ammonium vanadate | 7803-55-6

• 物质功能分类: 无机化工 - 无机盐 - 无机铵盐
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 各种混合金属/非金属
• 英文名称: ammonium vanadate
• 英文别名: ammonium metavanadate；azanium;oxido(dioxo)vanadium
• CAS: 7803-55-6；11115-67-6
• 化学式: H₄N*O₃V
• 分子量: 116.978
• InChiKey: UNTBPXHCXVWYOI-UHFFFAOYSA-O

物化性质

• 熔点：
  200 °C
• 密度：
  2.32 g/cm3 at 25 °C (lit.)
• 溶解度：
  可溶于水中
• 暴露限值：
  NIOSH: Ceiling 0.05 mg/m3
• 物理描述：
  Ammonium metavanadate appears as a white crystalline powder. Slightly soluble in water and denser than water. Decomposes at 410°F. May release toxic fumes. Moderately toxic. An irritant. Used as a dryer for paints and inks, and for dyes. Loses ammonia upon heating.
• 颜色/状态：
  White or slightly yellow, crystalline powder
• 稳定性/保质期：
  Stable under recommended storage conditions.
• 分解：
  >350 °C

计算性质

• 辛醇/水分配系数(LogP)：
  -1.05
• 重原子数：
  5
• 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：
  58.2
• 氢给体数：
  1
• 氢受体数：
  3

ADMET

代谢

在生物体组织中，由于存在大量的还原条件，V3+和V4+占据了主导地位；然而，在富含氧气的血浆中，形成了V5+。

Within tissues in organisms, V3+ and V4+ predominate because of largely reducing conditions; in plasma, however, which is high in oxygen, V5+ is formed.

来源:Hazardous Substances Data Bank (HSDB)

代谢

每天通过口腔给小牛喂食10-20毫克/千克的偏钒酸铵……肝脏中的钒含量从0.3到5.1 ppm（湿组织），在肾脏中从6.0到40。

/In/ calves given 10-20 mg/kg of ammonium metavanadate by mouth daily ...levels of vanadium in the liver ranged from 0.3 to 5.1 ppm of wet tissue, in the kidney from 6.0 to 40.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：醋酸铵是白色或微黄色的结晶性粉末。它用于羊毛织物的染色和印花；将木材染成黑色；制造钒黑和“不褪色墨水”；在陶器上产生钒光泽；作为摄影显影剂；在显微镜下的苏木精染色；作为分析化学中的试剂。由于它容易在高温下转化为五氧化二钒，因此它被用作替代品。 人类暴露和毒性：一名工人在6小时内大量暴露于干燥的醋酸铵尘埃中，当时他正在将粉末铲入料斗。开始工作后2小时内，报告出现眶后头痛、流泪、口干和舌头变绿。手指、阴囊和上腿的皮肤出现了明显的绿色变色。他的鼻子据报道是闷的，他也很迟钝。第二天，他的睾丸肿大且触痛，在暴露后第三天，他出现了喘息、呼吸困难，并产生了绿色痰液的咳嗽。在接下来的2周内，他出现了几次小量的咳血。喘息和呼吸困难持续了大约1个月；胸部症状在事件发生后的3周最为严重。在最后一次暴露6周后的检查中，他除了左鼻孔部分堵塞和鼻粘膜发红外，没有其他症状。胸部检查未发现异常。肺功能评估显示正常的肺容积、用力呼气流量率和气体转移。他的外周血中有轻度嗜酸性粒细胞增多。 在人类成纤维细胞培养中，VO3-可以诱导DNA合成和细胞生长。醋酸铵未能在人类白细胞中增加结构染色体畸变的频率，而数值畸变、微核和卫星关联的显著增加被发现。通过使用一种特定的α卫星着丝粒DNA探针，将荧光原位杂交（FISH）应用于人类淋巴细胞微核试验，证实了钒的的非整倍体生成潜力。 动物研究：在给小鼠注射醋酸铵溶液（按钒计算为20毫克/千克）后，展示了急性管状坏死、肺出血和淋巴组织的坏死。在一项为期3个月的研究中，大鼠在饮用水中接受了浓度为200毫克/升（按钒计算）的醋酸铵。动物表现出体重增长迟缓和贫血。大体病理学检查显示肝脏和肾脏实质营养不良，有些动物的肾小管中形成了圆柱体。在急性暴露（口服和皮下注射）狗和兔子的钒氧化物和盐（包括醋酸铵）后，报告了神经生理学效应。这些包括中枢神经系统紊乱（条件反射受损和神经肌肉兴奋性增加）。研究了醋酸铵的致畸性。每组20只怀孕的仓鼠在妊娠的第5至10天通过腹腔注射接受了0、0.47、1.88和3.75毫克/千克的醋酸铵。怀孕的雌性在妊娠第15天被处死。骨骼异常显著增加，雄性：雌性比例降低。醋酸铵增加了酿酒酵母D7株的转化子和回复子的频率；在没有代谢激活的情况下观察到最高的活性。在经口处理后，醋酸铵在小鼠骨髓的微核试验中呈阳性。相比之下，在处理24和36小时后进行的结构染色体畸变试验中，对照组和处理组动物之间没有发现差异。在浓度为5-40微摩尔的醋酸铵研究中，中国仓鼠V79细胞的hprt基因和hprt-/gpt+转基因细胞系G12的gpt位点上表现出了弱突变。每隔3天给雌性小鼠腹腔注射2.5、5或10毫克/千克的醋酸铵，持续3、6或9周，结果显示，在6周内对大肠杆菌内毒素致命性的抵抗力呈剂量相关增加，而对李斯特菌致命性的抵抗力呈剂量相关下降。还观察到肝脏和脾脏的肿大，以及脾脏巨核细胞和红细胞前体的增强形成。

IDENTIFICATION AND USE: Ammonium metavanadate is a white or slightly yellow, crystalline powder. It is used in dyeing and printing on woolens; staining wood black; manufacture of vanadium black and "indelible ink"; producing vanadium luster on pottery; as photographic developer; in hematoxylin staining in microscopy; as a reagent in analytical chemistry. Because of its ready conversion to vanadium pentoxide at elevated temperatures, it is used as a substitute. HUMAN EXPOSURE AND TOXICITY: One worker was exposed to large amounts of dry ammonium vanadate dust over a 6-hr period while shovelling powder into a bin. Within 2 hr of commencing work, retro-orbital headache, tears, dry mouth, and green discoloration of the tongue were reported. There was a marked green discoloration of the skin of the fingers, scrotum, and upper legs. His nose was reported to be stuffy, and he was lethargic. The next day, his testicles were swollen and tender, and, on the third day after exposure, he developed wheezing, dyspnea, and a cough productive of green sputum. He had several small hemoptyses over the following 2 weeks. Wheezing and dyspnea persisted for about 1 month; chest symptoms were at their worst 3 weeks after the incident. On examination 6 weeks after the last exposure, he was asymptomatic, with the exception of a partially blocked left nostril and the reddened appearance of nasal mucosa. Chest examination revealed no abnormality. Pulmonary function assessment showed normal lung volume, forced expiratory flow rate, and gas transfer. He had a mild eosinophilia of the peripheral blood. In human fibroblast cultures VO3- can induce DNA synthesis and cell growth. Ammonium metavanadate was not found to increase the frequency of structural chromosome aberrations in human leukocytes, whereas a significant increase in numerical aberrations, micronuclei, and satellite associations was found. Fluorescence in situ hybridization (FISH) applied to the human lymphocyte micronucleus assay, by means of an alphoid centromere-specific DNA probe, confirmed the aneuploidogenic potentiality of vanadium. ANIMAL STUDIES: Acute tubular necrosis, pulmonary hemorrhage, and necrosis of lymphoid tissue were demonstrated in mice receiving 20 mg vanadium/kg of ammonium metavanadate solutions. In a 3-month study, rats received ammonium metavanadate at a concentration of 200 mg/L (in terms of vanadium) in their drinking water. Animals exhibited retardation of body weight gain and anemia. Gross pathology examination revealed parenchymatous dystrophy of the liver and kidneys with the formation of cylinders in the tubules in some animals. Neurophysiological effects have been reported following acute exposure (oral and sc injection) of dogs and rabbits to vanadium oxides and salts including ammonium metavanadate. These include disturbances of the central nervous system (impaired conditioned reflexes and neuromuscular excitability). The teratogenicity of ammonium vanadate was studied in hamsters. Twenty pregnant hamsters per dose group received 0, 0.47, 1.88, and 3.75 mg/kg of ammonium vanadate by ip injection on gestation days 5 through 10. Pregnant females were killed on day 15. There was a statistically significant increase in skeletal abnormalities and a decrease in the male:female ratio. Ammonium metavanadate increased the convertant and revertant frequencies in the D7 strain of Saccharomyces cerevisiae; the highest activity was observed without metabolic activation. The micronucleus test was found to be positive for ammonium metavanadate in bone marrow of mice following intragastric treatment. In contrast, no difference was found between controls and treated animals in the structural chromosome aberration test performed 24 and 36 hr after treatment. In studies with ammonium metavanadate at concentrations of 5-40 uM, weak mutagenesis was demonstrated at the hprt gene of Chinese hamster V79 cells, and at the gpt locus of hprt-/gpt+ transgenic cell line G12. Female mice given ammonium metavanadate ip at doses of 2.5, 5, or 10 mg/kg, every 3 days for 3, 6, or 9 weeks, showed a dose-related increase in resistance to E. coli endotoxin lethality up to 6 weeks and a dose-related decrease in resistance to Listeria lethality. Enlargement of the liver and spleen with enhanced formation of splenic megakaryocytes and red blood cell precursors was also observed.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

该物质可以通过吸入其气溶胶和通过吞食被吸收进人体。

The substance can be absorbed into the body by inhalation of its aerosol and by ingestion.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 吸入症状

咳嗽。呼吸困难。

Cough. Laboured breathing.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 皮肤症状

Redness.

Redness.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 眼睛症状

红斑。疼痛。

Redness. Pain.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

安全信息

• TSCA：
  Yes
• 危险等级：
  6.1
• 危险品标志：
  T+
• 安全说明：
  S22,S26,S28,S36/37/39,S37/39,S45
• 危险类别码：
  R36/37/38,R25,R20
• WGK Germany：
  3
• 海关编码：
  28419030
• 危险品运输编号：
  UN 2859 6.1/PG 2
• 危险类别：
  6.1
• RTECS号：
  YW0875000
• 包装等级：
  II
• 危险标志：
  GHS06
• 危险性描述：
  H301,H315,H319,H330,H335
• 危险性防范说明：
  P260,P284,P301 + P310,P305 + P351 + P338,P310

制备方法与用途

理化性质

偏钒酸铵是一种白色乃至淡黄色结晶粉末，相对密度为2.326，具有毒性。在15℃时其溶解度为5.18%，32℃时则增加至10.4%。尽管常温下不溶于乙醇和乙醚，但在加热条件下会稍微溶解，并发生热分解生成五氧化二钒（V₂O₅）、氨气和水：NH₄VO₃ → V₂O₅ + 2NH₃ + H₂O。若加热过急，可能部分氨分子残留在结晶中导致分解不完全。

为了得到纯净的五氧化二钒，使用偏钒酸铵进行热分解比直接购买市场上的五氧化二钒更为可取。

水中溶解度(g/100ml)

不同温度下每100毫升水中溶解的克数如下：

• 20℃：0.48g
• 30℃：0.84g
• 40℃：1.32g
• 60℃：2.42g

毒性

偏钒酸铵是一种对机体有多种影响的毒物，能够引起血液循环、呼吸系统、神经系统和新陈代谢等方面的改变。长期接触可能导致结膜炎、鼻黏膜炎、支气管炎等疾病，并伴随皮肤苍白、舌呈蓝黑色等症状。预防措施包括佩戴防毒口罩以保护呼吸器官，在生产及应用过程中防止粉尘产生并安装通风设备。粉碎时要将材料喷湿，定期进行体检。

化学性质

偏钒酸铵的化学式为NH₄VO₃，分子量116.98。它是一种白色或略带淡黄色结晶粉末，微溶于冷水、热乙醇和乙醚，易溶于热水及稀氢氧化铵。其水溶液会迅速变黄。

偏钒酸铵在真空中加热至135℃开始分解，在超过210℃时则形成钒的低价氧化物V₂O₃ 和 V₂O₄。在空气中灼烧会生成五氧化二钒（V₂O₅）。

用途

偏钒酸铵广泛用于化学试剂、催化剂、催干剂、媒染剂等，也是陶瓷工业中常用的釉料，还可制备五氧化二钒。

此外，它还可用作色层分析试剂和显微染色剂，并可用于测定铜、钡、铬和磷。

生产方法 碱解法

将钒铁粉与木炭粉按一定比例混合后进行焙烧，随后与液碱反应生成钒酸钠。清液经浓缩、过滤后再用盐酸中和至pH值7.5～8，过滤后加热至70～80℃，搅拌下加入氯化铵溶液析出偏钒酸铵结晶。

化学方程式如下：

• V₂O₅?xFe₂O₃ + 6NaOH → 2Na₃VO₄ + 2Fe₂O₃ + 3H₂O
• Na₃VO₄ + 2HCl → NaVO₃ + 2NaCI + H₂O
• NaVO₃ + NH₄Cl → NH₄VO₃ + 3NaCl + 2NH₄OH

干法

向粗制五氧化二钒（含V₂O₅总量85%～90%）中加入碳酸钠，在1000～1300℃下焙烧。浸取后用温水过滤，调整滤液pH值以沉淀Fe、Si、Al等杂质并再次过滤。

向滤液中添加氯化铵促使偏钒酸铵沉淀出来，并经过滤、分离、洗涤和干燥后即得偏钒酸铵成品。其他方法还包括将氨水加入钒酸水溶液或向钒酸盐水溶液中加固体氯化铵至饱和度以上，以使其沉淀。

类别

有毒物品

毒性标准

• 总暴露限值（TWA）：五氧化二钒0.05毫克/立方米

可燃性危险特性

可燃；受热产生有毒氮氧化物、钒氧化物和氨烟雾

储运特性

库房应保持通风低温干燥，避免与可燃物、还原剂及食品分开储存运输。

灭火方法

干粉、泡沫、砂土、二氧化碳等。

反应信息

• 作为反应物：
  描述：

  ammonium vanadate 生成 氨
  参考文献：
  名称：

  MORENO-CASTILLA, CARLOS;RIVERA-UTRILLA, JOSE;LOPEZ-PEINADO, ANTONIO J., FUEL, 68,(1989) N, C. 968-971

  摘要：

  DOI：
• 作为产物：
  描述：

  三异丙氧基氧化钒 、 ammonium hydroxide 生成 ammonium vanadate
  参考文献：
  名称：

  KONNO, NORIDZIRO

  摘要：

  DOI：
• 作为试剂：
  描述：

  4-乙烯基-1-环己烯 在 ammonium vanadate 、 硝酸 作用下， 生成 1,2,4-丁烷三羧酸
  参考文献：
  名称：

  Applications of the Hunsdiecker Silver Salt Degradation. The Preparation of Dibromides and Tribromides¹

  摘要：

  DOI：

  10.1021/ja01101a041

文献信息

• Self-induced synthesis under neutral conditions and novel visible light photocatalytic activity of Ag₄V₂O₇ polyoxometalate
  作者：Dan Zhou、Yi-Xiang Chen、Xiao-Yu Yuan、Yi Lu、Min Zhang、Jin-Ku Liu

  DOI：10.1039/d1nj01390d

  日期：——

  polyoxometalates (POMs) with great potential in catalysis. Utilizing their excellent catalytic activity to tackle antibiotic residues in water is meaningful but challenging. In this work, the self-induced synthesis of Ag4V2O7 POM with a 3D nanorod-bundle structure was achieved by the local aggregation effect of the protons of sodium dodecyl sulfonate (SDS) under neutral conditions rather than an alkaline environment

  强质子酸和氧化的双重功能使多金属氧酸盐（POM）具有巨大的催化潜力。利用它们出色的催化活性来解决水中的抗生素残留是有意义的，但具有挑战性。在这项工作中，通过十二烷基磺酸钠（SDS）的质子在中性条件而不是碱性环境下的局部聚集效应，实现了具有3D纳米棒状结构的Ag 4 V 2 O 7 POM的自诱导合成。阴离子表面活性剂双官能度的发现为工业合成材料提供了更方便的方法。实验结果表明，Ag 4 V 2 O的降解速率和反应速率7种若丹明B染料的POM分别比纯AgVO 3催化剂高4.64倍和30.00倍。银钒氧化物（SVO）的A / V比增加导致价带发生负向移动，同时带隙减小。同时，光生载流子的有效分离和传输以及表面羟基密度的增加也增强了Ag 4 V 2 O 7 POM的光催化活性。特别地，将Ag 4 V 2 O 7 POM创造性地应用于抗生素降解，从而产生了一类用于降解抗生素的催化剂。
• Process for the production of aromatic dialdehydes
  申请人：Mitsubishi Gas Chemical Co., Inc.

  公开号：US04328374A1

  公开（公告）日：1982-05-04

  A process for the production of aromatic dialdehydes which comprises reacting xylene chloride selected from the group consisting of .alpha.,.alpha.,.alpha.'-trichloroxylene alone, or a mixture of .alpha.,.alpha.,.alpha.'-trichloroxylene and .alpha.,.alpha.'-dichloroxylene, a mixture of .alpha.,.alpha.,.alpha.'-trichloroxylene and .alpha.,.alpha.,.alpha.',.alpha.'-tetrachloroxylene and a mixture of .alpha.,.alpha.,.alpha.'-trichloroxylene, .alpha.,.alpha.'-dichloroxylene and .alpha.,.alpha.,.alpha.',.alpha.'-tetrachloroxylene with nitric acid.

  生产芳香二醛的方法包括将从羟基二氯甲苯中选择的二氯甲苯与硝酸反应。
• Process for producing aromatic aldehydes
  申请人：Mitsubishi Gas Chemical Company, Inc.

  公开号：US04399311A1

  公开（公告）日：1983-08-16

  In a process for producing aromatic aldehydes by reacting chlorinated methylbenzenes with nitric acid, the improvement wherein a lead compound is added to the residue left after separation and recovery of the resulting aromatic aldehydes from the reaction mixture thereby to remove a chlorine ion present in the residue as a precipitate of lead chloride, and the residue left after removal of the lead chloride is recycled to the reaction of the chlorinated methylbenzenes with nitric acid.

  在通过将氯化甲苯与硝酸反应制备芳香醛的过程中，改进在从反应混合物中分离和回收所得芳香醛后剩下的残渣中添加铅化合物，以去除残渣中存在的氯离子，使其沉淀为氯化铅，并在去除氯化铅后将残渣回收到氯化甲苯与硝酸的反应中。
• A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands
  作者：Xian-Yong Yu、Lin Deng、Baishu Zheng、Bi-Rong Zeng、Pinggui Yi、Xin Xu

  DOI：10.1039/c3dt51986d

  日期：——

  In order to understand the substitution effects of pyrazolylpyridine (pzpy) on the coordination reaction equilibria, the interactions between a series of pzpy-like ligands and biperoxidovanadate ([OV(O2)2(D2O)]−/[OV(O2)2(HOD)]−, abbrv. bpV) have been explored using a combination of multinuclear (1H, 13C, and 51V) magnetic resonance, heteronuclear single quantum coherence (HSQC), and variable temperature

  为了理解吡唑基吡啶（pzpy）对配位反应平衡的取代作用，一系列pzpy样配体与双过氧钒酸盐（[OV（O 2）2（D 2 O）] - / [OV（O 2）2（HOD）] -，abbbp。bpV）已在0.15中使用多核（1 H，13 C和51 V）磁共振，异核单量子相干（HSQC）和可变温度NMR的组合进行了研究摩尔L -1 NaCl D 2模拟生理条件的O​​溶液。首次报道了直接NMR数据和平衡常数。由于一些竞争性配位相互作用，形成了一系列新的七配位过氧钒酸盐[OV（O 2）2 L] -（L = pzpy样螯合配体）。根据bpV和pzpy样配体之间产物的平衡常数，发现配体的相对亲和力为pzpy> 2-Ester-pzpy≈2-Me-​​pzpy≈2-Amide-pzpy> 2-Et- pzpy。在bpV和pzpy之间的相互作用系统中，存在一对异构体（异构体A和BNH 4 [OV（O 2）2（pzpy）]·6H
• α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron–vanadium cofactor in nitrogenase
  作者：Can-Yu Chen、Mao-Long Chen、Hong-Bin Chen、Hongxin Wang、Stephen P. Cramer、Zhao-Hui Zhou

  DOI：10.1016/j.jinorgbio.2014.08.003

  日期：2014.12

  Unlike the most of α-alkoxy coordination in α-hydroxycarboxylates to vanadium, novel α-hydroxy coordination to vanadium(IV) has been observed for a series of chiral and achiral monomeric α-hydroxycarboxylato vanadyl complexes [VO(H2cit)(bpy)]·2H2O (1), [VO(Hmal)(bpy)]·H2O (2), [VO(H2cit)(phen)]·1.5H2O (3), [VO(Hmal)(phen)]·H2O (4), and [ΔVO(S-Hcitmal)(bpy)]·2H2O (5), [VO(H2cit)(phen)]2·6.5H2O (6),

  与 α-羟基羧酸盐与钒的大多数 α-烷氧基配位不同，在一系列手性和非手性单体 α-羟基羧酸氧钒络合物 [VO(H 2 cit)(bpy) 中观察到新型 α-羟基与钒 (IV) 的配位)]·2H 2 O ( 1 ), [VO(Hmal)(bpy)]·H 2 O ( 2 ), [VO(H 2 cit)(phen)]·1.5H 2 O ( 3 ), [VO( Hmal)(phen)]·H 2 O ( 4 )、[ Δ VO( S -Hcitmal)(bpy)]·2H 2 O ( 5 )、[VO(H 2 cit)(phen)] 2 ·6.5H 2 O ( 6 )，由硫酸氧钒与α-羟基羧酸盐和N-杂环配体在酸性溶液中反应分离得到。该配合物具有三齿柠檬酸盐、苹果酸盐或柠檬酸盐，通过其α-羟基、α-羧基和β-羧基与钒原子螯合；而柠檬酸的另一个β-羧酸基团可以自由地与晶格水分子形成强氢键。中性的α-羟基还与