Описание
Гидразойная кислота (азид водорода, HN3) — гидрид азота, сопряжённая кислота азид-аниона. Бесцветная летучая жидкость с невыносимым резким неприятным запахом, растворима в воде.
Основные атрибуты
- CAS №: 7782-79-8 (также CAS 127229-27-0, 57077-96-0, 227798-96-1)
- Химическая формула: HN3
- Молекулярный вес: 43,02804 (по расширенным данным 43,029); точная масса 43,01700; моноизотопная масса 43,017047045
- Номер ЕС: 231-965-8
- UNII: 6P5C4D5D7I
- Характеристика PSA: 61,24000 (по расширенным данным площадь топологической полярной поверхности 25,8)
- XLogP3: 0,42796 (по расширенным данным 1,7)
- Количество доноров водородных связей: 1; акцепторов: 2; тяжёлых атомов: 3; сложность: 23
Физико-химические характеристики
- Цвет/форма: бесцветная жидкость
- Плотность: 1,09 (25/4 °C)
- Температура плавления: -80 °C
- Температура кипения: 37 °C
- Давление пара: 484 мм рт. ст.
- Постоянная закона Генри: 8,29×10⁻⁵ атм·куб. м/моль при 25 °C
- pKa: 4,72
Токсичность
- LCL0 при вдыхании у крыс: 1100 частей на миллион за 1 час
- LD50 внутрибрюшинно у мышей: 22 мг/кг
- Класс токсичности: наиболее токсичный
- Сильное раздражение кожи, глаз и слизистых оболочек
Стабильность и опасная реактивность
Нестабильна, сильно взрывоопасна в концентрированном или чистом состоянии; легко образует взрывоопасные соединения с тяжёлыми металлами (реагирует с образованием очень нестабильных азидов тяжёлых металлов, бурно реагирует с кадмием, медью, никелем, азотной кислотой, фтором) и взрывоопасные соли с сероуглеродом. Взрывоопасна при поражении электрическим током или воздействии тепла, вибрации, ударов, трения.
Информация по технике безопасности
- Категория опасности: 1.1A
- Транспортные коды: 0473
- Номер RTECS: MW2800000
- Указание по опасности: H200 — нестабильное взрывчатое вещество
- Меры предосторожности: P201, P202, P260, P261, P264, P270, P271, P280, P281, P304+P340, P305+P351+P338, P307+P311, P312, P321, P337+P313, P372, P373, P380, P401, P403+P233, P405, P501
Условия хранения
Хранить в плотно закрытых контейнерах в прохладном, хорошо проветриваемом помещении вдали от несовместимых материалов, окислителей, легковоспламеняющихся материалов и пищевых продуктов; беречь от перегрева и ударов.
Способы получения
Получают реакцией гидразина с азотистой кислотой или закиси азота с амидом натрия при нагревании, а также действием серной кислоты на азид натрия.
Область применения
Промышленно гидразойная кислота используется при получении азидов тяжёлых металлов для оболочечных детонаторов. Кроме того, она образуется как побочный продукт при срабатывании автомобильных подушек безопасности, где азид натрия используется в качестве наполнителя: измеренная концентрация HN3 при этом составляет 0,15-7,3 промилле, а каждый грамм азида натрия выделяет 0,56 л азота при 25 °C и 1 атмосфере.
Судьба в окружающей среде
Расчётный коэффициент почвенной сорбции Koc ≈ 3 указывает на очень высокую подвижность в почве; вещество почти полностью существует в анионной форме при pH 5-9 (согласно pKa 4,72) и не улетучивается с влажных поверхностей, но испаряется с сухой почвы благодаря давлению пара 484 мм рт. ст. Период полураспада в атмосфере за счёт реакции с гидроксильными радикалами оценивается в 4-12 суток, при прямом фотолизе солнечным светом — 52 часа. Расчётный биоконцентрационный фактор (BCF) ≈ 3 при логарифмическом коэффициенте распределения Kow ≈ 1,16 указывает на низкий потенциал биоконцентрации в водных организмах.
Аналитический контроль
Метод OSHA ID-211 (ионная хроматография с УФ-детектором) определяет гидразойную кислоту в воздухе с пределом обнаружения 0,001 промилле (качественно) и 0,004 промилле (количественно) в пересчёте на HN3.
Colorless, volatile liquid; obnoxious odor.Soluble in water.
Colorless liquid with an intolerable pungent odor.
Hydrogen azide is a nitrogen hydride. It is a conjugate acid of an azide anion.
43.02804
43.01700
231-965-8
6P5C4D5D7I
Colorless liquid
61.24000
0.42796
Colorless liquid with an intolerable pungent odor.
1.09(25/4ºC)
-80 °C
37 °C
very soluble H2O [HAW93]
Store in tightly closed containers in a cool, well ventilated area away from incompatible materials ... Protect from heat or shock.
484 mmHg
Inhalation-rat LCL0: 1100 PPM/ 1 hour; abdominal cavity-mouse LD50: 22 mg/kg
Combustion produces toxic nitrogen oxide fumes
A dangerously sensitive explosive hazard when shocked or exposed to heat.
Obnoxious odor
Henry's Law constant = 8.29X10-5 atm-cu m/mol at 25 °C
pKa = 4.72
Dangerous explosion risk when shocked or heated|Volatile|When heated to decomposition it emits toxic fumes of NOx
1.1A
0473
MW2800000
Handle lightly; storeroom ventilated, away from open flames, high temperature, sunlight; stored separately from oxidants, flammable materials, food materials
High heat, vibration, impact, friction can be explosive
Unstable. Violently explosive in the concentrated or pure states. Readily forms explosive compounds with heavy metals. This is a dangerous and hard to handle substance which must not be prepared or handled by non-experts.
P201, P202, P260, P261, P264, P270, P271, P280, P281, P304+P340, P305+P351+P338, P307+P311, P312, P321, P337+P313, P372, P373, P380, P401, P403+P233, P405, P501
H200
SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal and plant life; and conformance with environmental and public health regulations.|May be destroyed by converting hydrazoic acid to sodium azide and the reaction mixture decomposed with nitrous acid.
Reacts with heavy metals to form very unstable heavy metal azides. Reacts violently with /cadmium, copper, nickel, nitric acid, fluorine/.|Forms explosive salts with carbon disulfide.
|Danger|H200: Unstable Explosive [Danger Explosives]|P201, P202, P260, P261, P264, P270, P271, P280, P281, P304+P340, P305+P351+P338, P307+P311, P312, P321, P337+P313, P372, P373, P380, P401, P403+P233, P405, and P501
Wear protective gloves and clothing to prevent any reasonable probability of skin contact ... Wear splash-proof chemical goggles and faceshield unless full facepiece respiratory protection is worn.|Where there is potential for exposure to the chemical, use a NIOSH/MSHA approved supplied-air respirator with a full facepiece operated in the positive pressure mode or with a full facepiece, hood, or helmet in the continuous flow mode, or use a NIOSH/MSHA approved self-contained breathing apparatus with a full facepiece operated in pressure-demand or other positive pressure mode.
Dangerously explosive material.
A dangerously sensitive explosive hazard when shocked or exposed to heat.
Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users or potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors or shows any signs of deforming), withdraw immediately to a secure position ... The only respirators recommended for fire fighting are self-contained breathing apparatuses that have full facepieces and are operated in a pressure-demand or other positive-pressure mode.
Evacuate and restrict persons not wearing protective equipment from area of spill or leak until clean-up is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep the chemical out of a confined space, such as a sewer, because of the possibility of an explosion, unless the sewer is designed to prevent the build-up of explosive concentrations. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your Department of Environmental Protection or your regional office of the federal EPA for specific recommendations.
SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.|SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. The completeness of the cleaning procedures should be considered before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at the end of shift, but should remain at employee's place of work for cleaning.|SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.
A severe irritant to skin, eyes, and mucous membranes.
Recommended Exposure Limit: Ceiling Value: 0.1 ppm (as NH3); skin. /Sodium azide/
Hydrazoic acid is released upon deployment of air bags with measured concentrations of 0.15-7.3 ppm (each gram of sodium azide generates 0.56 L nitrogen at 25 °C and 1 atmosphere)(1).
most toxic
LD50 Mouse ip 22 mg/kg
Hydrazoic acid's production and use as a chemical intermediate for heavy metal azides(1) may result in its release to the environment through various waste streams(SRC). It is formed upon deployment of air bags that use sodium azide as an inflating agent and sodium azide also forms hydrazoic acid rapidly in its use as a biocide(2), resulting in its direct release to the environment(SRC).
TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 3(SRC), determined from a structure estimation method(2), indicates that hydrazoic acid is expected to have very high mobility in soil(SRC). The pKa of hydrazoic acid is 4.72(3), indicating that this compound will exist almost entirely in anion form in the environment and anions generally do not adsorb more strongly to soils containing organic carbon and clay than their neutral counterparts(4). Volatilization from moist soil is not expected because the acid exists as an anion and anions do not volatilize(SRC). Hydrazoic acid is expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 484 mm Hg at 25 °C(SRC), determined from a fragment constant method(5). Biodegradation data in soil were not available(SRC, 2010).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 3(SRC), determined from a structure estimation method(2), indicates that hydrazoic acid is not expected to adsorb to suspended solids and sediment(SRC). A pKa of 4.72(3) indicates hydrazoic acid will exist almost entirely in the anion form at pH values of 5 to 9 and therefore volatilization from water surfaces is not expected to be an important fate process(4). According to a classification scheme(5), an estimated BCF of 3(SRC), from an estimated log Kow of 1.16(6) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Biodegradation data in water were not available(SRC, 2010).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), hydrazoic acid, which has an estimated vapor pressure of 484 mm Hg at 25 °C(SRC), determined from a fragment constant method(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase hydrazoic acid is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 4 to 12 days(SRC), calculated from rate constants of 3.9X10-12(3) and 1.3X10-12(4) cu cm/molecule-sec. Direct photolysis of hydrazoic acid in the gaseous phase by sunlight has a half-life of 52 hours(4).
Hydrolysis may not be an important environmental fate process since this compound lacks functional groups that hydrolyze under environmental conditions(1). The rate constant for the vapor-phase reaction of hydrazoic acid with photochemically-produced hydroxyl radicals has been measured as 1.3X10-12(2) and 3.9X10-12(3) cu cm/molecule-sec. These correspond to atmospheric half-lives of about 12 and 4 days, respectively, at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(4). Direct photolysis of hydrazoic acid in the gaseous phase by sunlight has a half-life of 52 hours(2).
An estimated BCF of 3 was calculated in fish for hydrazoic acid(SRC), using an estimated log Kow of 1.16(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).
Using a structure estimation method based on molecular connectivity indices(1), the Koc of hydrazoic acid can be estimated to be 3(SRC). According to a classification scheme(2), this estimated Koc value suggests that hydrazoic acid is expected to have very high mobility in soil. Hydrazoic acid has been reported to be quite mobile and readily leachable in most soils(3).
A pKa of 4.72(1) indicates hydrazoic acid will exist almost entirely in the anion form at pH values of 5 to 9 and therefore volatilization from water and moist soil surfaces is not expected to be an important fate process(2). Hydrazoic acid is expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 484 mm Hg(SRC), determined from a fragment constant method(3).
Occupational exposure to hydrazoic acid may occur through inhalation and dermal contact with this compound at workplaces where hydrazoic acid is produced or used. Monitoring data indicate that the general population may be exposed to hydrazoic acid via inhalation of gasses upon deployment of air bags(1).
/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on the left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Sodium Azide (NaN3) and Related Compounds/|/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist respirations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Sodium Azide (NaN3) and Related Compounds/|/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Early intubation, at the first sign of upper airway obstruction, may be necessary. Positive pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Sodium Azide (NaN3) and Related Compounds/
/SIGNS AND SYMPTOMS/ Short Term Exposure: Irritating to skin, eyes, and respiratory tract. Continued inhalation causes cough, headache, dizziness, weakness, fall in blood pressure, chills and fever, and collapse. Prolonged exposure to high concentration can cause fatal convulstions and death. Highly toxic. Long Term Exposure: Chronic exposure can affect the central nervous system: hypotension, palpitation, ataxia, and weakness.|/CASE REPORTS/ ... This article is a case report on two young male workers, who were unloading drums of sodium azide powder when they accidentally inhaled the powder while cleaning up the material. Hypotension, nausea, vomiting and weakness were the symptoms experienced, followed by a persistent reactive airway dysfunction syndrome. It has been postulated that both sodium azide and hydrazoic acid contributed to the observed adverse effects.|/SURVEILLANCE/ ... In 1994-1995, the National Institute for Occupational Safety and Health (NIOSH) conducted a cross-sectional study of health complaints reported by sodium azide production workers at the only continuous sodium azide production facility in the United States. The NIOSH evaluation consisted of a plant industrial hygiene survey, a symptom questionnaire, ambulatory blood pressure monitoring, and blood azide analysis. Personal breathing zone air monitoring revealed exposures to sodium azide and hydrazoic acid (a reactant product) at levels greater than the NIOSH Recommended Exposure Limits (RELs). In some cases, exposures exceeded the REL despite the use of air-supplied respirators. The questionnaire revealed that most workers reported headache (10 of 11 [91%]), episodes of low blood pressure (9 of 11 [82%]), and palpitations (8 of 11 [73%]) occurring in the production areas within the 6 months preceding the study. Mild headache (4 of 11 [36%]) was the only symptom reported during our 24-hr medical survey. Ambulatory blood pressure monitoring revealed one asymptomatic employee with a drop in blood pressure (defined as a drop in systolic [at least 20 mm Hg] and diastolic [at least 10 mm Hg] blood pressure) during a period of exposure to sodium azide at a level five times the NIOSH REL. Improvements in plant engineering controls, increased attention to employee hygiene practices, and a more comprehensive respiratory protection program were recommendations made by NIOSH to reduce exposures at the plant. All facilities handling sodium azide should be aware of the potential toxicity of sodium azide and hydrazoic acid.
hydrazoic acid
Reaction of hydrazine and nitrous acid, or of nitrous oxide and sodium amide (with heat)|Produced by the action of sulfuric acid on sodium azide.
Industrially in preparation of heavy metal azides for shell detonators.
Hydrazoic acid: ACTIVE
Method: OSHA ID-211; Procedure: ion chromatograph equipped with a UV detector; Analyte: hydrazoic acid; Matrix: air; Detection Limit: Qualitative 0.001 ppm as HN3; Quantitative 0.004 ppm as HN3.
Molecular Weight:43.029
XLogP3:1.7
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Exact Mass:43.017047045
Monoisotopic Mass:43.017047045
Topological Polar Surface Area:25.8
Heavy Atom Count:3
Complexity:23
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes
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