calcium chromate | 53568-70-0

• 物质功能分类: 染料及颜料 - 颜料 - 有机颜料
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 碱土金属氧阴离子化合物
• 英文名称: calcium chromate
• 英文别名: calcium;dioxido(dioxo)chromium
• CAS: 53568-70-0；13765-19-0；12205-18-4
• 化学式: Ca*CrO₄
• 分子量: 156.072
• InChiKey: RFAFBXGYHBOUMV-UHFFFAOYSA-N

物化性质

• 密度：
  2.500
• 溶解度：
  微溶于H2O；不溶于乙醇、丙酮
• 暴露限值：
  ACGIH: TWA 0.0002 mg/m3; STEL 0.0005 mg/m3 (Skin)OSHA: Ceiling 0.1 mg/m3NIOSH: IDLH 15 mg/m3; TWA 0.0002 mg/m3
• 物理描述：
  Calcium chromate is a yellow powder. It is slightly soluble in water. The primary hazard is the threat to the environment. Immediate steps should be taken to prevent its spread to the environment.
• 颜色/状态：
  Yellow monoclinic rhombic crystals
• 熔点：
  1000 °C (decomposes)
• 稳定性/保质期：
  在常温常压下稳定，应避免与还原剂、有机材料、金属粉末、卤素以及水分或潮湿接触。 黄色单斜菱柱形晶体，在200℃时会失去两个水分子。其在20℃的水中溶解度为16.3克/100毫升H₂O，在45℃时则增加到18.2克/100毫升H₂O，能够溶于酸和乙醇中。
• 分解：
  1020 °C

计算性质

• 辛醇/水分配系数(LogP)：
  -3.0
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  4

ADMET

毒理性

• 毒性总结

鉴定和使用：钙铬酸盐（CaCrO4）是一种鲜黄色的粉末。它被用作颜料、腐蚀抑制剂、氧化剂、电池的去极化剂和轻金属合金的涂层。人类暴露和毒性：钙铬酸盐被怀疑是人类的致癌物质。据报道，消除钙铬酸盐的形成，在铬酸盐生产工厂首次接触后的工人中显著降低了支气管癌的死亡率。在体外实验中，当CaCrO4暴露条件相等时，人类细胞比仓鼠细胞多出四倍的DNA断裂，比小鼠胚胎成纤维细胞多出两倍。碱性洗脱研究也表明，CaCrO4在所有三种细胞系中形成了DNA-蛋白质交联。与小鼠细胞相比，人类细胞中的交联水平高出四倍，仓鼠细胞比小鼠细胞高出两倍。在另一个体外实验中，用不同浓度的K2Cr2O7、CaCrO4和CrO3处理在BrdUrd存在下培养2个复制周期的人淋巴细胞。观察到姐妹染色单体交换（SCEs）。在所有情况下，浓度越高，每个中期和每条染色体的SCE频率越高。按浓度计算，产生SCE的有效性顺序是：CaCrO4远大于CrO3大于K2CrO7。动物研究：钙铬酸盐在大鼠经支气管内植入小丸后产生支气管癌，在大鼠和小鼠肌肉内植入小丸以及在大鼠胸膜内注射后产生注射部位肉瘤。在Drosophila melanogaster的饮食水平为500和700 ppm时，钙铬酸盐诱导了性连锁隐性突变。钙铬酸盐在小鼠淋巴瘤L5178Y TK+/TK-正向突变试验中呈阳性。研究了氯化镍、结晶硫化镍和CaCrO4处理后中国仓鼠卵巢细胞和C3H10T1/2细胞的染色体畸变。这三种化合物都以浓度和时间依赖性的方式增加了染色体畸变。碱性洗脱研究表明，CaCrO4在中国仓鼠卵巢细胞中引起了DNA单链断裂和DNA-蛋白质交联。生态毒性研究：200 ppm的钙铬酸盐使植物生长抑制了50%。

IDENTIFICATION AND USE: Calcium chromate (CaCrO4) is a bright yellow powder. It is used as a pigment, corrosion inhibitor, oxidizing agent, depolarizer for batteries, and coating for light metal alloys. HUMAN EXPOSURE AND TOXICITY: Calcium chromate is a suspected human carcinogen. It has been reported that eliminating the formation of calcium chromate, had resulted in a distinct reduction in bronchial carcinoma mortality among workers at chromate-producing factories exposed for the first time after the change-over. In vitro, human cells exhibited four times more DNA breaks than the hamster cells and two times more than mouse embryo fibroblast cells when the CaCrO4 exposure conditions were equivalent. Alkaline elution studies also demonstrated the formation of DNA-protein cross-links by CaCrO4 in all three cell lines. The level of cross-links was four times greater in the human cells compared to the mouse cells and was a factor of 2 greater in the hamster cells compared to the mouse cells. In other in vitro experiment, treatments with various concentrations of K2Cr2O7, CaCrO4, and CrO3 were given to human lymphocytes cultured in presence of BrdUrd for 2 replicative cycles. Sister-chromatid exchanges (SCEs) were visualized. In all cases, the higher the concentrations the higher the frequencies of SCEs per metaphase and per chromosome. On a concentration basis, the order of effectiveness in producing SCEs was: CaCrO4 much greater than CrO3 greater than K2Cr2O7. ANIMAL STUDIES: Calcium chromate produced bronchial carcinomas after implantation of an intrabronchial pellet in rats and injection-site sarcomas after intramuscular implantation in rats and mice and after intrapleural injection in rats. Calcium chromate was positive for the induction of sex linked recessive mutations in Drosophila melanogaster at dietary levels of 500 and 700 ppm. Calcium chromate was positive in the L5178Y TK+/TK- mouse lymphoma forward mutation assay. Chromosomal aberrations were studied in Chinese hamster ovary cells and in C3H10T1/2 cells following treatment with NiCl2, crystalline NiS, and CaCrO4. All three compounds caused an increase in chromosomal aberrations in a concentration- and time-dependent fashion. Alkaline elution studies demonstrated CaCrO4-induced DNA single strand breaks and DNA-protein crosslinks in Chinese hamster ovary cells. ECOTOXICITY STUDIES: Calcium chromate at 200 ppm inhibited plant growth by 50%.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A2；疑似人类致癌物。/铬酸钙，以Cr形式/

A2; Suspected human carcinogen. /Calcium chromate, as Cr/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

证据权重特征：根据当前指南（1986年），六价铬被归类为A组——已知的人类通过吸入途径的致癌物。通过口服途径的致癌性无法确定，被归类为D组。在拟议的指南（1996年）下，六价铬将被定性为通过吸入途径的已知人类致癌物，基于以下原因。已知六价铬通过吸入途径在人类中具有致癌性。职业流行病学研究的结果一致，研究人群和调查者对铬暴露的工人的一致性。已经建立了铬暴露与肺癌的剂量-反应关系。铬暴露工人接触三价铬和六价铬化合物。然而，只有六价铬在动物研究中被发现具有致癌性，因此得出结论，只有六价铬应该被归类为人类致癌物。动物数据与六价铬的人类致癌性数据一致。六价铬化合物在动物生物分析中具有致癌性，产生以下肿瘤类型：大鼠和小鼠的肌肉内注射部位肿瘤，各种六价铬化合物在大鼠的胸膜内植入部位肿瘤，各种六价铬化合物在大鼠的支气管内植入部位肿瘤，以及大鼠的皮下注射部位肉瘤。体外数据提示六价铬致癌性的潜在作用模式。六价铬的致癌性可能是由细胞内还原为三价形式后形成的致突变氧化DNA损伤的结果。六价铬容易通过细胞膜并迅速在细胞内还原，生成反应性的三价和四价铬中间体和活性氧种。在六价铬还原过程中形成许多潜在的致突变DNA损伤。六价铬在细菌分析、酵母和V79细胞中具有致突变性，六价铬化合物在体外降低DNA合成的准确性，并因DNA损伤产生非计划性DNA合成。铬酸已被证明能转化原代细胞和细胞系。 人类致癌性数据：职业暴露于铬化合物已在铬酸盐生产、镀铬、铬颜料、铁铬生产、金矿开采、皮革鞣制和铬合金生产行业中进行研究。铬酸盐行业的工人接触三价和六价的铬化合物。对日本、英国、西德和美国的铬酸盐生产厂进行的流行病学研究揭示了职业暴露于铬与肺癌之间的相关性，但没有确定引起癌症的具体铬形态……铬颜料工人的研究一致表明，职业铬暴露（主要是六价铬）与肺癌有关。对镀铬行业进行的几项研究已经证明了癌症与铬化合物暴露之间的正相关关系。 动物致癌性数据：动物数据与六价铬的人类流行病学研究结果一致……/六价铬/

WEIGHT OF EVIDENCE CHARACTERIZATION: Under the current guidelines (1986), Cr(VI) is classified as Group A - known human carcinogen by the inhalation route of exposure. Carcinogenicity by the oral route of exposure cannot be determined and is classified as Group D. Under the proposed guidelines (1996), Cr(VI) would be characterized as a known human carcinogen by the inhalation route of exposure on the following basis. Hexavalent chromium is known to be carcinogenic in humans by the inhalation route of exposure. Results of occupational epidemiological studies of chromium-exposed workers are consistent across investigators and study populations. Dose-response relationships have been established for chromium exposure and lung cancer. Chromium-exposed workers are exposed to both Cr(III) and Cr(VI) compounds. Because only Cr(VI) has been found to be carcinogenic in animal studies, however, it was concluded that only Cr(VI) should be classified as a human carcinogen. Animal data are consistent with the human carcinogenicity data on hexavalent chromium. Hexavalent chromium compounds are carcinogenic in animal bioassays, producing the following tumor types: intramuscular injection site tumors in rats and mice, intrapleural implant site tumors for various Cr(VI) compounds in rats, intrabronchial implantation site tumors for various Cr(VI) compounds in rats and subcutaneous injection site sarcomas in rats. In vitro data are suggestive of a potential mode of action for hexavalent chromium carcinogenesis. Hexavalent chromium carcinogenesis may result from the formation of mutagenic oxidatitive DNA lesions following intracellular reduction to the trivalent form. Cr(VI) readily passes through cell membranes and is rapidly reduced intracellularly to generate reactive Cr(V) and Cr(IV) intermediates and reactive oxygen species. A number of potentially mutagenic DNA lesions are formed during the reduction of Cr(VI). Hexavalent chromium is mutagenic in bacterial assays, yeasts and V79 cells, and Cr(VI) compounds decrease the fidelity of DNA synthesis in vitro and produce unscheduled DNA synthesis as a consequence of DNA damage. Chromate has been shown to transform both primary cells and cell lines. HUMAN CARCINOGENICITY DATA: Occupational exposure to chromium compounds has been studied in the chromate production, chromeplating and chrome pigment, ferrochromium production, gold mining, leather tanning and chrome alloy production industries. Workers in the chromate industry are exposed to both trivalent and hexavalent compounds of chromium. Epidemiological studies of chromate production plants in Japan, Great Britain, West Germany, and the United States have revealed a correlation between occupational exposure to chromium and lung cancer, but the specific form of chromium responsible for the induction of cancer was not identified ... Studies of chrome pigment workers have consistently demonstrated an association between occupational chromium exposure (primarily Cr(VI)) and lung cancer. Several studies of the chromeplating industry have demonstrated a positive relationship between cancer and exposure to chromium compounds. ANIMAL CARCINOGENICITY DATA: Animal data are consistent with the findings of human epidemiological studies of hexavalent chromium ... /Chromium (VI)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：有足够的人类证据证明铬(VI)化合物的致癌性。铬(VI)化合物会导致肺癌。此外，暴露于铬(IV)化合物与鼻咽癌之间也存在正相关关系。有足够的实验动物证据证明铬(VI)化合物的致癌性。铬(VI)化合物对人类具有致癌性（第1组）。/铬(VI)化合物/

Evaluation: There is sufficient evidence in humans for the carcinogenicity of chromium(VI) compounds. Chromium(VI) compounds cause cancer of the lung. Also positive associations have been observed between exposure to Chromium(IV) compounds and cancer of the nose and nasal sinuses. There is sufficient evidence in experimental animals for the carcinogenicity of chromium(VI) compounds. Chromium(VI) compounds are carcinogenic to humans (Group 1). /Chromium(VI) compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

铬 hexavalent 化合物：已知是人类致癌物。/铬 hexavalent 化合物/

Chromium Hexavalent Compounds: known to be human carcinogens. /Chromium hexavalent compound/

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• TSCA：
  Yes
• 危险等级：
  5.1

制备方法与用途

化学性质

钙铬黄的主要成分是铬酸钙（CaCrO₄），外观为柠檬黄色粉末。三氧化铬的理论含量约为64.1%，实际产品中也接近60%。由于钙（Ca）的原子量仅为40.08，因此它是铬酸盐防锈颜料中三氧化铬含量最高的品种之一。其主要特点是水溶解度高，比其他品种高出甚多，并且三氧化铬含量较高，因而毒性较所有铬酸盐防锈颜料更大。

用途

钙铬黄是一种无机防锈颜料，在配制防锈漆后，可以提供充足的铬酸根离子，从而增强钝化作用和提高防锈性能。然而，由于其水溶解度较大，可能会降低漆膜的抗水性，因此需选用具有良好抗水性的树脂作为基料。例如，可以使用钙铬黄配制钙黄过氯乙烯底漆、钙黄氯化橡胶底漆或钙黄环氧酯底漆等。此外，也可以与锌铬黄、锶铬黄、钡铬黄等配合使用，以取长补短。

用途

除了作为防锈颜料外，钙铬黄还可用于分析试剂和氧化剂。

生产方法

采用碳酸钙法生产钙铬黄。具体操作如下：以30份的碳酸钙与31份的铬酐配制成料液后送入带搅拌的蒸汽加热反应器中进行反应，加热至沸腾并持续2小时以上生成铬酸钙，直至反应终点时用少量细石灰乳液中和至pH值为8，再经过滤、分离、干燥得产品。

类别

氧化剂

毒性分级

高毒

急性毒性

口服-大鼠 LD₅₀: 327 毫克/公斤

爆炸物危险特性

与还原剂反应剧烈

可燃性危险特性

与硼混合明火猛烈燃烧

储运特性

库房应通风低温干燥，并与其他有机物、还原剂分开存放。

灭火剂

水、泡沫、二氧化碳、干粉

职业标准

TWA 0.0001 毫克(铬)/立方米

反应信息

• 作为反应物：
  描述：

  calcium chromate 在 二氧化碳 作用下， 以 水 为溶剂， 生成 chromium(VI) oxide
  参考文献：
  名称：

  FR823114

  摘要：

  公开号：
• 作为产物：
  描述：

  氢氧化钙 生成 calcium chromate
  参考文献：
  名称：

  EVTYUTOVA, I. N.;ALFEROVA, L. A.;SMIRNOV, E. M.;TROFIMOV, V. N.;CHIKIRINA+, ZH. PRIKL. XIMII, 62,(1989) N, S. 2047-2051

  摘要：

  DOI：

文献信息

• Expansion of the photoresponse window of a BiVO₄ photocatalyst by doping with chromium(<scp>vi</scp>)
  作者：Kazuya Okuno、Hideki Kato、Junie Jhon M. Vequizo、Akira Yamakata、Hisayoshi Kobayashi、Makoto Kobayashi、Masato Kakihana

  DOI：10.1039/c8ra07830k

  日期：——

  Photocatalytic O₂ evolution is induced by electrons/holes generated by excitation of a new absorption band formed by doping with Cr⁶⁺.

  使用Cr6+掺杂形成的新吸收带激发产生的电子/空穴诱导了光催化O2的产生。
• Formation, thermal redox reaction and crystal structure of δ-CaCr2O4
  作者：Jaegyeom Kim、Jinho Shin、Seung-Min Paek、Dae Sung Park、Seung-Joo Kim

  DOI：10.1016/j.jssc.2021.122669

  日期：2022.1

  The thermal redox reactions of a Ca–Cr–O system under different atmospheric conditions were investigated by cyclic thermodiffractometry and thermogravimetry. In the first heating process under a reductive atmosphere, CaCrO4 decomposed into CaO and δ-CaCr2O4, a metastable form, with the liberation of free oxygen. In the second process under an oxidizing atmosphere, the CaO and δ-CaCr2O4 produced in

  通过循环热衍射法和热重法研究了 Ca-Cr-O 体系在不同大气条件下的热氧化还原反应。在还原气氛下的第一次加热过程中，CaCrO 4分解为CaO和δ-CaCr 2 O 4，一种亚稳态形式，释放出游离氧。在氧化气氛下的第二个过程中，第一次还原过程中产生的CaO和δ-CaCr 2 O 4反应生成CaCrO 4，表明该氧化还原反应可以通过控制气氛可逆地进行。δ-CaCr 2 O 4的晶体结构首次根据高分辨率同步加速器粉末 X 射线衍射数据确定。δ-CaCr 2 O 4以单斜晶结构结晶，空间群为P 2 1 / m。该结构可以描述为由共享边缘的 CrO 6八面体组成的 CrO 2层的堆叠，钙离子就地驻留在层之间。钙离子由六个氧原子配位以在 CrO 2层之间形成三棱柱几何结构。δ-CaCr 2 O 4结构与低温β-CaCr 2 O 4 结构不同（扭曲的CaFe 2 O 4型）和高温α-CaCr 2 O
• Molten calcium nitrate tetrahydrate: the reactions of six chromium(VI) compounds
  作者：D.H. Kerridge、S.A. Tariq、A.M. Wei

  DOI：10.1016/0040-6031(86)85147-4

  日期：1986.9

  tetrahydrate as a molten salt solvent has a working range of 50°C before significant evaporation takes place, which can be extended to 90°C by covering the melt surface with a film of immiscible organic liquid. Potassium di-, tri- and tetrachromates dissolved but did not react until the temperature range of anhydrous calcium nitrate, when Lux-Flood acid-base reaction occurred forming chromate. Potassium chromate

  摘要 作为熔盐溶剂的四水硝酸钙在发生显着蒸发之前的工作温度范围为 50°C，通过用不混溶的有机液体薄膜覆盖熔体表面可以将其工作范围扩展到 90°C。二铬酸钾、三铬酸钾和四铬酸钾溶解但直到无水硝酸钙的温度范围才发生反应，此时发生Lux-Flood酸碱反应形成铬酸盐。铬酸钾轻微溶解，但不反应。报告了对熔体溶液的光谱测量。氧化铬 (VI) 在水合物熔体中反应形成硝酸和可能的重铬酸钙，后者在无水硝酸盐中解聚。铬酰氯也在水合物熔体中水解成氯化氢、硝酸和铬酸钙。高于 500°C，剩余的硝酸钙分解为氧化钙和氮氧化物，该反应可能被氯化物催化。当含有铬酸盐的溶液加热到 700°C 时，会形成少量的铬（III）。
• The Standard Gibbs energies of formation of ACrO4 (A = Ca, Sr or Ba) from EMF measurements
  作者：A.M. Azad、R. Sudha、O.M. Sreedharan

  DOI：10.1016/0040-6031(92)80011-k

  日期：1992.1

  electrolyte EMF method, there is no reliable thermodynamic information on SrCrO 4 . Hence the EMF of the galvanic cells Pt,O 2 (g)/ CaO,CaF 2 /CaF 2 /AF 2 ,ACrO 4 ,Cr 2 O 3 /Pt,O 2 (g) were studied under an atmosphere of pure oxygen at a pressure of 0.1 MPa over the ranges 788–1070, 851–1116 and 850–1168 K where A is Ca, Sr and Ba respectively. From the cell EMF data, the standard Gibbs energies of formation

  摘要 CaCrO 4 、BaCrO 4 和SrCrO 4 的热力学稳定性引起了材料科学家和核技术的关注，因为这些是快核反应堆事故条件下裂变产物与包壳化学相互作用的可能化合物。尽管有一些关于通过氟化物电解液 EMF 方法获得的 CaCrO 4 和 BaCrO 4 的热力学稳定性的报道，但没有关于 SrCrO 4 的可靠热力学信息。因此，原电池的 EMF Pt,O 2 (g)/ CaO,CaF 2 /CaF 2 /AF 2 ,ACrO 4 ,Cr 2 O 3 /Pt,O 2 (g) 在纯氧气氛下研究在 788-1070、851-1116 和 850-1168 K 范围内的压力为 0.1 MPa，其中 A 分别是 Ca、Sr 和 Ba。根据电池 EMF 数据，铬酸盐的标准吉布斯形成能 Δ G f XXX，
• Synthesis and Structure of Novel CrV–CrVI Mixed Valence Compounds, Nd1−xCaxCrO4 (x=0.02–0.20)
  作者：Y. Aoki、H. Konno

  DOI：10.1006/jssc.2000.9008

  日期：2001.2

  method. The calculated densities of Nd1−xCaxCrO4 (x=0–0.20) were in good agreement with the ones measured by the picnometry. XPS and Raman spectra indicated that Nd1−xCaxCrO4 (x=0.02–0.20) are mixed valence oxides containing two types of tetrahedra, CrVO3−4 and CrVIO2−4, having D2d symmetry in the structure, and this compensates the decrease of positive charges introduced by CaII ions. Though two types

  单相的Nd 1- X的Ca X的CrO 4（X = 0-0.20）氧化物通过选自Nd制备前体的热解合成的III -Ca II -Cr VI混合溶液。的Nd 1- X的Ca X的CrO 4具有X ≥0.25没有作为单相获得。所有Nd 1- x Ca x CrO 4均为锆石类型（四方晶系，I 4 1 / amd），组成几乎是化学计量的，没有任何本质上的缺陷，这是通过化学分析确定的。晶格常数和原子位置通过X射线Rietveld方法精制。Nd 1- x Ca x CrO 4（x = 0-0.20）的计算密度与通过皮法测量的密度相吻合。XPS和拉曼光谱表明的Nd 1- X的Ca X的CrO 4（X = 0.02〜0.20）是含有两种类型的四面体，铬混合价氧化物V ø 3- 4和Cr VI ö 2- 4，具有结构中的D 2d对称，这补偿了由Ca II离子引入的正电荷的减少。尽管无法通过XRD区分两种类