Lead(II) nitrate

Lead nitrate was first identified in 1597 by the alchemist Andreas Libavius, who called the substance plumbum dulce, meaning "sweet lead", because of its taste.{{cite book|first = Andreas|last = Libavius|author-link = Andreas Libavius|title = Alchemia Andreæ Libavii|location = Francofurti|publisher = Iohannes Saurius|year = 1595}} It is produced commercially by reaction of metallic lead with concentrated nitric acid in which it is sparingly soluble.{{cite EB1911 |wstitle=Lead |volume=16 |pages=314–320}}{{cite book|first = John|last = Macgregor|title = Progress of America to year 1846|publisher = Whittaker & Co|location = London|year = 1847|isbn = 0-665-51791-2}} It has been produced as a raw material for making pigments such as chrome yellow (lead(II) chromate, PbCrO₄) and chrome orange (basic lead(II) chromate, Pb₂CrO₅) and Naples yellow. These pigments were used for dyeing and printing calico and other textiles.{{cite book|title = A Text-book of Inorganic Chemistry|publisher = MacMillan|year = 1950|page = 838|first = James Riddick|last = Partington}} It has been used as an oxidizer in black powder and together with lead azide in special explosives.{{cite journal|title = Lead nitrate as an oxidizer in blackpowder|journal = Pyrotechnica |volume = 4 |date = October 1978|pages=16–18|first = J. B.|last = Barkley|publisher = Pyrotechnica Publications|location = Post Falls, Idaho}}

Lead nitrate is produced by reaction of lead(II) oxide with concentrated nitric acid:{{cite book| first = Norman N.|last = Greenwood|author2=Earnshaw, A. |year = 1997|title = Chemistry of the Elements| url = https://archive.org/details/chemistryelement00earn_612| url-access = limited|edition = 2nd|pages= [https://archive.org/details/chemistryelement00earn_612/page/n409 388], 456|location = Oxford|publisher = Butterworth-Heinemann|isbn = 0-7506-3365-4}}

: PbO + 2 HNO₃ (concentrated) → Pb(NO₃)₂↓ + H₂O

It may also be obtained by evaporation of the solution obtained by reacting metallic lead with dilute nitric acid.{{cite book|first = D. F.|last = Othmer|author-link = Donald Othmer|title = Kirk-Othmer Encyclopedia of Chemical Technology|edition = second completely revised|volume = 12 (Iron to Manganese)|year = 1967|publisher = John Wiley & Sons|location = New York|page = 272|isbn = 0-471-02040-0}}

: Pb + 4 HNO₃ → Pb(NO₃)₂ + 2 NO₂ + 2 H₂O

Solutions and crystals of lead(II) nitrate are formed in the processing of lead–bismuth wastes from lead refineries.{{cite web|title = Product catalog; other products|url = http://www.sidech.be/products.html|archive-url = https://web.archive.org/web/20070701013928/http://www.sidech.be/products.html|url-status=dead|archive-date = 2007-07-01|publisher = Sidech|location = Tilly, Belgium|access-date = 2008-01-05}}

File:Lead(II)-nitrate-xtal-Pb-coordination-3D-bs-17.png of the Pb²⁺ ion]]

Image:LeadNitrateCrystalStructure.png

The crystal structure of solid lead(II) nitrate has been determined by neutron diffraction.{{cite journal|first = W. C.|last = Hamilton|title = A neutron crystallographic study of lead nitrate|journal = Acta Crystallogr.|year = 1957|volume = 10|pages = 103–107|doi = 10.1107/S0365110X57000304|issue = 2|doi-access = }}{{cite journal|title = Structure refinement of lead nitrate|first = H.|last = Nowotny|author2=G. Heger |journal = Acta Crystallographica Section C|year = 1986 |volume = 42|pages = 133–35|doi = 10.1107/S0108270186097032|issue = 2|doi-access = }} The compound crystallizes in the cubic system with the lead atoms in a face-centred cubic system. Its space group is Pa3_Z=4 (Bravais lattice notation), with each side of the cube with length 784 picometres.

The black dots represent the lead atoms, the white dots the nitrate groups 27 picometres above the plane of the lead atoms, and the blue dots the nitrate groups the same distance below this plane. In this configuration, every lead atom is bonded to twelve oxygen atoms (bond length: 281 pm). All N–O bond lengths are identical, at 127 picometres.{{cite journal|url=https://scripts.iucr.org/cgi-bin/paper?a25608|title=Cấu trúc của chì nitrat|journal=Acta Crystallographica Section C|date=15 February 1986|volume=42 |issue=2 |pages=133–135 |doi=10.1107/S0108270186097032 |archive-url=|archive-date=|url-status=|accessdate =15 July 2019 |last1=Nowotny |first1=H. |last2=Heger |first2=G. }}

Research interest in the crystal structure of lead(II) nitrate was partly based on the possibility of free internal rotation of the nitrate groups within the crystal lattice at elevated temperatures, but this did not materialise.

{{Image frame

| caption=Solubility of lead nitrate in nitric acid at 26 °C.{{cite journal|first = L. M.|last = Ferris|title = Lead nitrate—Nitric acid—Water system|journal = Journal of Chemical & Engineering Data|year = 1959|doi = 10.1021/je60007a002|volume = 5|pages = 242|issue = 3}}

| content = {{Graph:Chart

| width=250| height=150

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| x=0,4.93,12.96,25.99,50.26,63.84,71.35

| y=37.41,24.75,12.22,4.26,0.53,0.06,0.008

| xAxisTitle=Nitric acid concentration /wt% | yAxisTitle=Solubility /wt% }}

}}

Lead nitrate is an oxidizer and has been used as such in pyrotechnics. It is soluble in water and dilute nitric acid.

Basic nitrates are formed when alkali is added to a solution. {{chem2|Pb2(OH)2(NO3)2}} is the predominant species formed at low pH. At higher pH {{chem2|Pb6(OH)5NO3}} is formed.{{cite journal|title = Basic Salts of Lead Nitrate Formed in Aqueous Media|first = J. L.|last = Pauley|author2=M. K. Testerman |journal = Journal of the American Chemical Society|year = 1954|volume = 76|issue = 16|pages = 4220–4222|doi = 10.1021/ja01645a062}} The cation {{chem2|\[Pb6O(OH)6\]^{4+} }} is unusual in having an oxide ion inside a cluster of 3 face-sharing {{chem2|PbO4}} tetrahedra.{{Greenwood&Earnshaw}} p. 395

There is no evidence for the formation of the hydroxide, {{chem2|Pb(OH)2}}, in aqueous solution below pH 12.

Solutions of lead nitrate can be used to form co-ordination complexes. Lead(II) is a hard acceptor; it forms stronger complexes with nitrogen and oxygen electron-donating ligands. For example, combining lead nitrate and pentaethylene glycol (shortened to EO5 in the referenced paper) in a solution of acetonitrile and methanol followed by slow evaporation produced the compound [{{chem2|Pb(NO3)2}}EO5].{{cite journal|title = Structural Chemistry of Poly (ethylene glycol). Complexes of Lead(II) Nitrate and Lead(II) Bromide|first = Robin D.|last = Rogers|author2=Andrew H. Bond |author3=Debra M. Roden |journal = Inorg. Chem.|year = 1996|issue = 24|pages = 6964–6973|doi = 10.1021/ic960587b|volume = 35|pmid=11666874}} In the crystal structure for this compound, the EO5 chain is wrapped around the lead ion in an equatorial plane similar to that of a crown ether. The two bidentate nitrate ligands are in trans configuration. The total coordination number is 10, with the lead ion in a bicapped square antiprism molecular geometry.

The complex formed by lead nitrate with a bithiazole bidentate N-donor ligand is binuclear. The crystal structure shows that the nitrate group forms a bridge between two lead atoms.{{cite journal|title = A Dimeric Mixed-Anions Lead(II) Complex: Synthesis and Structural Characterization of [Pb₂(BTZ)₄(NO₃)(H₂O)](ClO₄)₃ {BTZ = 4,4'-Bithiazole}|first = Ali Reza|last = Mahjoub|author2 = Ali Morsali|journal = Chemistry Letters|volume = 30|issue = 12|year = 2001|page= 1234|doi=10.1246/cl.2001.1234}} One aspect of this type of complexes is the presence of a physical gap in the coordination sphere; i.e., the ligands are not placed symmetrically around the metal ion. This is potentially due to a lone pair of lead electrons, also found in lead complexes with an imidazole ligand.{{cite journal|title = 2D 4.8² Network with threefold parallel interpenetration from nanometre-sized tripodal ligand and lead(II) nitrate|author = Shuang-Yi Wan|author2 = Jian Fan|author3 = Taka-aki Okamura|author4 = Hui-Fang Zhu|author5 = Xing-Mei Ouyang|author6 = Wei-Yin Sun|author7 = Norikazu Ueyama|name-list-style = amp|journal = Chem. Commun.|year = 2002|pages = 2520–2521|doi = 10.1039/b207568g|issue = 21}}

Lead nitrate has been used as a heat stabiliser in nylon and polyesters, as a coating for photothermographic paper, and in rodenticides.

Heating lead nitrate is convenient means of making nitrogen dioxide:

:2 Pb(NO_3)_2->[\Delta]2PbO + 4NO_2 +O_2

In the gold cyanidation process, addition of lead(II) nitrate solution improves the leaching process. Only limited amounts (10 to 100 milligrams lead nitrate per kilogram gold) are required.{{cite journal|first = Fathi|last = Habashi|title = Recent advances in gold metallurgy|year = 1998 |journal=Revisa de la Facultad de Ingeniera, Universidad Central de Venezuela|volume=13|issue=2|pages=43–54}}{{cite web|url = http://www.e-goldprospecting.com/html/auxiliary_agents_in_gold_cyani.html|title = Auxiliary agents in gold cyanidation|publisher = Gold Prospecting and Gold Mining|access-date = 2008-01-05}}

In organic chemistry, it may be used in the preparation of isothiocyanates from dithiocarbamates.{{OrgSynth|author =Dains, F. B.|author2 =Brewster, R. Q.|author3 =Olander, C. P. |title = Phenyl isothiocyanate|collvol = 1|collvolpages = 447|prep = cv1p0447}} Its use as a bromide scavenger during S_N1 substitution has been reported.

{{OrgSynth|author = Rapoport, H.|author2 = Jamison, T.|collvol = 9|collvolpages = 344|prep = cv9p0344|year = 1998|title = (S)-N-(9-Phenylfluoren-9-yl)alanine and (S)-Dimethyl-N-(9-phenylfluoren-9-yl)aspartate}}

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{{main|Lead poisoning}}

Lead(II) nitrate is toxic, and ingestion may lead to acute lead poisoning, as is applicable for all soluble lead compounds.{{cite web|title = Lead nitrate, Chemical Safety Card 1000|url = http://www.inchem.org/documents/icsc/icsc/eics1000.htm |publisher = International Labour Organization, International Occupational Safety and Health Information Centre|date=March 1999|access-date = 2008-01-19}} All inorganic lead compounds are classified by the International Agency for Research on Cancer (IARC) as probably carcinogenic to humans (Category 2A).{{cite journal|publisher=International Agency for Research on Cancer |year=1987 |url=http://monographs.iarc.fr/ENG/Monographs/suppl7/suppl7.pdf |title=Inorganic and Organic Lead Compounds |journal=IARC Monographs on the Evaluation of Carcinogenic Risks to Humans |volume=Suppl. 7 |access-date=2008-01-19 |page=239 |url-status=dead |archive-url=https://web.archive.org/web/20080306134819/http://monographs.iarc.fr/ENG/Monographs/suppl7/suppl7.pdf |archive-date=2008-03-06 }} They have been linked to renal cancer and glioma in experimental animals and to renal cancer, brain cancer and lung cancer in humans, although studies of workers exposed to lead are often complicated by concurrent exposure to arsenic.{{cite journal|publisher = International Agency for Research on Cancer|year = 2006|url = http://monographs.iarc.fr/ENG/Monographs/vol87/volume87.pdf|title = Inorganic and Organic Lead Compounds|journal = IARC Monographs on the Evaluation of Carcinogenic Risks to Humans|volume = 87|isbn = 92-832-1287-8|access-date = 2008-01-01|author = World Health Organization, International Agency for Research on Cancer|url-status=dead|archive-url = https://web.archive.org/web/20071021091930/http://monographs.iarc.fr/ENG/Monographs/vol87/volume87.pdf|archive-date = 2007-10-21}} Lead is known to substitute for zinc in a number of enzymes, including δ-aminolevulinic acid dehydratase (porphobilinogen synthase) in the haem biosynthetic pathway and pyrimidine-5′-nucleotidase, important for the correct metabolism of DNA and can therefore cause fetal damage.{{cite journal|last = Mohammed-Brahim|first = B.|author2 = Buchet, J.P. |author3=Lauwerys, R. |title = Erythrocyte pyrimidine 5'-nucleotidase activity in workers exposed to lead, mercury or cadmium|journal = Int Arch Occup Environ Health|year = 1985|volume = 55|issue = 3|pages = 247–52|pmid = 2987134|doi = 10.1007/BF00383757|s2cid = 40092031}}

{{reflist|30em}}

{{Commons category|Lead(II) nitrate}}

• {{cite journal|last = Woodbury|first = William D.|title = Lead|url = http://digicoll.library.wisc.edu/cgi-bin/EcoNatRes/EcoNatRes-idx?type=article&did=ECONATRES.MINYB1982V1.WWOODBURY&isize= |journal = Mineral Yearbook Metals and Minerals|year = 1982|publisher = Bureau of Mines|pages = 515–42|access-date = 2008-01-18}}
• {{cite journal|title = Lead|url = https://www.cdc.gov/niosh/npg/npgd0368.html|publisher = National Institute for Occupational Safety and Health|journal = NIOSH Pocket Guide to Chemical Hazards|date=September 2005|id = NIOSH 2005-149| access-date = 2008-01-19}}
• {{cite journal|title = Lead and Lead Compounds Fact Sheet|url = http://www.npi.gov.au/database/substance-info/profiles/50.html|journal = National Pollutant Inventory|publisher = Australian Government, Department of the Environment and Water Resources|date=July 2007| access-date = 2008-01-19| archive-url = https://web.archive.org/web/20080111154608/http://www.npi.gov.au/database/substance-info/profiles/50.html| archive-date = January 11, 2008}}
• {{cite journal|title = Lead|url = http://www.afhh.org/hhe/hhe_lead.htm|journal = A Healthy Home Environment, Health Hazards|publisher = US Alliance for healthy homes|access-date = 2008-01-19|url-status=dead|archive-url = https://web.archive.org/web/20080220005525/http://www.afhh.org/hhe/hhe_lead.htm|archive-date = 2008-02-20}}

;Material Safety Data Sheets

• [http://physchem.ox.ac.uk/MSDS/LE/lead_nitrate.html MSDS for lead nitrate, PTCL, Oxford University]
• [https://web.archive.org/web/20060328120306/http://www.sciencestuff.com/msds/C1980.html MSDS for lead nitrate, Science Stuff Inc]
• [https://web.archive.org/web/20060504233922/http://avogadro.chem.iastate.edu/MSDS/Pb(NO3)2.htm MSDS for lead nitrate, Iowa State University]

{{Lead compounds}}

{{nitrates}}

{{portal|Chemistry}}

{{DEFAULTSORT:Lead(Ii) Nitrate}}

Category:IARC Group 2A carcinogens

Category:Lead(II) compounds

Category:Nitrates

Category:Oxidizing agents