| Revision as of 12:37, 15 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 473592999 of page Gadolinium(III)_chloride for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 07:39, 24 May 2024 edit Thomasnlln (talk | contribs)2 editsNo edit summary |
| Line 1: |
Line 1: |
|
{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
|
|
{{chembox |
|
{{chembox |
|
|
| Verifiedfields = changed |
|
| Watchedfields = changed |
|
| Watchedfields = changed |
|
| verifiedrevid = 443831708 |
|
| verifiedrevid = 476995257 |
|
| ImageFileL1 = UCl3.png |
|
| ImageFileL1 = UCl3 without caption.png |
|
| ImageFileR1 = Cerium bromide (space filling) 2.png |
|
| ImageFileR1 = Cerium bromide (space filling) 2.png |
|
|
| ImageFile2 = Gadolinium(III) chloride.jpg |
|
| IUPACName = |
|
|
| OtherNames = Gadolinium trichloride |
|
| IUPACName = Gadolinium(III) chloride |
|
|
| OtherNames = Gadolinium trichloride<br/>Gadolinium chloride |
|
| Section1 = {{Chembox Identifiers |
|
|
|
|Section1={{Chembox Identifiers |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
|
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID = 55406 |
|
| ChemSpiderID = 55406 |
|
| InChI = 1/3ClH.Gd/h3*1H;/q;;;+3/p-3 |
|
| InChI = 1/3ClH.Gd/h3*1H;/q;;;+3/p-3 |
|
| ChEBI_Ref = {{ebicite|correct|EBI}} |
|
| ChEBI_Ref = {{ebicite|correct|EBI}} |
|
| ChEBI = 37288 |
|
| ChEBI = 37288 |
|
|
| ChEMBL_Ref = {{ebicite|changed|EBI}} |
|
|
| ChEMBL = 1697696 |
|
| SMILES = Cl(Cl)Cl |
|
| SMILES = Cl(Cl)Cl |
|
| InChIKey = MEANOSLIBWSCIT-DFZHHIFOAP |
|
| InChIKey = MEANOSLIBWSCIT-DFZHHIFOAP |
| Line 20: |
Line 23: |
|
| StdInChIKey = MEANOSLIBWSCIT-UHFFFAOYSA-K |
|
| StdInChIKey = MEANOSLIBWSCIT-UHFFFAOYSA-K |
|
| CASNo = 10138-52-0 |
|
| CASNo = 10138-52-0 |
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|
| CASNo2_Ref = {{cascite|changed|CAS}} |
|
| CASOther = <br> 19423-81-5 (hexahydrate) |
|
|
|
| CASNo2 = 19423-81-5 |
|
|
| CASNo2_Comment = (hydrate) |
|
|
| CASNo3_Ref = {{cascite|correct|CAS}} |
|
|
| CASNo3 = 13450-84-5 |
|
|
| CASNo3_Comment = (hexahydrate) |
|
|
|
|
|
| UNII_Ref = {{fdacite|correct|FDA}} |
|
|
| UNII = P7082WY76D |
|
|
|
|
| PubChem = 61486 |
|
| PubChem = 61486 |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|Section2={{Chembox Properties |
|
| Formula = GdCl<sub>3</sub> |
|
| Formula = GdCl<sub>3</sub> |
|
| MolarMass = 263.61 g/mol |
|
| MolarMass = 263.61 g/mol |
|
| Appearance = white crystals <br> ] |
|
| Appearance = white crystals<br>] |
|
| Density = 4.52 g/cm<sup>3</sup> |
|
| Density = 4.52 g/cm<sup>3</sup> |
|
| MeltingPt = 609 °C |
|
| MeltingPtC = 609 |
|
| BoilingPt = 1580 °C |
|
| BoilingPtC = 1580 |
|
|
| Solubility = 94.65 g/100mL, 25°C<ref>{{cite book |last1=Saeger |first1=Victor William |last2=Spedding |first2=F. H. |title=Some physical properties of rare-earth chlorides in aqueous solution |date=November 1960 |publisher=Ames Laboratory Technical Reports 46 |page=38 |url=https://lib.dr.iastate.edu/cgi/viewcontent.cgi?article=1043&context=ameslab_isreports |access-date=19 October 2020}}</ref> |
|
| Solubility = soluble |
|
|
|
| MagSus = +27,930·10<sup>−6</sup> cm<sup>3</sup>/mol |
|
}} |
|
}} |
|
| Section3 = {{Chembox Structure |
|
|Section3={{Chembox Structure |
|
| CrystalStruct = ], ] |
|
| CrystalStruct = ], ] |
|
| SpaceGroup = P6<sub>3</sub>/m, No. 176 |
|
| SpaceGroup = P6<sub>3</sub>/m, No. 176 |
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
|Section7={{Chembox Hazards |
|
| MainHazards = |
|
| MainHazards = |
|
| FlashPt = |
|
| FlashPt = |
|
| Autoignition = |
|
| AutoignitionPt = |
|
}} |
|
}} |
|
|
|Section8={{Chembox Related |
|
|
| OtherAnions = ]<br/>]<br/>] |
|
|
| OtherCations = ]<br/>] |
|
|
}} |
|
|
}} |
|
|
'''Gadolinium(III) chloride''', also known as '''gadolinium trichloride''', is '''GdCl<sub>3</sub>'''. It is a colorless, hygroscopic, water-soluble solid. The ] GdCl<sub>3</sub>∙6H<sub>2</sub>O is commonly encountered and is sometimes also called gadolinium trichloride. Gd<sup>3+</sup> species are of special interest because the ion has the maximum number of unpaired spins possible, at least for known elements. With seven valence electrons and seven available f-orbitals, all seven electrons are unpaired and symmetrically arranged around the metal. The high magnetism and high symmetry combine to make Gd<sup>3+</sup> a useful component in NMR spectroscopy and MRI. |
|
|
|
|
|
==Preparation== |
|
|
GdCl<sub>3</sub> is usually prepared by the "]" route, which involves the initial synthesis of (NH<sub>4</sub>)<sub>2</sub>. This material can be prepared from the common starting materials at reaction temperatures of 230 °C from ]:<ref> |
|
|
{{cite book |
|
|
| last =Meyer |
|
|
| first =G. |
|
|
| title =The Ammonium Chloride Route to Anhydrous Rare Earth Chlorides-The Example of YCl<sub>3</sub> |
|
|
| volume =25 |
|
|
| year =1989 |
|
|
| pages =146–150 |
|
|
| doi =10.1002/9780470132562.ch35 |
|
|
| isbn =978-0-470-13256-2| series =Inorganic Syntheses |
|
}} |
|
}} |
|
|
</ref> |
|
|
::10 NH<sub>4</sub>Cl + Gd<sub>2</sub>O<sub>3</sub> → 2 (NH<sub>4</sub>)<sub>2</sub> + 6 NH<sub>3</sub> + 3 H<sub>2</sub>O |
|
|
|
|
|
from hydrated gadolinium chloride: |
|
|
::4 NH<sub>4</sub>Cl + 2 GdCl<sub>3</sub>∙6H<sub>2</sub>O → 2 (NH<sub>4</sub>)<sub>2</sub> + 12 H<sub>2</sub>O |
|
|
<!--what are (NH<sub>4</sub>)<sub>2</sub> and NH<sub>4</sub>?-The Corbett reference refers to them as complex chlorides.--> |
|
|
|
|
|
from ] metal: |
|
|
::10 NH<sub>4</sub>Cl + 2 Gd → 2 (NH<sub>4</sub>)<sub>2</sub> + 6 NH<sub>3</sub> + 3 H<sub>2</sub> |
|
|
|
|
|
In the second step the pentachloride is decomposed at 300 °C: |
|
|
:: (NH<sub>4</sub>)<sub>2</sub> → GdCl<sub>3</sub> + 2 NH<sub>4</sub>Cl |
|
|
This pyrolysis reaction proceeds via the intermediacy of NH<sub>4</sub>. |
|
|
|
|
|
The ] route is more popular and less expensive than other methods. GdCl<sub>3</sub> can, however, also be synthesized by the reaction of solid Gd at 600 °C in a flowing stream of ].<ref>{{cite book |
|
|
| last =Corbett |
|
|
| first =John D. |
|
|
| title =Inorganic Syntheses |
|
|
| chapter =Trichlorides of the Rare Earth Elements, Yttrium, and Scandium |
|
|
| series =Inorganic Syntheses |
|
|
| volume =22 |
|
|
| year =1983 |
|
|
| pages =39–42 |
|
|
| doi =10.1002/9780470132531.ch8 |
|
|
| isbn =978-0-470-13253-1 |
|
|
}}</ref> |
|
|
::Gd + 3 HCl → GdCl<sub>3</sub> + 3/2 H<sub>2</sub> |
|
|
|
|
|
Gadolinium(III) chloride also forms a ], GdCl<sub>3</sub>∙6H<sub>2</sub>O. The hexahydrate is prepared by gadolinium(III) oxide (or chloride) in concentrated ] followed by evaporation.<ref>{{cite journal |
|
|
| last1 =Quill |
|
|
| first1 =L. L. |
|
|
| title =Preparation of Lanthanide Chloride Methanolates Using 2,2-Dimethoxypropane |
|
|
| journal =Inorganic Chemistry |
|
|
| volume =6 |
|
|
| year =1967 |
|
|
| pages =1433–1435 |
|
|
| doi =10.1021/ic50053a032 |
|
|
| last2 =Clink |
|
|
| first2 =George L. |
|
|
| issue =7 |
|
|
}}</ref> |
|
|
|
|
|
==Structure== |
|
|
GdCl<sub>3</sub> crystallizes with a hexagonal ] structure, as seen for other 4f trichlorides including those of ], ], ], ], ], ], ].<ref>{{cite book |
|
|
| first = A.F. |
|
|
| last = Wells |
|
|
| year = 1984 |
|
|
| title = Structural Inorganic Chemistry |
|
|
| publisher = Clarendon Press |
|
|
| location = Oxford |
|
|
}}</ref> <!--something wrong here:In contrast GdCl<sub>3</sub> crystallizes in the ] motif and-->The following crystallize in theYCl<sub>3</sub> motif: ], HoCl<sub>3</sub>, ], TmCl<sub>3</sub>, YdCl<sub>3</sub>, LuCl<sub>3</sub>, YCl<sub>3</sub>). The UCl<sub>3</sub> motif features 9-coordinate metal with a tricapped trigonal prismatic ]. In the hexahydrate of gadolinium(III) chloride and other smaller 4f trichlorides and tribromides, six H<sub>2</sub>O ] and 2 Cl<sup>−</sup> ] coordinate to the ] resulting in a coordination group of 8. |
|
|
|
|
|
==Properties, with applications to MRI== |
|
|
Gadolinium salts are of primary interest for relaxation agents in magnetic resonance imaging (]). This technique exploits the fact that Gd<sup>3+</sup> has an electronic configuration of f<sup>7</sup>. Seven is the largest number of unpaired electron spins possible for an atom, so Gd<sup>3+</sup> is a key component in the design of highly paramagnetic complexes.<ref>{{cite journal |
|
|
| last =Raduchel |
|
|
| first =B. |author2=Weinmann, H. |author3=Muhler, A. |
|
|
| title =Gadolinium Chelates: Chemistry, Safety, & Behavior |
|
|
| journal =Encyclopedia of Nuclear Magnetic Resonance |
|
|
| volume =4 |
|
|
| year =1996 |
|
|
| pages =2166–2172 |
|
|
}}</ref> |
|
|
To generate the relaxation agents, Gd<sup>3+</sup> sources such as GdCl<sub>3</sub>∙6H<sub>2</sub>O are converted to ]es. GdCl<sub>3</sub>∙6H<sub>2</sub>O can not be used as an ] contrasting agent due to its low solubility in water at the body's near neutral pH.<ref name="SpencerWilson1997">{{cite journal|last1=Spencer|first1=A. J.|last2=Wilson|first2=S. A.|last3=Batchelor|first3=J.|last4=Reid|first4=A.|last5=Pees|first5=J.|last6=Harpur|first6=E.|title=Gadolinium Chloride Toxicity in the Rat|journal=Toxicologic Pathology|volume=25|issue=3|year=1997|pages=245–255|issn=0192-6233|doi=10.1177/019262339702500301|pmid=9210255|s2cid=19838648}}</ref> "Free" gadolinium(III), e.g. <sup>+</sup>, is ], so chelating agents are essential for biomedical applications. Simple ] or even ] ligands will not suffice because they do not remain bound to Gd<sup>3+</sup> in solution. Ligands with higher coordination numbers therefore are required. The obvious candidate is ]<sup>4−</sup>, ethylenediaminetetraacetate, which is a commonly employed ] used to complex to transition metals. In lanthanides, however, exhibit coordination numbers greater than six, so still larger aminocarboxylates are employed. |
|
|
|
|
|
One representative chelating agent is H<sub>5</sub>DTPA, diethylenetriaminepentaacetic acid.<ref>{{cite journal |
|
|
| last1 =Aime |
|
|
| first1 =S. |
|
|
| title =Synthesis and Characterization of a Novel DPTA-like Gadolinium(III) Complex: A Potential Reagent for the Determination of Glycated Proteins by Water Proton NMR Relaxation Measurements |
|
|
| journal =Inorganic Chemistry |
|
|
| volume =32 |
|
|
| year =1993 |
|
|
| pages =2068–2071 |
|
|
| doi =10.1021/ic00062a031 |
|
|
| last2 =Botta |
|
|
| first2 =Mauro |
|
|
| last3 =Dastru |
|
|
| first3 =Walter |
|
|
| last4 =Fasano |
|
|
| first4 =Mauro |
|
|
| last5 =Panero |
|
|
| first5 =Maurizio |
|
|
| last6 =Arnelli |
|
|
| first6 =Aldo |
|
|
| issue =10 |
|
|
}}</ref> |
|
|
Chelation to the conjugate base of this ligand increases the ] of the Gd<sup>3+</sup> at the body's neutral pH ''and'' still allows for the ] effect required for an ] contrast agent. The DTPA<sup>5−</sup> ligand binds to Gd through five oxygen atoms of the carboxylates and three nitrogen atoms of the amines. A 9th binding site remains, which is occupied by a ] molecule. The rapid exchange of this water ligand with bulk water is a major reason for the signal enhancing properties of the chelate. The structure of <sup>2−</sup> is a distorted tricapped trigonal prism. |
|
|
|
|
|
The following is the reaction for the formation of Gd-DTPA: |
|
|
|
|
|
] |
|
|
|
|
|
==References== |
|
|
<references /> |
|
|
*{{cite web | title=Gadolinium| work=Magnetic Resonance TIP-MRI Database| url=http://www.mr-tip.com/serv1.php?type=db1&dbs=Gadolinium| access-date=February 22, 2006}} |
|
|
*{{cite web | title=Gadolinium| work=Webelements| url=http://www.webelements.com/webelements/compounds/text/Gd/Cl3Gd1-10138520.html| access-date=February 22, 2006 }} |
|
|
|
|
|
{{Gadolinium compounds}} |
|
|
{{Chlorides}} |
|
|
{{Lanthanide halides}} |
|
|
|
|
|
{{DEFAULTSORT:Gadolinium(Iii) Chloride}} |
|
|
] |
|
|
] |
|
|
] |
|
|
] |