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{{chembox {{chembox
|Watchedfields = changed
| verifiedrevid = 444854343
|verifiedrevid = 444854343
| ImageFileL1 =chloropicrin.png
|ImageFileL1 =chloropicrin.png
| ImageSizeL1 = 100px
| ImageFileR1 = Chloropicrin-3D-balls.png |ImageFileR1 = Chloropicrin-3D-balls.png
|IUPACName = Trichloro(nitro)methane
| ImageSizeR1 = 100px
|OtherNames = {{ubl|Nitrochloroform|Nitrotrichloromethane|PS|Tri-clor|Trichloronitromethane}}
| IUPACName = trichloro(nitro)methane
|Section1={{Chembox Identifiers
| OtherNames = PS
|IUPHAR_ligand = 6292
| Section1 = {{Chembox Identifiers
| InChI = 1/CCl3NO2/c2-1(3,4)5(6)7 |InChI = 1/CCl3NO2/c2-1(3,4)5(6)7
| InChIKey = LFHISGNCFUNFFM-UHFFFAOYAJ |InChIKey = LFHISGNCFUNFFM-UHFFFAOYAJ
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/CCl3NO2/c2-1(3,4)5(6)7 |StdInChI = 1S/CCl3NO2/c2-1(3,4)5(6)7
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = LFHISGNCFUNFFM-UHFFFAOYSA-N |StdInChIKey = LFHISGNCFUNFFM-UHFFFAOYSA-N
| CASNo = 76-06-2 |CASNo = 76-06-2
| CASNo_Ref = {{cascite|correct|CAS}} |CASNo_Ref = {{cascite|correct|CAS}}
| PubChem = |PubChem = 6423
| UNII_Ref = {{fdacite|correct|FDA}} |UNII_Ref = {{fdacite|correct|FDA}}
| UNII = I4JTX7Z7U2 |UNII = I4JTX7Z7U2
| ChEBI_Ref = {{ebicite|correct|EBI}} |ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 39285 |ChEBI = 39285
|ChEMBL = 1327143
| SMILES = ClC(Cl)(Cl)()=O
|Beilstein = 1756135
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
|Gmelin = 240197
| ChemSpiderID = 13861343
|EC_number = 200-930-9
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = C18445 |RTECS = PB6300000
|UNNumber = 1580
}}
|SMILES = ClC(Cl)(Cl)()=O
| Section2 = {{Chembox Properties
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| Formula = CCl<sub>3</sub>NO<sub>2</sub>
|ChemSpiderID = 13861343
| MolarMass = 164.375
|KEGG_Ref = {{keggcite|correct|kegg}}
| Appearance = colorless liquid
|KEGG = C18445
| Density = 1.692 g/ml<ref>http://msds.chem.ox.ac.uk/CH/chloropicrin.html</ref>
}}
| MeltingPt = -69 °C
|Section2={{Chembox Properties
| BoilingPt = 112 °C (dec)
|Formula = {{chem2|CCl3NO2}}
| Solubility =
|MolarMass = 164.375 g/mol
}}
|Appearance = colorless liquid
| Section3 = {{Chembox Hazards
|Odor = irritating<ref name=PGCH/>
| MainHazards = Extremely toxic and irritating to skin, eyes, and lungs.
|Density = 1.692&nbsp;g/ml
| FlashPt =
|MeltingPtC = -69
| Autoignition =
|BoilingPtC = 112
}}
|BoilingPt_notes = (decomposes)
|Solubility = 0.2%<ref name=PGCH/>
|VaporPressure = 18 mmHg (20°C)<ref name=PGCH/>
|MagSus = −75.3·10<sup>−6</sup> cm<sup>3</sup>/mol
}}
|Section7={{Chembox Hazards
|MainHazards = Extremely toxic and irritating to skin, eyes, and lungs. Carcinogenic.
|GHSPictograms = {{GHS05}}{{GHS06}}{{GHS08}}{{GHS09}}
|GHSSignalWord = Danger
|HPhrases = {{H-phrases|301|314|330|370|372|410}}
|PPhrases = {{P-phrases|260|264|270|271|273|280|284|301+310|301+330+331|303+361+353|304+340|305+351+338|307+311|310|314|320|321|330|363|391|403+233|405|501}}
|NFPA-H = 4
|NFPA-F = 0
|NFPA-R = 3
|PEL = TWA 0.1 ppm (0.7 mg/m<sup>3</sup>)<ref name=PGCH>{{PGCH|0132}}</ref>
|REL = TWA 0.1 ppm (0.7 mg/m<sup>3</sup>)<ref name=PGCH/>
|IDLH = 2 ppm<ref name=PGCH/>
|LC50 = 9.7 ppm (mouse, 4 hr)<br />117 ppm (rat, 20 min)<br />14.4 ppm (rat, 4 hr)<ref name=IDLH>{{IDLH|76062|Chloropicrin}}</ref>
|LCLo = 293 ppm (human, 10 min)<br />340 ppm (mouse, 1 min)<br />117 ppm (cat, 20 min)<ref name=IDLH/>
}}
}} }}


'''Chloropicrin''', also known as '''PS''' (from ]<ref>{{cite book|last1=Foulkes|first1=C. H.|title="GAS!" – The Story of the Special Brigade|date=31 January 2012|publisher=Andrews UK Limited|page=193}}</ref>) and '''nitrochloroform''', is a chemical compound currently used as a broad-spectrum antimicrobial, fungicide, ], ], and ].<ref name="RED Fact Sheet">{{cite web |title=RED Fact Sheet: Chloropicrin|url=http://www.epa.gov/oppsrrd1/REDs/factsheets/chloropicrin-fs.pdf|publisher=US Environmental Protection Agency|access-date=20 September 2013|page=2|date=10 July 2008}}</ref> It was used as a ] and the Russian military has been accused of using it in the ].<ref>{{Cite web |last=Office of the Spokesperson |date=1 May 2024 |title=Imposing New Measures on Russia for its Full-Scale War and Use of Chemical Weapons Against Ukraine |url=https://www.state.gov/imposing-new-measures-on-russia-for-its-full-scale-war-and-use-of-chemical-weapons-against-ukraine-2/#:~:text=The%20Department%20of%20State%20has,Chemical%20Weapons%20Convention%20(CWC). |url-status=live |archive-url=https://web.archive.org/web/20240523134544/https://www.state.gov/imposing-new-measures-on-russia-for-its-full-scale-war-and-use-of-chemical-weapons-against-ukraine-2/ |archive-date=23 May 2024 |access-date=23 May 2024 |website=U.S. Department of State}}</ref><ref>{{cite web | url=https://apnews.com/article/russia-explosion-head-of-nuclear-defense-forces-killed-9656bce946a9f552454df9debe5fbd18?utm_source=firefox-newtab-en-us | title=A top Russian general is killed in a Moscow bombing claimed by Ukraine | website=] |date=2024-12-17 |access-date=2024-12-18}}</ref> Its chemical structural formula is {{chem2|Cl3C\sNO2|auto=1}}.
'''Chloropicrin''', also known as '''PS''', is a ] with the structural formula Cl<sub>3</sub>CNO<sub>2</sub>. This colourless highly toxic liquid was once used in ] and is currently used as a ] and ].<ref name=fumigant>http://www.workcover.nsw.gov.au/Documents/Publications/AlertsGuidesHazards/DangerousGoodsExplosivesFireworksPyrotechnics/chloropicrin_fact_sheet_1371.pdf</ref><ref>http://books.google.com/books?id=cTA6AAAAMAAJ&pg=PA144&dq=Chloropicrin+in+chemical+warfare#PPA144,M1</ref>


==History== ==Synthesis==
Chloropicrin was first discovered in 1848 by a ] chemist ]. He prepared it by the reaction of a ] with ]:<!--eq is an approx guess--> Chloropicrin was discovered in 1848 by Scottish chemist ]. He prepared it by the reaction of ] with ]:<!--eq is an approx guess-->
:HOC<sub>6</sub>H<sub>2</sub>(NO<sub>2</sub>)<sub>3</sub> + 11 NaOCl → 3 Cl<sub>3</sub>CNO<sub>2</sub> + 3 Na<sub>2</sub>CO<sub>3</sub> + 3 NaOH + 2 NaCl
Because of the precursor he used, Stenhouse named the compound chloropicrin, although the two compounds are structurally dissimilar.


{{block indent|{{chem2|HOC6H2(NO2)3 + 11 NaOCl → 3 Cl3CNO2 + 3 ] + 3 ] + 2 ]}}}}
Arguably{{Weasel-inline|date=August 2011}}, chloropicrin's most famous use was in ]. In 1917, there were reports that the Germans were testing and using a new chemical in warfare.<ref name="chemweaponprevent">http://books.google.com/books?id=cTA6AAAAMAAJ&pg=PA144&dq=Chloropicrin+in+chemical+warfare&client=firefox-a#PPA144,M1</ref> That chemical was chloropicrin. While not as lethal as other chemical weapons, it caused ] and was a ].<ref name="chemweaponprevent"/> This combination of properties forced Allied soldiers to remove their masks to vomit, exposing them to toxic gases.<ref name="chemweaponprevent"/> This caused a large number of casualties on the Italian front.<ref name="chemweaponprevent"/>


Because of the precursor used, Stenhouse named the compound chloropicrin, although the two compounds are structurally dissimilar.
==Preparation==
Chloropicrin is manufactured by the reaction of ] with ]:<ref>Sheldon B. Markofsky "Nitro Compounds, Aliphatic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.</ref>
:H<sub>3</sub>CNO<sub>2</sub> + 3 NaOCl → Cl<sub>3</sub>CNO<sub>2</sub> + 3 NaOH


Today, chloropicrin is manufactured by the reaction of ] with ]:<ref>{{cite encyclopedia |first=Sheldon B. |last=Markofsky |title=Nitro Compounds, Aliphatic |encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry |publisher=Wiley-VCH |location=Weinheim |year=2005}}</ref>
==Properties==
As listed in the Table, chloropicrin is a colorless liquid that is insoluble in water, with which it is stable. With a vapor pressure of 24&nbsp;mm Hg, its volatility is between that of ] and ] in persistency, although closer to phosgene because it is related to the compound.<ref name=chemwarfarebook>http://books.google.com/books?id=cTA6AAAAMAAJ&pg=PA144&dq=Chloropicrin+in+chemical+warfare#PPA146,M1</ref> Tests have shown that chloropicrin causes humans to shut their eyes involuntarily.<ref name="chemweaponprevent"/> Chloropicrin can be absorbed systemically through inhalation, ingestion, and the skin. It is severely irritating to the lungs, eyes, and skin.<ref>. National Institute for Occupational Safety and Health. Emergency Response Safety and Health Database, August 22, 2008. Retrieved December 23, 2008.</ref> Because of these properties, chloropicrin can only be delivered in shell form as a chemical weapon.<ref name="chemwarfarebook"/>


{{block indent|{{chem2|H3CNO2 + 3 NaOCl → Cl3CNO2 + 3 NaOH}}}}
==Application==
Chloropicrin, today, is used as a fumigant to control pests found in the soil.<ref name="fumigant"/> Although less common, it can be used as a poison for vertebrates, such as rabbits.<ref name="fumigant"/> Chloropicrin is commonly used in combination with other fumigants, such as ] and ], for increased potency and as a warning agent.<ref name="fumigant"/>


Reaction of ] and ] also yields chloropicrin:<ref>{{cite journal |title=Chloropicrin |first=Kirby E. |last=Jackson |journal=Chemical Reviews |year=1934 |volume=14 |issue=2 |pages=251–286 |url=https://doi.org/10.1021/cr60048a003 |doi=10.1021/cr60048a003}}</ref>
Chloropicrin has been used in ]. It first appeared in 1917 when the Germans tested a new chemical weapon on the Italian front.<ref name=chemwarfarebook>http://books.google.com/books?id=cTA6AAAAMAAJ&pg=PA144&dq=Chloropicrin+in+chemical+warfare</ref> The new chemical weapon was devastating to the Allies at first, since they had never encountered it before.


{{block indent|{{Chem2|Cl3CH + HONO2 -> Cl3CNO2 + H2O}}}}
==Safety==
Chloropicrin is a highly toxic chemical:
NIOSH 1995 states that:


==Properties==
*Chloropicrin is a lacrimator and a severe irritant of the respiratory system in humans; it also causes severe skin irritation on contact. When splashed onto the eye chloropicrin has caused corneal ] and liquification of the ].
Chloropicrin's chemical formula is {{chem2|CCl3NO2}} and its molecular weight is 164.38 grams/mole.<ref name=DPR_ExecSum>{{cite web|title=Executive Summary - Evaluation of Chloropicrin As A Toxic Air Contaminant|url=http://www.cdpr.ca.gov/docs/emon/pubs/tac/exec_sum_0210.pdf|publisher=Department of Pesticide Regulation - California Environmental Protection Agency|access-date=20 September 2013|page=iv|date=February 2010|archive-url=https://web.archive.org/web/20131006220801/http://www.cdpr.ca.gov/docs/emon/pubs/tac/exec_sum_0210.pdf|archive-date=6 October 2013|url-status=dead}}</ref> Pure chloropicrin is a colorless liquid, with a boiling point of 112&nbsp;°C.<ref name="DPR_ExecSum"/> Chloropicrin is sparingly soluble in water with solubility of 2&nbsp;g/L at 25&nbsp;°C.<ref name="DPR_ExecSum"/> It is volatile, with a vapor pressure of 23.2 ] (mmHg) at 25&nbsp;°C; the corresponding ] constant is 0.00251&nbsp;atmosphere-cubic meter per mole.<ref name="DPR_ExecSum"/> The ] (''K''<sub>ow</sub>) of chloropicrin is estimated to be 269.<ref name="DPR_ExecSum"/> Its soil adsorption coefficient (''K''<sub>oc</sub>; normalized to soil organic matter content) is 25&nbsp;cm<sup>3</sup>/g.<ref name="DPR_ExecSum"/>
*Exposure to concentrations of 15 ppm cannot be tolerated for more than 1 minute, and exposure to 4 ppm for a few seconds is temporarily disabling.
*Exposure to 0.3-0.37 ppm chloropicrin for 3 to 30 seconds causes tearing and eye pain. Exposure to 15 ppm for a few seconds can cause respiratory tract injury.
*Exposure to 119 ppm in air for 30 minutes is lethal; death is caused by pulmonary oedema.


==Uses==
Examples of industrial exposure in humans: 27 workers in a cellulose factory who were exposed to high levels of chloropicrin for 3 minutes developed ] after 3 to 12 hours of irritated coughing and difficulty on breathing; they subsequently developed pulmonary oedema, and one died.
===Poison===
Chloropicrin was manufactured for use as ].<ref>{{cite book |last=Ayres |first=Leonard P. |title =The War with Germany |url=https://archive.org/details/warwithgermanya02ayregoog |publisher =United States Government Printing Office |edition =2nd |date =1919 |location =Washington, DC |page =}}</ref> In ], German forces used concentrated chloropicrin against Allied forces as a ]. While not as lethal as other chemical weapons, it induced ] and forced Allied soldiers to remove their masks to vomit, exposing them to more toxic gases used as weapons during the war.<ref>{{Cite journal |last=Heller |first=Charles E. |date=September 1984 |title=Chemical Warfare in World War I: The American Experience, 1917–1918 |url=https://www.armyupress.army.mil/Portals/7/combat-studies-institute/csi-books/leavenworth-papers-10-chemical-warfare-in-world-war-i-the-american-experience-1917-1918.pdf |journal=Leavenworth Papers |issue=10 |pages=23}}</ref>


===Agriculture===
EU classification of chloropicrin is:
In agriculture, chloropicrin is injected into soil prior to planting a crop to ] soil. Chloropicrin affects a broad spectrum of ], ] and ].<ref name="fumigant">{{cite web |url=http://www.workcover.nsw.gov.au/Documents/Publications/AlertsGuidesHazards/DangerousGoodsExplosivesFireworksPyrotechnics/chloropicrin_fact_sheet_1371.pdf |title=Factsheet: Chloropicrin |location=New South Wales |publisher=] |archive-url=https://web.archive.org/web/20090520095913/http://www.workcover.nsw.gov.au/Documents/Publications/AlertsGuidesHazards/DangerousGoodsExplosivesFireworksPyrotechnics/chloropicrin_fact_sheet_1371.pdf |archive-date=May 20, 2009}}</ref> It is commonly used as a stand-alone treatment or in combination / co-formulation with ] and ].<ref name="fumigant" /><ref name="google">{{cite book| first1 = Amos Alfred |last1=Fries|first2=Clarence Jay |last2=West| title = Chemical warfare| url = https://archive.org/details/chemicalwarfare00westgoog| year = 1921| publisher = McGraw-Hill | page = }}</ref> Chloropicrin is used as an indicator and repellent when fumigating residences for insects with ] which is an odorless gas.{{cn<!--Commercial link removed-->|date=December 2024}} Chloropicrin's ] is unknown<ref name="PPDB" /> (IRAC MoA 8B).<ref name="IRAC-MoAs-9.4" /> Chloropicrin may stimulate ] ], which can be useful when quickly followed by a more effective ].<ref name="Martin-2003">{{cite journal | last=Martin | first=Frank N. | title=Development of Alternative Strategies for Management of Soilborne Pathogens Currently Controlled with Methyl Bromide | journal=] | publisher=] | volume=41 | issue=1 | year=2003 | issn=0066-4286 | doi=10.1146/annurev.phyto.41.052002.095514 | pages=325–350| pmid=14527332}}</ref>
R22 Harmful if swallowed, R26 Very toxic by inhalation, R36/37/38 Irritating to eyes, skin and respiratory system, R43 May cause sensitisation by skin contact, R50/53 Very toxic to aquatic organisms, may cause long term adverse effects in the aquatic environment.


In 2008, the US ] re-approved chloropicrin as safe for use in agricultural settings, stating that treatments "can provide benefits to both food consumers and growers. For consumers, it means more fresh fruits and vegetables can be cheaply produced domestically year-round because several severe pest problems can be efficiently controlled."<ref>{{cite web|title=Amended Reregistration Eligibility Decision (RED) for Chloropicrin|url=http://www.epa.gov/oppsrrd1/REDs/chloropicrin-red-amended.pdf|publisher=United States Environmental Protection Agency|access-date=20 September 2013|date=May 2009}}</ref>{{dead link|date=May 2024}}<ref name=DPR_MitPro2>{{cite web|title=Chloropicrin Mitigation Proposal|url=http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|publisher=Department of Pesticide Regulation – California Environmental Protection Agency|access-date=20 September 2013|page=2|date=15 May 2013|archive-url=https://web.archive.org/web/20131006220459/http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|archive-date=6 October 2013|url-status=dead}}</ref> To ensure chloropicrin is used safely, the EPA requires a strict set of protections for handlers, workers, and persons living and working in and around farmland during treatments.<ref name=chloro_background>{{cite web|title=Chloropicrin – Background|url=http://www.chloropicrinfacts.org/background.html|access-date=20 September 2013}}</ref><ref name="DPR_MitPro2"/> EPA protections were increased in both 2011 and 2012, reducing ] exposures and significantly improving safety.<ref name=DPR_MitProQuote>{{cite web|title=Chloropicrin Mitigation Proposal|url=http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|publisher=Department of Pesticide Regulation – California Environmental Protection Agency|access-date=20 September 2013|page=2|date=15 May 2013|quote=The Amended RED incorporated final new safety measures to increase protections for agricultural workers and bystanders. These measures establish a baseline for safe use of the soil fumigants throughout the United States, reducing fumigant exposures and significantly improving safety.|archive-url=https://web.archive.org/web/20131006220459/http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|archive-date=6 October 2013|url-status=dead}}</ref> Protections include the training of certified applicators supervising pesticide application, the use of buffer zones, posting before and during pesticide application, fumigant management plans, and compliance assistance and assurance measures.{{cn|date=December 2024}}
Because of chloropicrin's stability, protection requires highly effective absorbents, such as ].<ref name="chemweaponprevent"/> Chloropicrin, unlike its relative compound ], is absorbed readily at any temperature, which may pose a threat in low or high temperature climates.<ref name="chemwarfarebook"/>


Used as a preplant soil treatment measure, chloropicrin suppresses soilborne pathogenic ] and some ] and ]. According to chloropicrin manufacturers, with a ] of hours to days, it is completely digested by soil organisms before the crop is planted, making it safe and efficient.{{cn|date=May 2024}} Contrary to popular belief, chloropicrin does not ] soil and does not ], as the compound is destroyed by sunlight. Additionally, chloropicrin has never been found in ], due to its low solubility.<ref>{{cite web |url= https://www.plantmanagementnetwork.org/edcenter/seminars/potato/Chloropicrin/ |title=Chloropicrin Soil Fumigation in Potato Production Systems|work=Plant Management Network |publisher=American Phytopathological Society |access-date= 1 Apr 2019}}</ref>
The use of the substance has been restricted by the ], although such restriction is outdated now <ref name=rupr>{{cite web
| last = ]
| first =
| authorlink =
| coauthors =
| title = Restricted Use Products (RUP) Report: Six Month Summary List
| work =
| publisher =
| date =
| url = http://www.epa.gov/opprd001/rup/rup6mols.htm
| doi =
| accessdate = 1 December 2009}}</ref>


====California====
==Portrayal in Media==
In ], experience with acute effects of chloropicrin when used as a soil fumigant for ] and other ] led to the release of regulations in January 2015 creating buffer zones and other precautions to minimize exposure of farm workers, neighbors, and passersby.<ref name=CDPR01615>{{cite web|title=Control Measures for Chloropicrin|url=http://www.cdpr.ca.gov/docs/whs/pdf/control_measures_chloropicrin_summary.pdf|publisher=California Department of Pesticide Regulation|access-date=January 15, 2015|date=January 6, 2015|quote=added controls for chloropicrin when it is used as a soil fumigant. The controls are intended to reduce risk from acute (short-term) exposures that might occur near fields fumigated with products containing chloropicrin.|archive-url=https://web.archive.org/web/20150128143316/http://www.cdpr.ca.gov/docs/whs/pdf/control_measures_chloropicrin_summary.pdf|archive-date=January 28, 2015|url-status=dead}}</ref><ref name=DPR_MitProQuote2>{{cite web|title=Chloropicrin Mitigation Proposal|url=http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|publisher=Department of Pesticide Regulation – California Environmental Protection Agency|access-date=20 September 2013|page=2|date=15 May 2013|quote=The new measures appearing on soil fumigant Phase 2 labels include buffer zones and posting, emergency preparedness and response measures, training for certified applicators supervising applications, Fumigant Management Plans, and notice to State Lead Agencies who wish to be informed of applications in their states.|archive-url=https://web.archive.org/web/20131006220459/http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|archive-date=6 October 2013|url-status=dead}}</ref>
In the 1987 Movie ], detectives Joe Friday (]) and Pep Streebeck (]) thwart an attempt by mad cultists to release a tanker truck of ] at a party attended by several prominent Los Angeles city officials.
==Safety==
At a national level, chloropicrin is regulated in the ] by the ] as a restricted use ].<ref name=DPR_MitPro1>{{cite web|title=Chloropicrin Mitigation Proposal|url=http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|publisher=Department of Pesticide Regulation – California Environmental Protection Agency|access-date=20 September 2013|page=1|date=15 May 2013|archive-url=https://web.archive.org/web/20131006220459/http://www.cdpr.ca.gov/docs/whs/pdf/dpr_chloropicrin_mitigation_proposal_and_app_1-3.pdf|archive-date=6 October 2013|url-status=dead}}</ref> Because of its toxicity and ]icity, distribution and use of chloropicrin is available only to licensed professionals and specially certified growers who are trained in its proper and safe use.<ref name="DPR_MitPro1"/> In the US, occupational exposure limits have been set at 0.1 ppm over an eight-hour time-weighted average.<ref name=cdc>{{cite web|title = NIOSH Pocket Guide to Chemical Hazards|url=https://www.cdc.gov/niosh/npg/npgd0132.html|publisher=Centers for Disease Control and Prevention|access-date=7 November 2013}}</ref>
===High concentrations===
]
Chloropicrin is harmful to humans. It can be absorbed systemically through inhalation, ingestion, and the skin. At high concentrations, it is severely irritating to the lungs, eyes, and skin.<ref>{{cite web |url=https://www.cdc.gov/niosh/ershdb/EmergencyResponseCard_29750034.html |title=Chloropicrin (PS): Lung Damaging Agent |publisher=National Institute for Occupational Safety and Health |work=Emergency Response Safety and Health Database |date=August 22, 2008 |access-date=December 23, 2008}}</ref>


==Damage to protective gear==
The effects cited in explaining the substance (vomiting, suffocation, and death) are consistent with the actual chemical.
Chloropicrin and its derivative ] have been known to damage or compromise earlier generations of personal protective equipment. Some of the soldiers attacked mentioned a white smoke emerging from their gas masks.{{citation needed|date=July 2022}}

==See also==
*]
*]


==References== ==References==
{{reflist}} {{reflist|refs=

<ref name="IRAC-MoAs-9.4">{{cite web|url=http://irac-online.org/documents/moa-classification/|title=IRAC Mode of Action Classification Scheme Version 9.4|website=IRAC (])|type=pdf|date=March 2020}}</ref>

<ref name="PPDB">{{PPDB|148}}, ], accessed 2021-03-10.</ref>

}}


{{Chemical warfare}} {{Chemical warfare}}
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Latest revision as of 12:37, 20 December 2024

Chloropicrin
Names
IUPAC name Trichloro(nitro)methane
Other names
  • Nitrochloroform
  • Nitrotrichloromethane
  • PS
  • Tri-clor
  • Trichloronitromethane
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 1756135
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.847 Edit this at Wikidata
EC Number
  • 200-930-9
Gmelin Reference 240197
IUPHAR/BPS
KEGG
PubChem CID
RTECS number
  • PB6300000
UNII
UN number 1580
CompTox Dashboard (EPA)
InChI
  • InChI=1S/CCl3NO2/c2-1(3,4)5(6)7Key: LFHISGNCFUNFFM-UHFFFAOYSA-N
  • InChI=1/CCl3NO2/c2-1(3,4)5(6)7Key: LFHISGNCFUNFFM-UHFFFAOYAJ
SMILES
  • ClC(Cl)(Cl)()=O
Properties
Chemical formula CCl3NO2
Molar mass 164.375 g/mol
Appearance colorless liquid
Odor irritating
Density 1.692 g/ml
Melting point −69 °C (−92 °F; 204 K)
Boiling point 112 °C (234 °F; 385 K) (decomposes)
Solubility in water 0.2%
Vapor pressure 18 mmHg (20°C)
Magnetic susceptibility (χ) −75.3·10 cm/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Extremely toxic and irritating to skin, eyes, and lungs. Carcinogenic.
GHS labelling:
Pictograms GHS05: CorrosiveGHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Signal word Danger
Hazard statements H301, H314, H330, H370, H372, H410
Precautionary statements P260, P264, P270, P271, P273, P280, P284, P301+P310, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P307+P311, P310, P314, P320, P321, P330, P363, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
4 0 3
Lethal dose or concentration (LD, LC):
LC50 (median concentration) 9.7 ppm (mouse, 4 hr)
117 ppm (rat, 20 min)
14.4 ppm (rat, 4 hr)
LCLo (lowest published) 293 ppm (human, 10 min)
340 ppm (mouse, 1 min)
117 ppm (cat, 20 min)
NIOSH (US health exposure limits):
PEL (Permissible) TWA 0.1 ppm (0.7 mg/m)
REL (Recommended) TWA 0.1 ppm (0.7 mg/m)
IDLH (Immediate danger) 2 ppm
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Chloropicrin, also known as PS (from Port Sunlight) and nitrochloroform, is a chemical compound currently used as a broad-spectrum antimicrobial, fungicide, herbicide, insecticide, and nematicide. It was used as a poison gas in World War I and the Russian military has been accused of using it in the Russo-Ukrainian War. Its chemical structural formula is Cl3C−NO2.

Synthesis

Chloropicrin was discovered in 1848 by Scottish chemist John Stenhouse. He prepared it by the reaction of sodium hypochlorite with picric acid:

HOC6H2(NO2)3 + 11 NaOCl → 3 Cl3CNO2 + 3 Na2CO3 + 3 NaOH + 2 NaCl

Because of the precursor used, Stenhouse named the compound chloropicrin, although the two compounds are structurally dissimilar.

Today, chloropicrin is manufactured by the reaction of nitromethane with sodium hypochlorite:

H3CNO2 + 3 NaOCl → Cl3CNO2 + 3 NaOH

Reaction of chloroform and nitric acid also yields chloropicrin:

Cl3CH + HONO2 → Cl3CNO2 + H2O

Properties

Chloropicrin's chemical formula is CCl3NO2 and its molecular weight is 164.38 grams/mole. Pure chloropicrin is a colorless liquid, with a boiling point of 112 °C. Chloropicrin is sparingly soluble in water with solubility of 2 g/L at 25 °C. It is volatile, with a vapor pressure of 23.2 millimeters of mercury (mmHg) at 25 °C; the corresponding Henry's law constant is 0.00251 atmosphere-cubic meter per mole. The octanol-water partition coefficient (Kow) of chloropicrin is estimated to be 269. Its soil adsorption coefficient (Koc; normalized to soil organic matter content) is 25 cm/g.

Uses

Poison

Chloropicrin was manufactured for use as poison gas in World War I. In World War I, German forces used concentrated chloropicrin against Allied forces as a tear gas. While not as lethal as other chemical weapons, it induced vomiting and forced Allied soldiers to remove their masks to vomit, exposing them to more toxic gases used as weapons during the war.

Agriculture

In agriculture, chloropicrin is injected into soil prior to planting a crop to fumigate soil. Chloropicrin affects a broad spectrum of fungi, microbes and insects. It is commonly used as a stand-alone treatment or in combination / co-formulation with methyl bromide and 1,3-dichloropropene. Chloropicrin is used as an indicator and repellent when fumigating residences for insects with sulfuryl fluoride which is an odorless gas. Chloropicrin's mode of action is unknown (IRAC MoA 8B). Chloropicrin may stimulate weed germination, which can be useful when quickly followed by a more effective herbicide.

In 2008, the US EPA re-approved chloropicrin as safe for use in agricultural settings, stating that treatments "can provide benefits to both food consumers and growers. For consumers, it means more fresh fruits and vegetables can be cheaply produced domestically year-round because several severe pest problems can be efficiently controlled." To ensure chloropicrin is used safely, the EPA requires a strict set of protections for handlers, workers, and persons living and working in and around farmland during treatments. EPA protections were increased in both 2011 and 2012, reducing fumigant exposures and significantly improving safety. Protections include the training of certified applicators supervising pesticide application, the use of buffer zones, posting before and during pesticide application, fumigant management plans, and compliance assistance and assurance measures.

Used as a preplant soil treatment measure, chloropicrin suppresses soilborne pathogenic fungi and some nematodes and insects. According to chloropicrin manufacturers, with a half-life of hours to days, it is completely digested by soil organisms before the crop is planted, making it safe and efficient. Contrary to popular belief, chloropicrin does not sterilize soil and does not deplete the ozone layer, as the compound is destroyed by sunlight. Additionally, chloropicrin has never been found in groundwater, due to its low solubility.

California

In California, experience with acute effects of chloropicrin when used as a soil fumigant for strawberries and other crops led to the release of regulations in January 2015 creating buffer zones and other precautions to minimize exposure of farm workers, neighbors, and passersby.

Safety

At a national level, chloropicrin is regulated in the United States by the United States Environmental Protection Agency as a restricted use pesticide. Because of its toxicity and carcinogenicity, distribution and use of chloropicrin is available only to licensed professionals and specially certified growers who are trained in its proper and safe use. In the US, occupational exposure limits have been set at 0.1 ppm over an eight-hour time-weighted average.

High concentrations

Gas identification art for chloropicrin

Chloropicrin is harmful to humans. It can be absorbed systemically through inhalation, ingestion, and the skin. At high concentrations, it is severely irritating to the lungs, eyes, and skin.

Damage to protective gear

Chloropicrin and its derivative phosgene oxime have been known to damage or compromise earlier generations of personal protective equipment. Some of the soldiers attacked mentioned a white smoke emerging from their gas masks.

See also

References

  1. ^ NIOSH Pocket Guide to Chemical Hazards. "#0132". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ "Chloropicrin". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. Foulkes, C. H. (31 January 2012). "GAS!" – The Story of the Special Brigade. Andrews UK Limited. p. 193.
  4. "RED Fact Sheet: Chloropicrin" (PDF). US Environmental Protection Agency. 10 July 2008. p. 2. Retrieved 20 September 2013.
  5. Office of the Spokesperson (1 May 2024). "Imposing New Measures on Russia for its Full-Scale War and Use of Chemical Weapons Against Ukraine". U.S. Department of State. Archived from the original on 23 May 2024. Retrieved 23 May 2024.
  6. "A top Russian general is killed in a Moscow bombing claimed by Ukraine". Associated Press News. 2024-12-17. Retrieved 2024-12-18.
  7. Markofsky, Sheldon B. (2005). "Nitro Compounds, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH.
  8. Jackson, Kirby E. (1934). "Chloropicrin". Chemical Reviews. 14 (2): 251–286. doi:10.1021/cr60048a003.
  9. ^ "Executive Summary - Evaluation of Chloropicrin As A Toxic Air Contaminant" (PDF). Department of Pesticide Regulation - California Environmental Protection Agency. February 2010. p. iv. Archived from the original (PDF) on 6 October 2013. Retrieved 20 September 2013.
  10. Ayres, Leonard P. (1919). The War with Germany (2nd ed.). Washington, DC: United States Government Printing Office. p. 80.
  11. Heller, Charles E. (September 1984). "Chemical Warfare in World War I: The American Experience, 1917–1918" (PDF). Leavenworth Papers (10): 23.
  12. ^ "Factsheet: Chloropicrin" (PDF). New South Wales: WorkCover. Archived from the original (PDF) on May 20, 2009.
  13. Fries, Amos Alfred; West, Clarence Jay (1921). Chemical warfare. McGraw-Hill. p. 144.
  14. Chloropicrin in the Pesticide Properties DataBase (PPDB), University of Hertfordshire, accessed 2021-03-10.
  15. "IRAC Mode of Action Classification Scheme Version 9.4". IRAC (Insecticide Resistance Action Committee) (pdf). March 2020.
  16. Martin, Frank N. (2003). "Development of Alternative Strategies for Management of Soilborne Pathogens Currently Controlled with Methyl Bromide". Annual Review of Phytopathology. 41 (1). Annual Reviews: 325–350. doi:10.1146/annurev.phyto.41.052002.095514. ISSN 0066-4286. PMID 14527332.
  17. "Amended Reregistration Eligibility Decision (RED) for Chloropicrin" (PDF). United States Environmental Protection Agency. May 2009. Retrieved 20 September 2013.
  18. ^ "Chloropicrin Mitigation Proposal" (PDF). Department of Pesticide Regulation – California Environmental Protection Agency. 15 May 2013. p. 2. Archived from the original (PDF) on 6 October 2013. Retrieved 20 September 2013.
  19. "Chloropicrin – Background". Retrieved 20 September 2013.
  20. "Chloropicrin Mitigation Proposal" (PDF). Department of Pesticide Regulation – California Environmental Protection Agency. 15 May 2013. p. 2. Archived from the original (PDF) on 6 October 2013. Retrieved 20 September 2013. The Amended RED incorporated final new safety measures to increase protections for agricultural workers and bystanders. These measures establish a baseline for safe use of the soil fumigants throughout the United States, reducing fumigant exposures and significantly improving safety.
  21. "Chloropicrin Soil Fumigation in Potato Production Systems". Plant Management Network. American Phytopathological Society. Retrieved 1 Apr 2019.
  22. "Control Measures for Chloropicrin" (PDF). California Department of Pesticide Regulation. January 6, 2015. Archived from the original (PDF) on January 28, 2015. Retrieved January 15, 2015. added controls for chloropicrin when it is used as a soil fumigant. The controls are intended to reduce risk from acute (short-term) exposures that might occur near fields fumigated with products containing chloropicrin.
  23. "Chloropicrin Mitigation Proposal" (PDF). Department of Pesticide Regulation – California Environmental Protection Agency. 15 May 2013. p. 2. Archived from the original (PDF) on 6 October 2013. Retrieved 20 September 2013. The new measures appearing on soil fumigant Phase 2 labels include buffer zones and posting, emergency preparedness and response measures, training for certified applicators supervising applications, Fumigant Management Plans, and notice to State Lead Agencies who wish to be informed of applications in their states.
  24. ^ "Chloropicrin Mitigation Proposal" (PDF). Department of Pesticide Regulation – California Environmental Protection Agency. 15 May 2013. p. 1. Archived from the original (PDF) on 6 October 2013. Retrieved 20 September 2013.
  25. "NIOSH Pocket Guide to Chemical Hazards". Centers for Disease Control and Prevention. Retrieved 7 November 2013.
  26. "Chloropicrin (PS): Lung Damaging Agent". Emergency Response Safety and Health Database. National Institute for Occupational Safety and Health. August 22, 2008. Retrieved December 23, 2008.
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