of or , often using in the presence of catalysts like sodium to yield DL-tartaric acid. Alternatively, biotechnological methods involve of glucose using molds such as species, first reported in , which oxidizes glucose to intermediates like 5-keto-D-gluconate before conversion to L-tartaric acid. These routes enable high-purity tartaric acid suitable for further processing into potassium bitartrate. The core reaction for forming potassium bitartrate involves partial neutralization of tartaric acid with potassium hydroxide, proceeding as follows: \text{H}_2\text{C}_4\text{H}_4\text{O}_6 + \text{KOH} \rightarrow \text{KHC}_4\text{H}_4\text{O}_6 + \text{H}_2\text{O} Tartaric acid is dissolved in water, and an equimolar amount of potassium hydroxide is added to achieve a pH of approximately 3.5–4.0, ensuring monobasic salt formation; potassium carbonate can substitute for hydroxide, releasing carbon dioxide during the reaction. The solution is then cooled to induce crystallization of potassium bitartrate, which is filtered, washed, and dried. On a laboratory scale, this process involves small-batch operations with precise (typically 0–5°C for ) to yield high-purity product, often exceeding 99% for analytical or pharmaceutical applications where impurities from could compromise efficacy. Industrial synthetic production scales this up using continuous reactors for neutralization and automated , offering advantages in purity and consistency for sectors demanding contaminant-free material, though it remains less common than wine-derived methods due to cost.

Applications and Uses

Culinary and Baking Applications

Potassium bitartrate, commonly known as cream of tartar, serves as an acidic component in baking that reacts with baking soda (sodium bicarbonate) to produce carbon dioxide gas, facilitating the leavening process in doughs and batters. This acid-base reaction is essential for creating light, airy textures in baked goods. \ce{KHC4H4O6 + NaHCO3 -> KNaC4H4O6 + H2O + CO2} In culinary applications, it stabilizes whipped egg whites by lowering the , which helps maintain structure and volume in items like meringues and angel food cakes. Additionally, it inhibits sugar crystallization during , resulting in smoother textures for confections such as or . Typical dosages in baking recipes range from 1/8 per for stabilization to about 1/2 per of substitute for leavening, often scaled to roughly 2/3 per of when combined with . In cookies, it contributes a tangy and enhances the chewy by reacting with and preventing excessive spreading. As a , potassium bitartrate is designated E336 in the and is affirmed as (GRAS) by the U.S. for use in various food products.

Household and Cleaning Uses

Potassium bitartrate, commonly known as cream of tartar, serves as a mild acidic and agent in , effectively removing , stains, and buildup from metals and other surfaces without harsh chemicals. Its acidity helps dissolve oxidation on aluminum and complexes iron in stains, while its fine powder texture provides gentle scrubbing action. When mixed with baking soda or , it forms effervescent pastes or solutions that enhance polishing and stain removal. For cleaning aluminum cookware and coffee pots, fill the item with hot water and add 2 tablespoons of cream of tartar per ; bring to a boil and let sit for 10-15 minutes before scrubbing and rinsing, which removes discoloration and deposits safely without damaging the surface. To polish or items, prepare a paste by mixing equal parts cream of tartar and lemon juice, apply it to the surface, allow it to sit for 5 minutes, then rinse with warm water; this method by reacting with metal oxides. For stainless steel pans, a simple paste of cream of tartar and water can be used to scrub away stuck-on residues, followed by rinsing for a streak-free finish. Rust and hard water stains in bathtubs or on porcelain sinks respond well to a paste made from cream of tartar and white vinegar; apply, let it fizz for several minutes to loosen deposits, then wipe clean—these mixtures are suitable for light-colored surfaces and should be rinsed thoroughly to avoid residue. For fabric stains like rust spots, sprinkle cream of tartar directly on the area and squeeze on a few drops of lemon juice before laundering, which helps lift iron particles without bleaching. To maintain drains, combine 1 cup baking soda, 1/4 cup cream of tartar, and 1 cup salt, then pour a few tablespoons down the drain weekly; the reaction produces carbon dioxide bubbles that dislodge minor clogs. Cream of tartar is widely available in food-grade form at grocery stores and is safe for these household applications when used as directed, though it should be tested on small areas of delicate surfaces first.

Pharmaceutical and Medicinal Uses

Potassium bitartrate serves as a key component in formulations, particularly when combined with to produce carbon dioxide-releasing suppositories for the relief of occasional . This combination induces bowel contractions through mechanical distension caused by gas formation, providing a gentle purgative effect. For example, in products like Ceo-Two suppositories, it is present at 0.9 g alongside 0.6 g of , and it is recognized as a medicinal ingredient in such carbon dioxide-releasing s at doses of 0.9 g or more daily when paired with . In pharmaceutical applications, potassium bitartrate functions as a buffering agent in oral syrups and suspensions to maintain stability, and as a stabilizer in effervescent tablets where it aids in controlled release and . It is also employed as an in various tablet formulations, including extended-release versions of medications like zolpidem tartrate (e.g., Ambien CR), contributing to structural integrity and processing efficiency. Additionally, in non-hormonal contraceptive products such as Phexxi vaginal gel, it is combined with and at 20 mg per 5 g dose to create an acidic environment that immobilizes sperm, preventing pregnancy as an on-demand method. Historically, has been used since the as a and mild in human remedies, often derived from wine byproducts for its purgative properties. In modern , it continues to be applied as a and for domestic animals, though caution is advised due to potential risks in high doses. These uses underscore its role in both therapeutic and formulation contexts, supported by its approval as a substance by regulatory bodies like the FDA.

Industrial and Chemical Applications

Potassium bitartrate serves as a in metallurgical processes, particularly in fire assays for precious metals, where it acts as a to facilitate the separation of metals from ores by lowering the of the mixture and preventing oxidation. In historical contexts, impure forms like argol were combined with and for fluxes during the 16th and 17th centuries, aiding in the cleaning and flow of molten metals. Modern applications extend to galvanic and metal coloring, where it functions as a agent to inhibit oxidation on metal surfaces. In , potassium bitartrate is employed as a precipitant in volumetric methods for determination, forming insoluble potassium bitartrate crystals that allow quantitative analysis through or . It also serves as a standard in buffered solutions, providing a point for acidity measurements due to its consistent and ionization properties in aqueous media. Additionally, it reduces in chemical preparations, such as mordants, by acting as a mild to control reaction rates and prevent excessive oxidation. Within the , potassium bitartrate functions as a adjuster in dye baths, acidifying solutions to optimize uptake and color fastness on fibers like , while also serving as a to enhance adhesion and prevent fabric degradation during processing. In mordanting, it softens fibers and moderates the uptake of metallic mordants, contributing to brighter and more stable hues in natural dyeing processes. Potassium bitartrate is utilized as a in photographic developers, where it retards the development rate in alkaline solutions to improve and prevent overexposure, often incorporated into fixing agents for consistent processing. Its buffering capacity maintains optimal pH levels during emulsion , ensuring uniform reduction without fogging. Non-food industrial applications consume significant quantities, with bulk production supporting factory-scale operations in chemical processing and manufacturing, though exact volumes vary by region and sector.

Safety and Regulatory Aspects

Toxicity and Handling

Potassium bitartrate exhibits low acute toxicity via oral administration, with an LD50 value exceeding 3 g/kg in animal models, indicating minimal risk from ingestion at typical exposure levels. In powder form, it acts as a mild irritant to the eyes and skin upon direct contact, potentially causing redness, discomfort, or temporary inflammation, though severe effects are uncommon. Exposure risks primarily involve inhalation of dust, which can lead to irritation, coughing, or in sensitive individuals or during prolonged handling without protection. Ingestion is generally safe in small amounts used in applications, but excessive can result in purgative effects, promoting bowel movements due to its mild properties, as historically utilized in medical contexts. Systemic toxicity from absorption is low, with no significant chronic effects reported at occupational or dietary exposures. Safe handling requires the use of (PPE), including gloves, safety goggles, and a or in dusty environments to minimize , eye, and risks. should occur in a cool, dry, well-ventilated area in tightly sealed containers to prevent moisture absorption and caking, which could increase dust generation. Spill cleanup involves vacuuming or wet sweeping to avoid airborne particles, followed by thorough washing of contaminated surfaces. Regulatory limits treat potassium bitartrate as a under OSHA standards, with a (PEL) of 15 mg/m³ for total over an 8-hour workday. In food applications, it is affirmed as (GRAS) by the FDA, with usage limited to current good manufacturing practices (GMP).

Environmental Impact

The production of potassium bitartrate, primarily through from wine lees and processes in the , contributes to environmental impacts via generation. often exhibits high (BOD), estimated at about 66% of the (COD), due to dissolved organics including tartrates from bitartrate and cleaning operations. This organic load can lead to of streams, degradation, and damage if discharged untreated. Synthetic methods, though less common, involve chemical reactions that require energy inputs, though specific consumption data is limited; however, the predominance of wine-derived minimizes reliance on such processes. Potassium bitartrate demonstrates high biodegradability in the , readily breaking down through microbial action on the component, which serves as an accessible carbon source for and other microorganisms. This natural degradation pathway reduces long-term persistence in and systems, mitigating accumulation risks from waste disposal. Under the European Union's REACH regulation, potassium bitartrate is classified as non-ous to human health and the , with a water hazard class (WGK) of 1, indicating slight potential. However, in viticulture regions, runoff from containing elevated potassium levels raises concerns for and structural stability, potentially affecting long-term land use if practices are not managed. Sustainability efforts in potassium bitartrate management include from wine , such as lees, which reduces overall winery volumes and associated disposal impacts while promoting . Alternatives like for wine stabilization offer environmental benefits over traditional cold treatment by lowering energy and water consumption, though resin regeneration can introduce minor chemical concerns. These practices support broader approaches in the wine sector, minimizing ecological footprints.

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