How to Make Corned Beef Without Sodium Nitrate

Portmanteau name for nitrite derivatives

Nitrite

Names
Systematic IUPAC name dioxidonitrate(1−)
Other names nitrite
Identifiers
CAS Number	14797-65-0 Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:16301
ChemSpider	921
EC Number	233-272-6
PubChem CID	946
UNII	J39976L608 Y
InChI InChI=1S/HNO2/c2-1-3/h(H,2,3)/p-1 Key: IOVCWXUNBOPUCH-UHFFFAOYSA-M InChI=1/HNO2/c2-1-3/h(H,2,3)/p-1 Key: IOVCWXUNBOPUCH-REWHXWOFAR
SMILES N(=O)[O-]
Properties
Chemical formula	NO − 2
Molar mass	46.005 g·mol−1
Conjugate acid	Nitrous acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Chemical compound

The nitrite ion has the chemical formula NO ⁻
₂ . Nitrite (mostly sodium nitrite) is widely used throughout chemical and pharmaceutical industries.^[1] The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name nitrite can also refer to organic compounds with the – ONO group, which are esters of nitrous acid.

Production [edit]

Sodium nitrite is made industrially by passing a mixture of nitrogen oxides into aqueous sodium hydroxide or sodium carbonate solution:^{[2] [1]}

${\displaystyle {\ce {{NO}+ {NO2}}}+{\begin{Bmatrix}{\ce {2NaOH}}\\{\ce {Na2CO3}}\end{Bmatrix}}{\ce {-> 2 NaNO2}}+{\begin{Bmatrix}{\ce {H2O}}\\{\ce {CO2}}\end{Bmatrix}}}$

The product is purified by recrystallization. Alkali metal nitrites are thermally stable up to and beyond their melting point (441 °C for KNO₂). Ammonium nitrite can be made from dinitrogen trioxide, N₂O₃, which is formally the anhydride of nitrous acid:

2 NH₃ + H₂O + N₂O₃ → 2 NH₄NO₂

Structure [edit]

The nitrite ion has a symmetrical structure (C_2v symmetry), with both N–O bonds having equal length and a bond angle of about 115°. In valence bond theory, it is described as a resonance hybrid with equal contributions from two canonical forms that are mirror images of each other. In molecular orbital theory, there is a sigma bond between each oxygen atom and the nitrogen atom, and a delocalized pi bond made from the p orbitals on nitrogen and oxygen atoms which is perpendicular to the plane of the molecule. The negative charge of the ion is equally distributed on the two oxygen atoms. Both nitrogen and oxygen atoms carry a lone pair of electrons. Therefore, the nitrite ion is a Lewis base.

Reactions [edit]

Acid-base properties [edit]

Nitrite is the conjugate base of the weak acid nitrous acid:

HNO₂ ⇌ H⁺ + NO ⁻
₂ ; pK _a ≈ 3.3 at 18 °C^[3]

Nitrous acid is also highly volatile – in the gas phase it exists predominantly as a trans-planar molecule. In solution, it is unstable with respect to the disproportionation reaction:

3 HNO₂ (aq) ⇌ H₃O⁺ + NO ⁻
₃ + 2 NO

This reaction is slow at 0 °C.^[2] Addition of acid to a solution of a nitrite in the presence of a reducing agent, such as iron(II), is a way to make nitric oxide (NO) in the laboratory.

Oxidation and reduction [edit]

The formal oxidation state of the nitrogen atom in nitrite is +3. This means that it can be either oxidized to oxidation states +4 and +5, or reduced to oxidation states as low as −3. Standard reduction potentials for reactions directly involving nitrous acid are shown in the table below:^[4]

Half-reaction	E 0 (V)
NO − 3 + 3 H+ + 2 e− ⇌ HNO2 + H2O	+0.94
2 HNO2 + 4 H+ + 4 e− ⇌ H2N2O2 + 2 H2O	+0.86
N2O4 + 2 H+ + 2 e− ⇌ 2 HNO2	+1.065
2 HNO2+ 4 H+ + 4 e− ⇌ N2O + 3 H2O	+1.29

The data can be extended to include products in lower oxidation states. For example:

H₂N₂O₂ + 2 H⁺ + 2 e ⁻ ⇌ N₂ + 2 H₂O; E ⁰ = +2.65 V

Oxidation reactions usually result in the formation of the nitrate ion, with nitrogen in oxidation state +5. For example, oxidation with permanganate ion can be used for quantitative analysis of nitrite (by titration):

5 NO ⁻
₂ + 2 MnO ⁻
₄ + 6 H⁺ → 5 NO ⁻
₃ + 2 Mn²⁺ + 3 H₂O

The product of reduction reactions with nitrite ion are varied, depending on the reducing agent used and its strength. With sulfur dioxide, the products are NO and N₂O; with tin(II) (Sn²⁺) the product is hyponitrous acid (H₂N₂O₂); reduction all the way to ammonia (NH₃) occurs with hydrogen sulfide. With the hydrazinium cation (N
₂ H ⁺
₅ ) the product of nitrite reduction is hydrazoic acid (HN₃), an instable and explosive compound:

HNO₂ + N
₂ H ⁺
₅ → HN₃ + H₂O + H₃O⁺

which can also further react with nitrite:

HNO₂ + HN₃ → N₂O + N₂ + H₂O

This reaction is unusual in that it involves compounds with nitrogen in four different oxidation states.^[2]

Analysis of nitrite [edit]

Nitrite is detected and analyzed by the Griess Reaction, involving the formation of a deep red-colored azo dye upon treatment of a NO ⁻
₂ -containing sample with sulfanilic acid and naphthyl-1-amine in the presence of acid.^[5]

Coordination complexes [edit]

Nitrite is an ambidentate ligand and can form a wide variety of coordination complexes by binding to metal ions in several ways.^[2] Two examples are the red nitrito complex [Co(NH₃)₅(ONO)]²⁺ is metastable, isomerizing to the yellow nitro complex [Co(NH₃)₅(NO₂)]²⁺. Nitrite is processed by several enzymes, all of which utilize coordination complexes.

Biochemistry [edit]

A schematic representation of the microbial nitrogen cycle.^{[6] [7]} ANAMMOX is anaerobic ammonium oxidation, DNRA is dissimilatory nitrate reduction to ammonium, and COMMAMOX is complete ammonium oxidation.

In nitrification, ammonium is converted to nitrite. Important species include Nitrosomonas. Other bacterial species such as Nitrobacter, are responsible for the oxidation of the nitrite into nitrate.

Nitrite can be reduced to nitric oxide or ammonia by many species of bacteria. Under hypoxic conditions, nitrite may release nitric oxide, which causes potent vasodilation. Several mechanisms for nitrite conversion to NO have been described, including enzymatic reduction by xanthine oxidoreductase, nitrite reductase, and NO synthase (NOS), as well as nonenzymatic acidic disproportionation reactions.

Toxicity [edit]

The existence of nitrite ions in water samples and human food product sources can cause various human diseases. For example, nitrites can produce N-nitrosamines in the presence of secondary amines which are suspected to cause stomach cancer.^{[ citation needed ]} These materials can also react with hemoglobin producing methemoglobin which decreases blood oxygen-carrying capacity in the concentration of 50 mg kg⁻¹ of baby foods in infants and young children. The presence of nitrate can cause the same effect due to its transformation to nitrite in the digestive system or by a microbial reduction in food products.^[8] Epidemiological studies consistently show that consumption of food treated with nitrite is linked to higher cancer risks.^{[9] [10]}

Uses [edit]

Chemical precursor [edit]

Azo dyes and other colorants are prepared by the process called diazotization, which requires nitrite.^[1]

Nitrite in food preservation and biochemistry [edit]

Sodium nitrite is used to speed up the curing of meat and also impart an attractive colour.^[11] A 2022 study by the British Meat Producers Association determined that legally permitted levels of nitrite have no effect on the growth of the Clostridium botulinum bacteria which causes botulism, in line with the UK's Advisory Committee on the Microbiological Safety of Food opinion that nitrites are not required to prevent Clostridium botulinum growth and extend shelf life.^[12] In the U.S., meat cannot be labeled as "cured" without the addition of nitrite.^{[13] [14] [15]} In some countries, cured-meat products are manufactured without nitrate or nitrite, and without nitrite from vegetable source. Parma ham, produced without nitrite since 1993, was reported in 2022 to have caused no cases of botulism.^[11]

In mice, food rich in nitrites together with unsaturated fats can prevent hypertension, which is one explanation for the apparent health effect of the Mediterranean diet.^[16] However, adding nitrites to meat has been shown to generate known carcinogens; the World Health Organization (WHO) advises that eating 50 g (1.8 oz) of nitrite processed meat a day would raise the risk of getting bowel cancer by 18% over a lifetime.^[11] The recommended maximum limits by the World Health Organization in drinking water are 3 mg L⁻¹ and 50 mg L⁻¹ for nitrite and nitrate ions, respectively.^[8]

Curing of meat [edit]

In a reaction with the meat's myoglobin, nitrite gives the product a desirable pink-red "fresh" color, such as with corned beef. In the US, nitrite has been formally used since 1925. According to scientists working for the industry group American Meat Institute, this use of nitrite started in the Middle Ages.^[17] Historians^[18] and epidemiologists^[19] argue that the widespread use of nitrite in meat-curing is closely linked to the development of industrial meat-processing. French investigative journalist Guillaume Coudray asserts that the meat industry chooses to cure its meats with nitrite even though it is established that this chemical gives rise to cancer-causing nitroso-compounds.^[20]

Organic nitrites [edit]

In organic chemistry, nitrites are esters of nitrous acid and contain the nitrosoxy functional group. Nitro compounds contain the C–NO₂ group. Nitrites have the general formula RONO, where R is an aryl or alkyl group. Amyl nitrite and other alkyl nitrites have a vasodilating action and must be handled in the laboratory with caution. They are sometimes used in medicine for the treatment of heart diseases. A classic named reaction for the synthesis of alkyl nitrites is the Meyer synthesis ^{[21] [22]} in which alkyl halides react with metallic nitrites to a mixture to nitroalkanes and nitrites.

Safety [edit]

Adding nitrites to meat has been shown to generate known carcinogens such as nitrosamines; the World Health Organization (WHO) advises that each 50 g (1.8 oz) of processed meat eaten a day would raise the risk of getting bowel cancer by 18% over a lifetime; processed meat refers to meat that has been transformed through fermentation, nitrite curing, salting, smoking, or other processes to enhance flavour or improve preservation. The World Health Organization's review of more than 400 studies concluded, in 2015, that there was sufficient evidence that processed meats caused cancer, particularly colon cancer; the WHO's International Agency for Research on Cancer (IARC) classified processed meats as carcinogenic to humans (Group 1).^{[11] [23]}

Nitrite (ingested) under conditions that result in endogenous nitrosation, specifically the production of nitrosamine, has been classified as "Probably carcinogenic to humans" (Group 2A) by the IARC.^{[24] [25]}

See also [edit]

• Curing (food preservation)
• Alkyl nitrites

References [edit]

1. ^ ^{a b c} Laue W, Thiemann M, Scheibler E, Wiegand KW (2006). "Nitrates and Nitrites". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_265.
2. ^ ^{a b c d} Greenwood, pp. 461–464.
3. ^ IUPAC SC-Database A comprehensive database of published data on equilibrium constants of metal complexes and ligands
4. ^ Greenwood, p. 431.
5. ^ V. M. Ivanov (2004). "The 125th Anniversary of the Griess Reagent". Journal of Analytical Chemistry. 59 (10): 1002–1005. doi:10.1023/B:JANC.0000043920.77446.d7. S2CID 98768756. Translated from V. M. Ivanov (2004). Zhurnal Analiticheskoi Khimii. 59 (10): 1109–1112.
6. ^ Sparacino-Watkins, Courtney; Stolz, John F.; Basu, Partha (16 December 2013). "Nitrate and periplasmic nitrate reductases". Chem. Soc. Rev. 43 (2): 676–706. doi:10.1039/c3cs60249d. ISSN 1460-4744. PMC4080430. PMID 24141308.
7. ^ Simon, Jörg; Klotz, Martin G. (2013). "Diversity and evolution of bioenergetic systems involved in microbial nitrogen compound transformations". Biochimica et Biophysica Acta (BBA) - Bioenergetics. 1827 (2): 114–135. doi:10.1016/j.bbabio.2012.07.005. PMID 22842521.
8. ^ ^{a b} Bagheri, H.; Hajian, A.; Rezaei, M.; Shirzadmehr, A. (2017). "Composite of Cu metal nanoparticles—multiwall carbon nanotubes—reduced graphene oxide as a novel and high performance platform of the electrochemical sensor for simultaneous determination of nitrite and nitrate". Journal of Hazardous Materials. 324 (Pt B): 762–772. doi:10.1016/j.jhazmat.2016.11.055. PMID 27894754.
9. ^ Chazelas, Eloi (March 2022). "Nitrites and nitrates from food additives and natural sources and cancer risk: results from the NutriNet-Santé cohort". Int. J. Epidemiology. doi:10.1093/ije/dyac046. PMID 35303088. Retrieved 24 May 2022.
10. ^ Chris, Eliott. "Strongest link yet between nitrites and cancer". Queen's University Belfast . Retrieved 23 May 2022.
11. ^ ^{a b c d} Wilson, Bee (1 March 2018). "Yes, bacon really is killing us". The Guardian. London. ISSN 0261-3077. Archived from the original on 10 February 2021. Retrieved 14 February 2021. In trade journals of the 1960s, the firms who sold nitrite powders to ham-makers spoke quite openly about how the main advantage was to increase profit margins by speeding up production.
12. ^ Doward, Jamie (23 March 2019). "Revealed: no need to add cancer-risk nitrites to ham". The Observer. London. Archived from the original on 26 January 2021. Retrieved 14 February 2021. The results show that there is no change in levels of inoculated C. botulinum over the curing process, which implies that the action of nitrite during curing is not toxic to C. botulinum spores at levels of 150ppm [parts per million] ingoing nitrite and below.
13. ^ De Vries, John (1997). Food Safety and Toxicity. CRC Press. p. 70. ISBN978-0-8493-9488-1.
14. ^ sodium nitrite and nitrate facts Accessed Dec 12, 2014
15. ^ Doyle, Michael P.; Sperber, William H. (23 September 2009). Compendium of the Microbiological Spoilage of Foods and Beverages. p. 78. ISBN9781441908261.
16. ^ Charles, R. L.; Rudyk, O.; Prysyazhna, O.; Kamynina, A.; Yang, J.; Morisseau, C.; Hammock, B. D.; Freeman, B. A.; Eaton, P. (2014). "Protection from hypertension in mice by the Mediterranean diet is mediated by nitro fatty acid inhibition of soluble epoxide hydrolase". Proceedings of the National Academy of Sciences. 111 (22): 8167–72. Bibcode:2014PNAS..111.8167C. doi:10.1073/pnas.1402965111. PMC4050620. PMID 24843165.
17. ^ Binkerd, E. F.; Kolari, O. E. (1 January 1975). "The history and use of nitrate and nitrite in the curing of meat". Food and Cosmetics Toxicology. 13 (6): 655–661. doi:10.1016/0015-6264(75)90157-1. ISSN 0015-6264. PMID 1107192.
18. ^ coudray, guillaume, eric (2017). Cochonneries : comment la charcuterie est devenue un poison. paris: Decouverte. pp. part I, chapter 2 (p. 40–55) and chapter 3 (p. 56–70). ISBN9782707193582. OCLC 1011036745.
19. ^ Lauer, Klaus (1 January 1991). "The history of nitrite in human nutrition: A contribution from German cookery books". Journal of Clinical Epidemiology. 44 (3): 261–264. doi:10.1016/0895-4356(91)90037-A. ISSN 0895-4356. PMID 1999685.
20. ^ "Guillaume Coudray on the Nitro Meat Cancer Connection". 14 April 2021.
21. ^ Victor Meyer (1872). "Ueber die Nitroverbindungen der Fettreihe". Justus Liebig's Annalen der Chemie. 171 (1): 1–56. doi:10.1002/jlac.18741710102. ; Victor Meyer, J. Locher (1876). "Ueber die Pseudonitrole, die Isomeren der Nitrolsäuren". Justus Liebig's Annalen der Chemie. 180 (1–2): 133–55. doi:10.1002/jlac.18761800113. ; V. Meyer and Stüber (1872). "Vorläufige Mittheilung". Chemische Berichte. 5: 203–05. doi:10.1002/cber.18720050165. ; Victor Meyer, O. Stüber (1872). "Ueber die Nitroverbindungen der Fettreihe". Chemische Berichte. 5: 399–406. doi:10.1002/cber.187200501121. ; Victor Meyer, A. Rilliet (1872). "Ueber die Nitroverbindungen der Fettreiche. Dritte Mittheilung". Chemische Berichte. 5 (2): 1029–34. doi:10.1002/cber.187200502133. ; Victor Meyer, C. Chojnacki (1872). "Ueber die Nitroverbindungen der Fettreihe. Vierte Mittheilung". Chemische Berichte. 5 (2): 1034–38. doi:10.1002/cber.187200502134.
22. ^ Robert B. Reynolds, Homer Adkins (1929). "The Relationship of the Constitution of Certain Alky Halides to the Formation of Nitroparaffins and Alkyl Nitrites". Journal of the American Chemical Society. 51 (1): 279–87. doi:10.1021/ja01376a037.
23. ^ "IARC Monographs evaluate consumption of red meat and processed meat" (PDF). International Agency for Research on Cancer. 26 October 2015. Archived from the original (PDF) on 18 January 2021. Retrieved 14 February 2021. Processed meat was classified as carcinogenic to humans (Group 1), based on sufficient evidence in humans that the consumption of processed meat causes colorectal cancer.
24. ^ "List of classifications, Volumes 1–116 - IARC Monographs on the Evaluation of Carcinogenic Risks to Humans". International Agency for Research on Cancer (IARC) - World Health Organization (WHO). 2010. Archived from the original on 10 June 2017. Retrieved 25 September 2016.
25. ^ VOLUME 94 - Ingested Nitrate and Nitrite, and Cyanobacterial Peptide Toxins - IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. International Agency for Research on Cancer (IARC) - World Health Organization (WHO). 2010. ISBN9789283212942 . Retrieved 25 September 2016.

Bibliography [edit]

• Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN978-0-08-037941-8.
• Coudray, Guillaume. Who poisoned your bacon. London: Icon Books, 2021. ISBN 9-781-78578612-9

External links [edit]

Wikimedia Commons has media related to Nitrites.

• Material Safety Data Sheet, sodium nitrite (archive)
• ATSDR – Case Studies in Environmental Medicine – Nitrate/Nitrite Toxicity (archive) - US Department of Health and Human Services (public domain)
• Article about Toxicity of Nitrite

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Source: https://en.wikipedia.org/wiki/Nitrite

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