Caesium vanadium(III) sulfate dodecahydrate
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Product Description
Cesium vanadium(III) sulfate dodecahydrate is a sulfate complex salt crystalline compound containing trivalent vanadium ions. Cesium ions (Cs⁺) and vanadium(III) ions (V³⁺) are bridged by sulfate ions (SO₄²⁻) to form an extended structure, crystallizing to bind twelve water molecules. This compound belongs to the vanadium family and typically exhibits a typical octahedral coordination environment. The V³⁺ ion is located at the center of the hexahydrate [V(H₂O)₆]³⁺ unit, forming a stable lattice with sulfate and cesium ions through a network of ionic and hydrogen bonds. In solid-state chemistry and materials science, it is often used as a model system to study the electron paramagnetic properties, low-temperature magnetic behavior, and geometric frustration potential of vanadium(III). It can also serve as a precursor for the synthesis of other vanadium-based functional materials.
Other Information
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Classification: It is a specific member of the vanadium alum series (e.g., analogous to ammonium vanadium alum).
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Context: Vanadium is a "chameleon" element, with compounds exhibiting different colors (purple V²⁺, green/blue V³⁺, blue V⁴⁺, yellow V⁵⁺) and properties across its oxidation states.
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Research Significance: Compounds like this are at the frontier of research into quantum materials, low-dimensional magnetism, and electronic correlation effects.
Synthesis and Production
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General Method: Prepared by mixing stoichiometric aqueous solutions of vanadium(III) sulfate, V₂(SO₄)₃, and cesium sulfate, Cs₂SO₄.
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Key Reaction: V₂(SO₄)₃ + Cs₂SO₄ + 24H₂O → 2 CsV(SO₄)₂·12H₂O
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Critical Conditions: Synthesis must be performed under an inert atmosphere (e.g., nitrogen or argon) to prevent oxidation of the V³⁺ ion. High-quality crystals are typically obtained via slow evaporation or controlled cooling of the solution.
Uses and Applications
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Primary Use: A research compound in fundamental scientific studies.
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Application Areas:
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Solid-State Physics & Magnetism: Serves as a model system for studying electron paramagnetic resonance (EPR), low-temperature magnetic behavior (e.g., paramagnetism, geometric frustration, and ferromagnetic ordering), and quantum spin systems.
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Materials Science & Inorganic Chemistry: Used as a precursor for synthesizing other vanadium-based functional materials. It is an ideal subject for studies on crystal growth, ligand field theory, and the structure-property relationships of alums.
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Spectroscopy: Single crystals are used to study the electronic structure and d-d transitions of the [V(H₂O)₆]³⁺ ion via UV/Vis absorption spectroscopy at low temperatures.
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Chemical and Physical Properties
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Chemical Formula: CsV(SO₄)₂·12H₂O (Commonly accepted). This is a double sulfate salt (Tutton's salt-type) belonging to the alum family (general formula: XM³⁺(SO₄)₂·12H₂O).
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Appearance: Colored crystalline solid, typically exhibiting green, violet, or blue-green hues due to the d² electron configuration of V³⁺.
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Molecular Weight: ~645 g/mol (varies slightly based on calculation, ~592 g/mol also cited).
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Crystal Structure:
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System: Cubic.
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Space Group: Pa-3.
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Coordination: The V³⁺ ion is located in an octahedral [V(H₂O)₆]³⁺ complex. Cs⁺ ions are 12-coordinated. The structure is held together by a network of ionic bonds and hydrogen bonds from the 12 water molecules and sulfate ions.
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Physical Properties:
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Density: ~2.00 g/cm³ (calculated).
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Solubility: Readily soluble in water (characteristic of metal sulfates).
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Thermal Stability: Undergoes stepwise dehydration upon heating, losing water molecules in stages before final decomposition.
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Electronic & Magnetic Properties:
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Band Gap: ~2.7 eV (calculated, indicating an insulator/wide-bandgap semiconductor).
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Magnetism: Paramagnetic with a magnetic moment consistent with V³⁺ (d²). Exhibits ferromagnetic ordering.
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Formation Energy: Thermodynamically favorable but metastable (slightly above the convex hull of stability at 0K).
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Safety and Handling
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Toxicity: Vanadium(III) compounds are considered toxic. Exposure to dust or ingestion should be strictly avoided.
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Handling Precautions:
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Use in a well-ventilated area or fume hood.
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Wear appropriate personal protective equipment (PPE), including gloves and safety goggles.
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Minimize dust generation during handling.
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Environmental & Disposal: Waste material must be collected and disposed of as hazardous chemical waste, in accordance with local regulations. It must not be released into the environment or sewer system.