单氟磷酸 | 13537-32-1

• 物质功能分类: 无机化工 - 无机盐 - 磷化物、金属的磷酸、偏磷酸、次磷酸和焦磷酸盐
• 分子结构分类: 无机化合物 - 均质非金属化合物 - 非金属氧阴离子化合物
• 中文名称: 单氟磷酸
• 中文别名: 氟磷酸；一氟磷酸；氟化磷酸
• 英文名称: fluorophosphoric acid
• 英文别名: fluorophosphonic acid
• CAS: 13537-32-1
• 化学式: FH₂O₃P
• 分子量: 99.9862
• InChiKey: DWYMPOCYEZONEA-UHFFFAOYSA-N

物化性质

• 密度：
  1.83 g/mL at 25 °C
• 溶解度：
  极易溶于H2O
• 物理描述：
  Fluorophosphoric acid, anhydrous appears as a colorless liquid. Corrosive to metals and tissue. Used in metal cleaning, as a chemical polishing agent and as a catalyst.
• 颜色/状态：
  COLORLESS LIQUID
• 气味：
  Practically no odor
• 蒸汽密度：
  3.45
• 粘度：
  VISCOUS LIQUID
• 腐蚀性：
  Corrosive to glass since HF is present in the aqueous acid and can be generated by hydrolysis of the anhydrous acid.
• 解离常数：
  pK1 = 5.5; pK2 = 8.5
• 稳定性/保质期：
  在常温常压下，该物质是稳定的。应避免与氧化物和碱接触。在70℃时会固化，在中性和弱碱性溶液中缓慢水解。纯酸或浓溶液会腐蚀大多数金属和合金，包括不锈钢。但对于银、铂和铝则呈惰性。稀溶液可能会腐蚀金属铝和钛。

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 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：
  57.5
• 氢给体数：
  2
• 氢受体数：
  4

ADMET

毒理性

• 副作用

Dermatotoxin - 皮肤烧伤。

Dermatotoxin - Skin burns.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 相互作用

DEXTRANASE 抑制了在给予致龋饮食并接种变形链球菌的大鼠中牙菌斑和牙垢的形成。通过向水中添加单氟磷酸盐，这种效果得到了增强。

DEXTRANASE INHIBITED FORMATION OF DENTAL PLAQUE & CARRIES IN RATS GIVEN A CARIOGENIC DIET AND INOCULATED WITH STREPTOCOCCUS MUTANS. THIS EFFECT WAS INCR BY ADDN OF MONOFLUOROPHOSPHATE TO THE WATER.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

监测血浆氟化物水平，因为单氟磷酸可能会增加血浆氟化物水平并降低血浆钙水平。

Monitor plasma fluoride level because monofluorophosphoric acid may increase plasma fluoride levels and decrease plasma calcium.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

强烈刺激组织。

STRONG IRRITANT TO TISSUE.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

在一项双盲试验中，460名老年人（237名接受治疗，233名对照）接受了单氟磷酸盐（每天25毫克氟化物）治疗8个月，未观察到身高、住院或死亡率方面的差异。在接受氟化物治疗的一组中，骨折和关节炎加重的发生率更高。脊椎X光片没有显示出差异。治疗结束2个月后，接受氟化物治疗组的血浆中自由离子态氟化物水平仍然比对照组高两倍。

IN A DOUBLE-BLIND TRIAL WITH MONOFLUOROPHOSPHATE (25 MG FLUORIDE/DAY) GIVEN TO 460 AGED PERSONS (237 TREATED, 233 CONTROLS) FOR 8 MO, NO DIFFERENCE WAS OBSERVED IN HEIGHT, ADMISSION TO HOSPITAL, OR MORTALITY. FRACTURES AND EXACERBATION OF ARTHROSIS WERE MORE FREQUENT IN THE FLUORIDE GROUP. VERTEBRAL X-RAY FILMS SHOWED NO DIFFERENCE. THE FREE IONIZED FLUORIDE LEVELS IN THE PLASMA OF THE FLUORIDE-TREATED GROUP WERE STILL TWICE AS HIGH 2 MO AFTER TREATMENT ENDED.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

使用含氟牙膏刷牙后保留的总氟化物量平均为应用的19.3%，而使用2% NAF溶液局部应用4分钟后保留的量为13.6%。用10毫升500 PPM NAF溶液冲洗30秒后保留的量为11.6%，咀嚼含有1毫克F的片剂后保留的量为8.9%。口腔冲洗或局部应用后，24-48小时内可以在唾液中检测到残留的氟化物。在使用含有单氟磷酸盐的牙膏或氟化物片剂后，唾液中只能检测到氟化物90-120分钟。

THE AMOUNT OF TOTAL FLUORIDE RETAINED AFTER BRUSHING WITH A DENTIFRICE WAS AN AVG 19.3% OF THAT APPLIED, WHILE THAT AFTER TOPICAL APPLICATION OF 2% NAF SOLN FOR 4 MIN WAS 13.6%. AFTER RINSING WITH 10 ML OF 500 PPM NAF SOLN FOR 30 SEC 11.6%, & AFTER CRUNCHING TABLET CONTAINING 1 MG F, 8.9% WAS RETAINED. AFTER MOUTH RINSING OR TOPICAL APPLICATION, RESIDUAL FLUORIDE WAS FOUND IN SALIVA FOR 24-48 HR. SALIVARY FLUORIDE WAS FOUND FOR ONLY 90-120 MIN AFTER APPLICATION OF MONOFLUOROPHOSPHATE CONTAINING DENTIFRICE OR FLUORIDE TABLETS.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  8
• 危险品标志：
  T,C
• 危险类别码：
  R23/24/25,R34
• 危险品运输编号：
  UN 1776 8/PG 2
• WGK Germany：
  3
• RTECS号：
  TE5000000
• 包装等级：
  II
• 危险类别：
  8
• 安全说明：
  S26,S27,S36/37/39,S45
• 储存条件：
  常温下应保持密闭存放，选择阴凉、通风且干燥的地方。

SDS

Name:	Fluorophosphoric Acid 70% Material Safety Data Sheet
Synonym:	Monofluorophosphoric Acid; Phosphorofluoridic Acid
CAS:	13537-32-1

Section 1 - Chemical Product MSDS Name:Fluorophosphoric Acid 70% Material Safety Data Sheet
Synonym:Monofluorophosphoric Acid; Phosphorofluoridic Acid

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
13537-32-1	Fluorophosphoric Acid	70%	unlisted

Hazard Symbols: T
Risk Phrases: 23/24/25 34

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Toxic by inhalation, in contact with skin and if swallowed. Causes burns.Hygroscopic (absorbs moisture from the air).Corrosive.
Potential Health Effects
Eye:
Causes eye burns. May cause chemical conjunctivitis and corneal damage.
Skin:
Causes skin burns. May cause skin rash (in milder cases), and cold and clammy skin with cyanosis or pale color.
Ingestion:
May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May cause perforation of the digestive tract. The toxicological properties of this substance have not been fully investigated. May cause systemic effects.
Inhalation:
May cause irritation of the respiratory tract with burning pain in the nose and throat, coughing, wheezing, shortness of breath and pulmonary edema. Causes chemical burns to the respiratory tract.
Inhalation may be fatal as a result of spasm, inflammation, edema of the larynx and bronchi, chemical pneumonitis and pulmonary edema.
Aspiration may lead to pulmonary edema. May cause systemic effects.
Chronic:
Effects may be delayed.

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Section 4 - FIRST AID MEASURES
Eyes: Get medical aid immediately. Do NOT allow victim to rub eyes or keep eyes closed. Extensive irrigation with water is required (at least 30 minutes).
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Destroy contaminated shoes.
Ingestion:
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Get medical aid immediately. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to keep fire-exposed containers cool. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. Containers may explode when heated.
Extinguishing Media:
Use dry chemical. Cool containers with flooding quantities of water until well after fire is out.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Keep container tightly closed. Do not get on skin or in eyes. Do not ingest or inhale. Use with adequate ventilation. Use and store under nitrogen. Use only in a chemical fume hood. Discard contaminated shoes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Corrosives area. Store protected from moisture.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 13537-32-1: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to minimize contact with skin.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Liquid
Color: colorless
Odor: pungent odor
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: None.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: soluble
Specific Gravity/Density: 1.8300g/cm3
Molecular Formula: H2PO3F
Molecular Weight: 99.99

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, moisture, excess heat, exposure to moist air or water.
Incompatibilities with Other Materials:
Moisture, strong bases, strong oxidizing agents.
Hazardous Decomposition Products:
Phosphine, irritating and toxic fumes and gases, hydrogen fluoride gas.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 13537-32-1: TE5000000 LD50/LC50:
Not available.
Carcinogenicity:
Fluorophosphoric Acid - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: FLUOROPHOSPHORIC ACID, ANHYDROUS
Hazard Class: 8
UN Number: 1776
Packing Group: II
IMO
Shipping Name: FLUOROPHOSPHORIC ACID, ANHYDROUS
Hazard Class: 8
UN Number: 1776
Packing Group: II
RID/ADR
Shipping Name: FLUOROPHOSPHORIC ACID, ANHYDROUS
Hazard Class: 8
UN Number: 1776
Packing group: II

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 23/24/25 Toxic by inhalation, in contact with skin
and if swallowed.
R 34 Causes burns.
Safety Phrases:
S 28A After contact with skin, wash immediately with
plenty of water.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
S 38 In case of insufficient ventilation, wear
suitable respiratory equipment.
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 13537-32-1: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 13537-32-1 is listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 13537-32-1 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途：可用作金属去污剂、化学上光剂、催化剂以及金属表面防腐剂等。

反应信息

• 作为反应物：
  描述：

  单氟磷酸 在 H₂O 作用下， 以 not given 为溶剂， 生成 磷酸
  参考文献：
  名称：

  Studies of Fluorophosphoric Acids and Their Derivatives. XIII. Preparation of Anhydrous Monofluorophosphoric Acid¹

  摘要：

  DOI：

  10.1021/ja01197a030
• 作为产物：
  描述：

  六氟磷酸锂 在 碳酸乙烯酯 、 碳酸二甲酯 作用下， 以 氘代二甲亚砜 为溶剂， 反应 0.5h， 生成 单氟磷酸
  参考文献：
  名称：

  详细的拉曼光谱和NMR光谱分析 LiPF 6基锂离子电池电解质 的热分解初始阶段

  摘要：

  与特定的电极化学性质无关，基于LiPF 6的最先进的锂离子电池电解质在有机溶剂中的耐热性低，并且在高温下的循环寿命差。在此，我们使用拉曼光谱和NMR光谱对在85°C下存储的EC / DMC中LiPF 6热分解的初始阶段进行详细研究。如在拉曼光谱中检测到的那样，在储存过程中（长达160小时），放出了大量的CO 2。时间分辨的1 H，31 P和19 F NMR光谱显示POF 3，POF（OH）2，POF 2（OCH 2 CH2） n F和POF 2 OMe作为反应性分解产物。我们独特的19 F NMR方法（在加热的同时以高能量和高时间分辨率进行测量）可以对进化出的物种进行首次定量分析，并揭示了在最初的30分钟至72小时内的几种分解反应，其中HF和POF的速率2 OMe的形成令人惊讶地是线性的。发现EC与DMC相比反应性低得多。所有信息都用于制定基于LiPF 6的电解质的更新分解路径图。

  DOI：

  10.1039/c3ra42611d
• 作为试剂：
  描述：

  苯甲醛 、 2-氨基苯酚 在 单氟磷酸 作用下， 以 乙醇 为溶剂， 反应 2.4h， 以90%的产率得到2-苯基苯并恶唑
  参考文献：
  名称：

  氟化磷酸作为一种多功能有效催化剂，用于在室温下合成一系列苯并咪唑、苯并恶唑和苯并噻唑

  摘要：

  摘要 本工作描述了通过 1, 2-苯二胺、2-氨基苯硫酚或 2-氨基苯酚与芳基、脂肪族和杂芳基醛环化合成一系列苯并咪唑、苯并恶唑和苯并噻唑。本合成方案在室温下在乙醇溶剂中存在 5 mol% 氟磷酸作为催化剂时非常有效。更短的反应时间、简单的后处理技术、高产率和容易获得是本合成方法的特定补偿。

  DOI：

  10.1080/10426507.2020.1871345

文献信息

• Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries
  作者：Christopher L. Campion、Wentao Li、Brett L. Lucht

  DOI：10.1149/1.2083267

  日期：——

  The thermal decomposition of lithium-ion battery electrolytes 1.0 M LiPF 6 in one or more carbonate solvents has been investigated. Electrolytes containing diethyl carbonate (DEC), ethylene carbonate (EC), a 1:1 mixture of EC/dimethyl carbonate (DMC), and a 1:1:1 mixture EC/DMC/DEC have been investigated by multinuclear nuclear magnetic spectroscopy, gas chromatography with mass selective detection

  已经研究了锂离子电池电解质 1.0 M LiPF 6 在一种或多种碳酸酯溶剂中的热分解。已通过多核核磁光谱研究了含有碳酸二乙酯 (DEC)、碳酸亚乙酯 (EC)、EC/碳酸二甲酯 (DMC) 的 1:1 混合物和 EC/DMC/DEC 的 1:1:1 混合物的电解质，具有质量选择检测器的气相色谱和尺寸排阻色谱。热分解产生的产物包括：二氧化碳 (CO 2 )、乙烯 (CH 2 CH 2 )、二烷基醚 (R 2 O)、烷基氟化物 (RF)、氟氧化磷 (OPF 3 )、氟磷酸盐 [OPF 2 OR、OPF(OR ) 2 ]、氟磷酸[OPF 2 OH、OPF(OH) 2 ]和低聚环氧乙烷。在所有 LiPF 6 /碳酸盐电解质中，分解机制是相似的。痕量质子杂质导致 OPF 2 OR 的生成，其自动催化分解 LiPF 6 和碳酸盐。DEC的存在导致乙烯的生成，而EC的存在导致封端的低聚环氧乙烷[OPF
• Preparation and properties of difluorophosphino-derivatives of phosphorus(V) hydroxy-compounds
  作者：E. A. V. Ebsworth、George M. Hunter、David W. H. Rankin

  DOI：10.1039/dt9830000245

  日期：——

  Phosphoric acid and other hydroxy-derivatives of phosphorus(V) react with S(PF2)2 to give difluorophosphino-esters. Tris(difluorophosphino) phosphate, PO(OPF2)3, and bis(difluorophosphino) monofluorophosphate, PFO(OPF2)2, have been prepared and characterised by n.m.r., mass, and vibrational spectroscopy. The reaction of PO(OPF2)3 with diborane is described. The formation and n.m.r. spectra of PO(OPF2)2Ph

  磷酸和磷（V）的其他羟基衍生物与S（PF 2）2反应，生成二氟膦酸酯。已经制备了三（二氟膦基）磷酸酯PO（OPF 2）3和双（二氟膦基）单氟磷酸酯（PFO（OPF 2）2），并通过核磁共振，质谱和振动光谱对其进行了表征。描述了PO（OPF 2）3与乙硼烷的反应。还报道了PO（OPF 2）2 Ph和PO（OPF 2）Ph 2的形成和核磁共振谱。
• Synthesis and Structural and Magnetic Characterization of Cobalt(II) Phosphonate Cage Compounds
  作者：Stuart Langley、Madeleine Helliwell、Roberta Sessoli、Simon J. Teat、Richard E. P. Winpenny

  DOI：10.1021/ic700984r

  日期：2008.1.1

  Reaction of cobalt salts with phosphonic acids in the presence of 6-chloro-2-hydroxypyridine as a co-ligand, normally in its deprotonated form, leads to a series of new polymetallic cobalt cages. The most common structural type is a Co(14)} cage which resembles a fragment of cobalt hydroxide. Variation of the phosphonate present and the cobalt salt leads to Co(6)}, Co(8)}, Co(10)}, Co(11)}, Co(12)}

  钴盐与膦酸在作为共配体的6-氯-2-羟基吡啶存在下（通常为去质子化形式）反应，会生成一系列新的多金属钴笼。最常见的结构类型是Co（14）}笼，类似于氢氧化钴的片段。存在的膦酸酯和钴盐的变化会导致Co（6）}，Co（8）}，Co（10）}，Co（11）}，Co（12）}，Co（13） }}和Co（20）}笼子，它们均已通过X射线晶体学表征。这些笼子的磁性研究表明，产品chi（m）T与T总体下降，但对于Co（6）}，Co（8）}和Co（12）}，在低温下存在最大值，这表明非反磁性基态。
• Two Modifications of NH4HPO3F: Synthesis and Crystal Structure
  作者：H. A. Prescott、S. I. Troyanov、E. Kemnitz

  DOI：10.1002/1521-3749(200201)628:1<152::aid-zaac152>3.0.co;2-o

  日期：2002.1

  Modifikationen von NH4HPO3F: Synthese und Kristallstruktur Die α- und β-Modifikationen von NH4HPO3F wurden synthesiert und mit Einkristallstrukturanalytik charakterisiert. Die Kristallstruktur von α-NH4HPO3F wurde bei 180 K gemessen und ist monoklin, Raumgruppe P21/n, mit a = 7,4650(1), b = 15,586(2), c = 7,5785(9) A, β = 108,769(9)°, V = 834,9(2) A3, Z = 8, und R1 = 0,0376 and wR2 = 0,0818. β-NH4HPO3F

  合成了 NH4HPO3F 的 α 和 β 变体，并用单晶 X 射线衍射表征。在180 K测定的α-NH4HPO3F晶体结构为单斜晶系，空间群P21/n，a = 7.4650(1), b = 15.586(2), c = 7.5785(9) A, β = 108.769(9)° , V = 834.9(2) A3，Z = 8，R1 = 0.0376 和 wR2 = 0.0818。在 310 K 下测量的 β-NH4HPO3F 在三斜空间群 P 1 中结晶，a = 7.481(1), b = 7.511(1), c = 7.782(1) A, α = 84.31(1), β = 84.20 (1)，γ = 68.67(2)°，V = 404.31(9) A3，Z = 4，R1 = 0.0254 和 wR2 = 0.0735。对于 β-NH4HPO3F，在 180 和 310 K 之间未观察到相变。NH4HPO4F
• Formation of monofluorophosphate from fluoride in phosphoric acid – water and phosphoric acid – sulfuric acid – water mixtures
  作者：Kenneth E Newman、Raymond E Ortlieb、Nicole Pawlik、Jason Reedyk

  DOI：10.1139/v07-027

  日期：2007.5.1

  When dissolved in concentrated phosphoric acid, sodium fluoride reacts rapidly to form monofluorophosphate. In less concentrated acid, the reaction does not proceed to completion, and the reaction kinetics become very much slower. The equilibrium and rate constants for the reaction have been determined. In ternary mixtures of phosphoric acid, sulfuric acid, and water, the formation of monofluorophosphate is considerably enhanced, and the kinetics are rapid. The results are interpreted in terms of the very low water activity coefficients in strong-acid solutions.Key words: monofluorophosphate, monofluorophosphoric acid, ¹⁹F NMR, ³¹P NMR, phosphoric acid, sulufric acid, equilibria, kinetics.

  当氟化钠溶于浓磷酸时，会迅速反应生成一氟磷酸盐。在浓度较低的酸中，反应不会完全进行，反应动力学也变得非常缓慢。该反应的平衡常数和速率常数已经确定。在磷酸、硫酸和水的三元混合物中，单氟磷酸盐的生成显著增强，且反应动力学迅速。关键词：单氟磷酸盐；单氟磷酸；19F NMR；31P NMR；磷酸；硫酸；平衡；动力学。