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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid [{{fullurl:Zinc_phosphide|oldid=470341565}} 470341565] of page [[Zinc_phosphide]] with values updated to verified values.}} |
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{{chembox |
{{chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 403105509 |
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| Watchedfields = changed |
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| Name = Zinc phosphide |
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| verifiedrevid = 470636688 |
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| Name = Zinc phosphide |
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| Reference = <ref name="hand"> |
| Reference = <ref name="hand"> |
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{{Cite book | last = Lide | first = David R. | year = 1998 |
{{Cite book | last = Lide | first = David R. | year = 1998 |
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| title = Handbook of Chemistry and Physics | edition = 87 | |
| title = Handbook of Chemistry and Physics | edition = 87 | location = Boca Raton, FL |
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| publisher = CRC Press | isbn = 0-8493-0594-2 |
| publisher = CRC Press | isbn = 0-8493-0594-2 |
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| pages = 4–100 }}</ref> |
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| pages = 4–95 | postscript = <!-- Bot inserted parameter. Either remove it; or change its value to "." for the cite to end in a ".", as necessary. -->{{inconsistent citations}}}}</ref> |
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| ImageFile = Zn3P2structure.jpg |
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| ImageSize = |
| ImageSize = |
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| ImageName = Zinc phosphide |
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| OtherNames = trizinc diphosphide |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 11344765 |
| ChemSpiderID = 11344765 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 813396S1PC |
| UNII = 813396S1PC |
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| PubChem = 25113606 |
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| EC_number = 234-867-3 |
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| InChI = 1/2P.3Zn/rP2Zn3/c3-1-5-2-4 |
| InChI = 1/2P.3Zn/rP2Zn3/c3-1-5-2-4 |
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| InChIKey = NQDYSWQRWWTVJU-WGUIJFGEAN |
| InChIKey = NQDYSWQRWWTVJU-WGUIJFGEAN |
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| StdInChIKey = NQDYSWQRWWTVJU-UHFFFAOYSA-N |
| StdInChIKey = NQDYSWQRWWTVJU-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = |
| CASNo = 1314-84-7 |
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| CASNo_Comment = ({{chem|Zn|3|P|2}}) |
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}} |
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| CASNo1_Ref = {{cascite|changed|??}} |
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| Section2 = {{Chembox Properties |
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| CASNo1 = 12037-79-5 |
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| Formula = Zn<sub>3</sub>P<sub>2</sub> |
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| CASNo1_Comment = ({{chem|Zn|P|2}}) |
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| MolarMass = 258.12 g/mol |
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| CASNo2_Ref = {{cascite|changed|??}} |
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| Appearance = gray [[tetragonal]] crystals |
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| CASNo2 = 51810-70-9 |
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| Density = 4.55 g/cm<sup>3</sup> |
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| CASNo2_Comment = ({{chem|Zn|x|P|x}}) |
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| Solubility = insoluble |
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}} |
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|Section2={{Chembox Properties |
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| Formula = Zn<sub>3</sub>P<sub>2</sub> |
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| MolarMass = 258.12 g/mol |
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| Appearance = dark gray |
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| Odor = characteristic<ref name="ThermoFisher-SDS"/> |
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| Density = 4.55 g/cm<sup>3</sup> |
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| Solubility = reacts |
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| SolubleOther = insoluble in [[ethanol]], soluble in [[benzene]], reacts with [[acid]]s |
| SolubleOther = insoluble in [[ethanol]], soluble in [[benzene]], reacts with [[acid]]s |
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| MeltingPtC = 1160 |
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| MeltingPt = 420°C |
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| BandGap = 1.4-1.6 eV (direct)<ref>{{Cite journal|title=Photoelectric Detectors Based on Inorganic p-Type Semiconductor Materials|journal=Advanced Materials|last1=Teng|first1=F.|pages=1706262|last2=Hu|first2=K.|doi=10.1002/adma.201706262|last3=Ouyang|first3=W.|last4=Fang|first4=X.|year=2018|volume=30|issue=35|pmid=29888448|bibcode=2018AdM....3006262T |s2cid=47016453 }}</ref> |
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| BoilingPt = 1100°C |
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}} |
}} |
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|Section3={{Chembox Structure |
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| CrystalStruct = [[Tetragonal]], [[Pearson symbol|tP40]] |
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| SpaceGroup = P4<sub>2</sub>/nmc, No. 137 |
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| LattConst_a = 8.0785 Å |
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}} |
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| LattConst_c = 11.3966 Å |
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| Section7 = {{Chembox Hazards |
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| LattConst_ref = <ref name="JSC">{{Cite journal|title=Structure of Zn<sub>3</sub>P<sub>2</sub>|journal=Journal of Structural Chemistry|last1=Zanin|first1=I. E.|volume=45|pages=844–848|last2=Aleinikova|first2=K. B.|issue=5|doi=10.1007/s10947-005-0067-9|year=2004|last3=Afanasiev|first3=M. M.|last4=Antipin|first4=M. Yu.|s2cid=101460207}}</ref> |
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| EUClass = |
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| UnitCellFormulas = 8 |
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}} |
}} |
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|Section7={{Chembox Hazards |
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| ExternalSDS = ThermoFisher Scientific, revised 02/2020<ref name="ThermoFisher-SDS"/> |
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| GHSPictograms = {{GHS02}} {{GHS06}} |
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| GHS_ref = <ref name="ThermoFisher-SDS">{{Cite web|url=https://www.fishersci.com/store/msds?partNumber=AA4545904&productDescription=ZINC+PHOSPHIDE%2C+99.999%25+2G&vendorId=VN00024248&countryCode=US&language=en |title=ThermoFisher Scientific safety data sheet|date=2020-02-21|access-date=2020-11-02| website=fishersci.com| publisher=Thermo Fisher Scientific}}</ref> |
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| GHSSignalWord = Danger |
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| IngestionHazard = Fatal, acutely toxic |
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| InhalationHazard = High |
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| HPhrases = {{H-phrases|260|300}} |
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| PPhrases = {{P-phrases|223|231+232|264|270|280|301+310|321|330|335+334|370+378|402+404|405|501}} |
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| NFPA-H = 4 |
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| NFPA-R = 2 |
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| NFPA-F = 3 |
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| NFPA-S = W |
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| NFPA_ref = <ref name="ThermoFisher-SDS"/> |
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| LD50='''Oral'''<BR>42.6 mg/kg (Rat)<BR>12 mg/kg (Rat)<BR>'''Dermal'''<BR>1123 mg/kg (Rat)<BR>2000 mg/kg (Rabbit)<ref name="ThermoFisher-SDS"/> |
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}} |
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'''Zinc phosphide''' ([[Zinc|Zn<sub>3</sub>]][[Phosphorus|P<sub>2</sub>]]) is an [[inorganic]] [[chemical compound]]. It is a grey solid, although commercial samples are often dark or even black. It is used as a [[rodenticide]].<ref>{{ cite encyclopedia |author1=Bettermann, G. |author2=Krause, W. |author3=Riess, G. |author4=Hofmann, T. | chapter = Phosphorus Compounds, Inorganic | encyclopedia = Ullmann's Encyclopedia of Industrial Chemistry | year = 2002 | publisher = Wiley-VCH | location = Weinheim | doi = 10.1002/14356007.a19_527 |isbn=3527306730 }}</ref> Zn<sub>3</sub>P<sub>2</sub> is a [[List of semiconductor materials|II-V]] [[semiconductor]] with a direct band gap of 1.5 [[electron volt|eV]]<ref name="KimballMüller2009">{{cite journal|last1=Kimball|first1=Gregory M.|last2=Müller|first2=Astrid M.|last3=Lewis|first3=Nathan S.|last4=Atwater|first4=Harry A.|title=Photoluminescence-based measurements of the energy gap and diffusion length of Zn[sub 3]P[sub 2]|journal=Applied Physics Letters|volume=95|issue=11|year=2009|pages=112103|issn=0003-6951|doi=10.1063/1.3225151|bibcode=2009ApPhL..95k2103K |url=https://authors.library.caltech.edu/16318/1/ApplPhysLett_95_112103.pdf}}</ref> and may have applications in [[Solar cell|photovoltaic cells]].<ref>Specialist Periodical Reports, Photochemistry, 1981, Royal Society of Chemistry, {{ISBN|9780851860954}}</ref> A second compound exists in the zinc-phosphorus system, [[zinc diphosphide|zinc diphosphide (ZnP<sub>2</sub>)]]. |
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==Synthesis and reactions== |
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Zinc phosphide can be prepared by the reaction of [[zinc]] with [[phosphorus]]; however, for critical applications, additional processing to remove [[arsenic]] compounds may be needed.<ref>F. Wagenknecht and R. Juza "Zinc Phosphides" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1080-1.</ref> |
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:6 Zn + P<sub>4</sub> → 2 Zn<sub>3</sub>P<sub>2</sub> |
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Another method of preparation include reacting tri-n-octylphosphine with [[dimethylzinc]].<ref name="LuberMobarok2013">{{cite journal|last1=Luber|first1=Erik J.|last2=Mobarok|first2=Md Hosnay|last3=Buriak|first3=Jillian M.|title=Solution-Processed Zinc Phosphide (α-Zn<sub>3</sub>P<sub>2</sub>) Colloidal Semiconducting Nanocrystals for Thin Film Photovoltaic Applications|journal=ACS Nano|volume=7|issue=9|year=2013|pages=8136–8146|issn=1936-0851|doi=10.1021/nn4034234|pmid=23952612}}</ref> |
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Zinc phosphide reacts with water to produce highly toxic [[phosphine]] (PH<sub>3</sub>) and [[zinc hydroxide]] (Zn(OH)<sub>2</sub>): |
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:Zn<sub>3</sub>P<sub>2</sub> + 6 H<sub>2</sub>O → 2 PH<sub>3</sub> + 3 Zn(OH)<sub>2</sub> |
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==Structure== |
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Zn<sub>3</sub>P<sub>2</sub> has a room-temperature [[Tetragonal crystal system|tetragonal]] form that converts to a [[Cubic crystal system|cubic]] form at around 845 °C.<ref name = Tonkov>Evgeniĭ I︠U︡rʹevich Tonkov, 1992, High Pressure Phase Transformations: A Handbook, Vol 2, Gordon and Breach Science Publishers, {{ISBN|9782881247590}}</ref> In the room-temperature form there are discrete P atoms, zinc atoms are tetrahedrally coordinated and phosphorus six coordinate, with zinc atoms at 6 of the vertices of a distorted cube.<ref>Wells A.F. (1984) ''Structural Inorganic Chemistry'' 5th edition Oxford Science Publications {{ISBN|0-19-855370-6}}</ref> |
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The crystalline structure of zinc phosphide is very similar to that of [[cadmium arsenide]] (Cd<sub>3</sub>As<sub>2</sub>), [[zinc arsenide]] (Zn<sub>3</sub>As<sub>2</sub>) and [[cadmium phosphide]] (Cd<sub>3</sub>P<sub>2</sub>). These compounds of the [[Zinc cadmium phosphide arsenide|Zn-Cd-P-As quaternary system]] exhibit full continuous solid-solution.<ref name="Trukhan">{{Cite journal|title=Compounds and solid solutions of the Zn-Cd-P-As system in semiconductor electronics|journal=Inorganic Materials|last1=Trukhan|first1=V. M.|volume=50|pages=868–873|last2=Izotov|first2=A. D.|issue=9|doi=10.1134/S0020168514090143|year=2014|last3=Shoukavaya|first3=T. V.|s2cid=94409384}}</ref> |
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== Applications == |
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=== Photovoltaics === |
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Zinc phosphide is an ideal candidate for thin film photovoltaic applications, for it has strong optical absorption and an almost ideal band gap (1.5eV). In addition to this, both zinc and phosphorus are found abundantly in the Earth's crust, meaning that material extraction cost is low compared with that of other thin film [[photovoltaics]]. Both zinc and phosphorus are also nontoxic, which is not the case for other common commercial thin film photovoltaics, like [[cadmium telluride]].<ref>{{cite journal|doi=10.1021/nn4034234 | volume=7 | issue=9 | title=Solution-Processed Zinc Phosphide (α-Zn 3 P 2 ) Colloidal Semiconducting Nanocrystals for Thin Film Photovoltaic Applications | journal=ACS Nano | pages=8136–8146 | last1 = Luber | first1 = Erik J.| year=2013 | pmid=23952612 }}</ref> |
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Researchers at the [[University of Alberta]] were the first to successfully synthesize colloidal zinc phosphide. Before this, researchers were able to create efficient [[solar cell]]s from bulk zinc phosphide, but their fabrication required temperatures greater than 850 °C or complicated vacuum deposition methods. By contrast, colloidal zinc phosphide [[nanoparticle]]s, contained in a zinc phosphide “ink”, allows for inexpensive, easy large-scale production, by means of slot-die coating or spray coating.<ref>{{cite web |url=http://nanotechweb.org/cws/article/tech/54627 |url-status=dead |archive-url=https://web.archive.org/web/20130916163436/http://nanotechweb.org/cws/article/tech/54627 |archive-date=2013-09-16 |title=Colloidal zinc phosphide for photovoltaics - nanotechweb.org}}</ref> |
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The testing and development of these zinc phosphide thin films is still in its early stages, but early results have been positive. Prototype heterojunction devices fabricated from zinc phosphide nanoparticle ink exhibited a rectification ratio of 600 and [[photosensitivity]] with an on/off ratio near 100. These are both acceptable suitability benchmarks for solar cells. Development still needs to be made on optimizing the nanoparticle ink formation and device architecture before commercialization is possible, but commercial spray-on zinc phosphide solar cells may be possible within ten years.<ref>{{Cite web|url=http://www.solarnovus.com/zinc-phosphide-nonocrystals-for-spray-on-solar-thin-films_N7005.html|title = Home}}</ref> |
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=== Pest control === |
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====Rodenticide==== |
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Metal phosphides have been used as [[rodenticide]]s. A mixture of food and zinc phosphide is left where the rodents can eat it. The acid in the digestive system of the rodent reacts with the phosphide to generate toxic [[phosphine]] gas. This method of vermin control has possible use in places where rodents are immune to other common poisons. Other pesticides similar to zinc phosphide are [[aluminium phosphide]] and [[calcium phosphide]]. |
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: Zn<sub>3</sub>P<sub>2</sub> + 6H<sup>+</sup> → 3Zn<sup>++</sup> + PH<sub>3</sub> ↑<ref>{{Cite web|title=Zinc Phosphide Technical Fact Sheet|url=http://npic.orst.edu/factsheets/archive/znptech.html#:~:text=Phospine%20in%20this%20fact%20sheet%20refers%20to%20the%20gaseous%20form%20of%20this%20compound%20The%20chemical%20reaction%20that%20releases%20phosphine%20is11:%20Zn3P2%20+%206H%20%E2%86%92%20PH3%20%E2%86%91%20+%203Zn++|access-date=|website=npic.orst.edu}}</ref> |
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Zinc phosphide is typically added to rodent baits in amount of around 0.75-2%. Such baits have a strong, pungent [[garlic]]-like odor characteristic of phosphine liberated by [[hydrolysis]]. The odor attracts rodents, but has a repulsive effect on other animals; However, birds, notably [[wild turkey]]s, are not sensitive to the smell. The baits have to contain sufficient amount of zinc phosphide in sufficiently attractive food in order to kill rodents in a single serving; a sublethal dose may cause aversion towards zinc phosphide baits encountered by surviving rodents in the future. |
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Rodenticide-grade zinc phosphide usually comes as a black powder containing 75% of zinc phosphide and 25% of [[Potassium antimony tartrate|antimony potassium tartrate]], an [[emetic]] to cause vomiting if the material is accidentally ingested by humans or domestic animals. However, it is still effective against rats, mice, guinea pigs and rabbits, none of which have a vomiting reflex.<ref>{{cite web|url=http://www.ratbehavior.org/vomit.htm |title=Why rats can't vomit |publisher=Ratbehavior.org |access-date=2013-08-17}}</ref><!-- see [[Fancy mouse]] --> |
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==== Pest control in New Zealand==== |
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The New Zealand [[Environmental Protection Authority (New Zealand)|Environmental Protection Authority]] has approved the import and manufacture of Microencapsulated Zinc Phosphide (MZP Paste) for the ground control of [[common brushtail possum|possums]]. The application was made by Pest Tech Limited, with support from Connovation Ltd, [[Lincoln University (New Zealand)|Lincoln University]] and the [[Animal Health Board (New Zealand)|Animal Health Board]]. It will be used as an additional vertebrate poison in certain situations. Unlike [[sodium fluoroacetate|1080 poison]], it cannot be used for aerial application.<ref>{{cite web |
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| last = Environment Risk Management Authority New Zealand| title = Zinc phosphide pest poison approved with controls| access-date = 2011-08-14| url = http://www.epa.govt.nz/news/erma-media-releases/Pages/Zinc-phosphide-pest-poison-approved-with-controls-.aspx}}</ref> |
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==Safety== |
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Zinc phosphide is highly toxic, especially when ingested or inhaled. The reason for its toxicity is the release of phosphorus compounds, usually [[phosphine]], when it reacts with water and acids. Phosphine is very toxic and, with trace amounts of [[Diphosphane|P<sub>2</sub>H<sub>4</sub>]], [[pyrophoric]]. Phosphine is also denser than air and may remain close to the ground without sufficient [[Ventilation (architecture)|ventilation]]. |
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==References== |
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{{Reflist}} |
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==External links== |
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* [http://extoxnet.orst.edu/pips/zincphos.htm Zinc Phosphide Pesticide Information Profile - Extension Toxicology Network] |
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* [http://www.epa.gov/pesticides/factsheets/chemicals/rodenticides_fs.htm EPA Proposed Risk Mitigation Decision for Nine Rodenticides] |
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*{{PPDB|1730}} |
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* [http://www.michigan.gov/dnr/0,1607,7-153-10370_12150_12220-26326--,00.html Zinc phosphide properties and use in Michigan] |
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* [https://web.archive.org/web/20071008081142/http://milmed.pmk.ac.th/md0173%20PESTICIDES%20IN%20THE%20MILITARY.pdf MD0173] - Pesticides in the military |
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{{Zinc compounds}} |
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{{Phosphorus compounds}} |
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{{Phosphides}} |
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{{rodenticides}} |
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[[Category:Phosphides]] |
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[[Category:Zinc compounds|phosphide]] |
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[[Category:Rodenticides]] |
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[[Category:II-V semiconductors]] |
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[[Category:II-V compounds]] |
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[[Category:Foul-smelling chemicals]] |