Red fuming nitric acid: Difference between revisions

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 {{Chembox
+| Verifiedfields = changed
-| verifiedrevid = 445998230
+| Watchedfields = changed
-| ImageFile =
+| verifiedrevid = 451432930
+| ImageFile = Fuming nitric acid 40ml.jpg
 | ImageSize =
+| ImageAlt =40-milliliter container of red fuming nitric acid
-| ImageAlt =
-| IUPACName = Nitric Acid
+| IUPACName = Nitric acid
-| OtherNames = Red Fuming Nitric Acid
+| OtherNames = Red fuming nitric acid
-| Section1 = {{Chembox Identifiers
+|Section1={{Chembox Identifiers
 | PubChem =
+| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
-| CASNo = 78989-43-2
-| SMILES = }}
+| ChemSpiderID = None
+| CASNo_Ref = {{cascite|correct|??}}
-| Section2 = {{Chembox Properties
+| CASNo = 52583-42-3
-| Formula = {{hydrogen}}{{nitrogen}}{{oxygen|3}} + {{nitrogen}}{{oxygen|2}}
+| SMILES =
+ }}
+|Section2={{Chembox Properties
+| Formula = {{chem2|HNO3}} + {{chem2|NO2}}
 | MolarMass =
-| Appearance = Liquid, Red fumes
+| Appearance = Liquid, red fumes
-| Density = Increases as free NO2 content increases
+| Density = Increases as free {{chem2|NO2}} content increases
 | MeltingPt =
-| BoilingPt = 120.5°C
+| BoilingPtC = 83
-| Solubility = miscible in water}}
+| Solubility = Miscible in water
+ }}
-| Section3 = {{Chembox Hazards
+|Section3={{Chembox Hazards
-| MainHazards = Skin and metal corrosion; serious eye damage; toxic (oral, dermal, inhale); severe burns
+| MainHazards = Skin and metal corrosion; serious eye damage; toxic (oral, dermal, pulmonary); severe burns
 | FlashPt =
+| AutoignitionPt =
-| Autoignition = }}
+ }}
 }}<!-- Text starts below-->
-'''Red fuming nitric acid''' ('''RFNA''') is a storable [[oxidizer]] used as a [[rocket propellant]].  It consists mainly of [[nitric acid]] ({{hydrogen}}{{nitrogen}}{{oxygen|3}}), also containing 13% [[dinitrogen tetroxide]] and 3% [[water]].  The dissolved nitrogen dioxide is very concentrated and can be found at room temperature{{Clarify|date=May 2011}}. The color of the resulting red fuming nitric acid is due to the dinitrogen tetroxide, which breaks down partially to form [[nitrogen dioxide]].  [[White fuming nitric acid]] does not contain free dinitrogen tetroxide. RFNA gives off a suffocating odor. It increases the flammability of combustible materials and is highly exothermic when reacted with water.
+'''Red fuming nitric acid''' ('''RFNA''') is a storable [[oxidizer]] used as a [[rocket propellant]].  It consists of 84% [[nitric acid]] ({{chem2|auto=1|HNO3}}), 13% [[dinitrogen tetroxide]] ({{chem2|auto=1|N2O4}}) and 1–2% [[water]].<ref>{{cite journal
+ |title=Problems in Storage and Handling of Red Fuming Nitric Acid
+ |journal=Defence Science Journal
+ |volume=33 |issue=4 |date=October 1983 |pages=331–337
+ |author1=V. S. Sugur |author2=G. L. Manwani
+ |doi=10.14429/dsj.33.6188 |doi-access=free
+ }}</ref> The color of red fuming nitric acid is due to the dinitrogen tetroxide, which breaks down partially to form [[nitrogen dioxide]]. The nitrogen dioxide dissolves until the liquid is saturated, and produces toxic fumes with a suffocating odor. RFNA increases the flammability of combustible materials and is highly exothermic when reacting with water.
-It is usually used with an [[Corrosion inhibitor|inhibitor]] (with various, sometimes secret, substances, including [[hydrogen fluoride]];<ref>{{Cite book | last = Clark | first = John D. | authorlink = John D. Clark | title = Ignition! An Informal History of Liquid Rocket Propellants | publisher = Rutgers University Press | date = 1972 | page = 62 | isbn = 0813507251 }}</ref> any such combination is called "inhibited RFNA" '''IRFNA''') because nitric acid attacks most container materials.
+It is usually used with an [[corrosion inhibitor|inhibitor]] (with various, sometimes secret, substances, including [[hydrogen fluoride]];<ref name=Clark2018>{{cite book |isbn = 978-0-8135-9918-2 |title = Ignition!: An Informal History of Liquid Rocket Propellants |last1 = Clark |first1 = John Drury |author-link=John Drury Clark |date = 23 May 2018 |publisher = Rutgers University Press |url=https://books.google.com/books?id=BdU4DwAAQBAJ&q=red%20fuming  |pages=302 |oclc=281664}}</ref>{{rp|62}} any such combination is called ''inhibited RFNA'', ''IRFNA'') because nitric acid attacks most container materials. Hydrogen fluoride for instance will [[passivation (chemistry)|passivate]] the container metal with a thin layer of metal fluoride, making it nearly impervious to the nitric acid.
-It can also be a component of a [[monopropellant]]; with substances like amine nitrates dissolved in it, it can be used as the sole fuel in a rocket. It is not normally used this way however.
+It can also be a component of a [[monopropellant]]; with substances like amine nitrates dissolved in it, it can be used as the sole fuel in a rocket. This is inefficient and it is not normally used this way.
-During [[World War II]], the German military used RFNA in some rockets. The mixtures used were called '''S-[[List of stoffs|Stoff]]''' (96% nitric acid with 4% [[ferric chloride]]) and '''SV-Stoff''' (94% nitric acid with 6% dinitrogen tetroxide).
+During [[World War II]], the German military used RFNA in some rockets. The mixtures used were called ''S-[[List of stoffs|Stoff]]'' (96% nitric acid with 4% [[ferric chloride]] as an ignition catalyst<ref name=Clark2018 />{{rp|115–9}}) and ''SV-Stoff'' (94% nitric acid with 6% dinitrogen tetroxide) and nicknamed ''Salbei'' ([[Salvia officinalis|sage]]).
+Inhibited RFNA was the oxidizer of the world's most-launched light orbital rocket, the [[Kosmos-3M]]. In former-Soviet countries inhibited RFNA is known as [[Mélange (rocket fuel component)|Mélange]].
-Inhibited RFNA, used in [[Al Hussein (missile)|modified SS-1 Scud]] missiles as an oxidizer by the Iraqi military during the 1991 Persian [[Gulf War]], was suggested as a possible factor causing [[Gulf War Syndrome]].{{Citation needed|date=May 2010}}  However, this theory was later refuted.{{Citation needed|date=May 2010}}
-Other uses for RFNA include fertilizers, dye intermediates, explosives, and pharmaceutic aid as acidifier. It can also be used as a laboratory reagent in photoengraving, metal etching.<ref>{{Cite book | last = O'Neil  | first = Maryadele J. | authorlink =  | title = The Merck index: an encyclopedia of chemicals, drugs, and biologicals | publisher = Merck | date = 2006 | page = 6576 | isbn = 9780911910001 }}</ref>
+Other uses for RFNA include fertilizers, dye intermediates, explosives, and pharmaceutical acidifiers. It can also be used as a laboratory reagent in photoengraving and metal etching.<ref>{{Cite book | last = O'Neil  | first = Maryadele J. | title = The Merck index: an encyclopedia of chemicals, drugs, and biologicals | publisher = Merck | year = 2006 | page = 6576 | isbn = 978-0-911910-00-1 }}</ref>
 ==Compositions==
-*'''IRFNA IIIa''': 83.4% [[nitric acid|HNO<sub>3</sub>]], 14% [[nitrogen dioxide|NO<sub>2</sub>]], 2% [[water (molecule)|H<sub>2</sub>O]], 0.6% [[hydrogen fluoride|HF]]
+* ''IRFNA IIIa'': 83.4% [[nitric acid|HNO<sub>3</sub>]], 14% [[nitrogen dioxide|NO<sub>2</sub>]], 2% [[water (molecule)|H<sub>2</sub>O]], 0.6% [[hydrogen fluoride|HF]]
-*'''IRFNA IV HDA''': 54.3% HNO<sub>3</sub>, 44% NO<sub>2</sub>, 1% H<sub>2</sub>O, 0.7% HF
+* ''IRFNA IV HDA'': 54.3% HNO<sub>3</sub>, 44% NO<sub>2</sub>, 1% H<sub>2</sub>O, 0.7% HF
-*'''S-Stoff''': 96% HNO<sub>3</sub>, 4% [[ferric chloride|FeCl<sub>3</sub>]]
+* ''S-Stoff'': 96% HNO<sub>3</sub>, 4% [[ferric chloride|FeCl<sub>3</sub>]]
-*'''SV-Stoff''': 94% HNO<sub>3</sub>, 6% [[dinitrogen tetroxide|N<sub>2</sub>O<sub>4</sub>]]
+* ''SV-Stoff'': 94% HNO<sub>3</sub>, 6% [[dinitrogen tetroxide|N<sub>2</sub>O<sub>4</sub>]]
-*'''AK20''': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>
+* ''AK20'': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>
-*'''AK20F''': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, fluorine-based inhibitor
+* ''AK20F'': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, fluorine-based inhibitor
-*'''AK20I''': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, iodine-based inhibitor
+* ''AK20I'': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, iodine-based inhibitor
-*'''AK20K''': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, unknown inhibitor
+* ''AK20K'': 80% HNO<sub>3</sub>, 20% N<sub>2</sub>O<sub>4</sub>, potassium-based inhibitor
-*'''AK27I''': 73% HNO<sub>3</sub>, 27% N<sub>2</sub>O<sub>4</sub>, iodine-based inhibitor
+* ''AK27I'': 73% HNO<sub>3</sub>, 27% N<sub>2</sub>O<sub>4</sub>, iodine-based inhibitor
-*'''AK27P''': 73% HNO<sub>3</sub>, 27% N<sub>2</sub>O<sub>4</sub>, unknown inhibitor
+* ''AK27P'': 73% HNO<sub>3</sub>, 27% N<sub>2</sub>O<sub>4</sub>, phosphorus-based inhibitor
-==Experiments==
+==Corrosion==
+; Hydrofluoric acid content of IRFNA<ref name="ReferenceA">{{Cite journal |last1=Karplan |first1=Nathan |last2=Andrus |first2=Rodney J. |date=October 1948 |title=Corrosion of Metals in Red Fuming Nitric Acid and in Mixed Acid |journal=Industrial and Engineering Chemistry |volume= 40 |issue=10 |pages=1946–1947 |doi=10.1021/ie50466a021 }}</ref><ref>{{cite tech report| url=https://apps.dtic.mil/sti/tr/pdf/AD0090526.pdf| archive-url=https://web.archive.org/web/20180727002438/http://www.dtic.mil/dtic/tr/fulltext/u2/090526.pdf| url-status=live| archive-date=July 27, 2018| title=Corrosion Studies in Fuming Nitric Acid| access-date=2024-01-02 |date=October 1955 |first1=Edson H. |last1=Phelps |first2=Fredrick S. |last2=Lee |first3=Raymond B. |last3=Robinson |publisher=[[Wright Air Development Center]] |number=55-109}}</ref>: When RFNA is used as an oxidizer for rocket fuels, it usually has a [[hydrogen fluoride|HF]] content of about 0.6%. The purpose of the HF is to act as a corrosion inhibitor by forming a metal fluoride layer on the surface of the storage vessels.
-*[[Hydrofluoric Acid]] Content of RFNA<ref>Baker, Berstil B. (June 1958). "Rapid Estimation of Hydrofluoric Acid in Red Fuming Nitric Acid". ''Analytical Chemistry''. 30(6) pp.1085-1086</ref>
+; Water content of RFNA<ref>{{cite journal|doi=10.1021/ac60205a055|pages=1967–1970|title=Determination of Water in Red Fuming Nitric Acid by Karl Fischer Titration|year=1963|last1=Burns|first1=E. A.|last2=Muraca|first2=R. F.|journal=Analytical Chemistry|volume=35|issue=12}}</ref>: To test the water content, a sample of 80% HNO<sub>3</sub>, 8–20% NO<sub>2</sub>, and the rest H<sub>2</sub>O depending on the varied amount of NO<sub>2</sub> in the sample. When the RFNA contained HF, there was an average H<sub>2</sub>O% between 2.4% and 4.2%. When the RFNA did not contain HF, there was an average H<sub>2</sub>O% between 0.1% and 5.0%. When the metal impurities from corrosion were taken into account, the H<sub>2</sub>O% increased, and the H<sub>2</sub>O% was between 2.2% and 8.8%
-:When RFNA is used as an oxidizer for rocket fuels, it usually has a [[hydrogen fluoride|HF]] content of about .6%. The purpose of the HF is to act as a corrosion inhibitor. RFNA was tested for HF with a standard solution containing 12% of NO<sub>2</sub> and a density of 1.57. These experiments were performed using an electrometric method. It was determined that the hydrofluoric acid content was about .5% by weight. This is very close to the usually .6% in rocket fuels.
+; Corrosion of metals in RFNA<ref name="ReferenceA"/>: Stainless steel, aluminium alloys, iron alloys, chrome plates, tin, gold and tantalum were tested to see how RFNA affected the corrosion rates of each. Experiments were performed using 16% and 6.5% RFNA samples and the different substances listed above. Many different stainless steels showed resistance to corrosion. Aluminium alloys did not endure as well as stainless steels especially in high temperature, but the corrosion rates were not high enough to prohibit the use of this with RFNA. Tin, gold and [[tantalum]] showed high corrosion resistance similar to that of stainless steel. These materials are better though because at high temperatures the corrosion rates did not increase much. Corrosion rates at elevated temperatures increase in the presence of phosphoric acid. Sulfuric acid decreased corrosion rates.
-*[[Water]] content of RFNA<ref>Burns, E. A. and Muraca, R. F. (November 1963). "Determination of Water in Red Fuming Nitric Acid by Karl Fischer Titration". ''Analytical Chemistry''. 35(12) pp.1967-1970</ref>
-:To test the water content, a sample of 80% HNO<sub>3</sub>, 8-20% NO<sub>2</sub>, and the rest H<sub>2</sub>O depending on the varied amount of NO<sub>2</sub> in the sample. When the RFNA contained HF, there was an average H<sub>2</sub>O% between 2.4% and 4.2%. When the RFNA did not contain HF, there was an average H<sub>2</sub>O% between .1% and 5.0%. When the metal impurities from corrosion were taken into account, the H<sub>2</sub>O% increased, and the H<sub>2</sub>O% was between 2.2% and 8.8%
-*Corrosion of metals in RFNA<ref>Karplan, Nathan and Andrus, Rodney J. (October 1948). "Corrosion of Metals in Red Fuming Nitric Acid and in Mixed Acid". ''Industrial and Engineering Chemistry''. 40(10) pp.1946-1947</ref>
-:Stainless steel, aluminum alloys, iron alloys, chrome plates, tin, gold and tantalum were tested to see how RFNA affected the corrosion rates of each. This is important to understand because the containers that RFNA is kept in will affect the RFNA. Experiments were performed using 16% and 6.5% RFNA samples and the different substances listed above. Many different stainless steels showed resistance to corrosion. Aluminum alloys did not hold up as well as stainless steels especially in high temperatures but the corrosion rates were not high enough to prohibit the use of this with RFNA. Tin, gold and tantalum showed high resistance such like that of stainless steel. These are better though because at high temperatures, the corrosion rates were still kept low. It is important to note that at higher temperatures and the presence of phosphoric acid, the corrosion rates increase while sulfuric acid helped the corrosion rates and kept the substances from corrosion.
-==Related==
+==See also==
 * [[White fuming nitric acid]]
-* [[Nitric Acid]]
 ==References==
 {{Reflist}}
 ==External links==
-*[http://www.npi.gov.au/database/substance-info/profiles/65.html National Pollutant Inventory - Nitric Acid Fact Sheet]
+* [https://web.archive.org/web/20060408080735/http://www.npi.gov.au/database/substance-info/profiles/65.html National Pollutant Inventory – Nitric Acid Fact Sheet]
-* http://www.astronautix.com/props/nitidjpx.htm
+* https://web.archive.org/web/20030429160808/http://www.astronautix.com/props/nitidjpx.htm
 [[Category:Rocket oxidizers]]
+[[Category:Oxidizing acids]]
-[[de:RFNA]]
-[[fr:Acide nitrique fumant rouge]]
-[[it:Acido nitrico fumante rosso inibito]]
-[[ja:赤煙硝酸]]
-[[ru:Красная дымящаяся азотная кислота]]
-[[fi:RFNA]]
-[[sv:Röd rykande salpetersyra]]