المعرفة

كلوريد الحديد الثلاثي

(تم التحويل من Iron(III) chloride)

Iron(III) chloride describes the inorganic compounds with the formula FeCl
3(H2O)x. Also called ferric chloride, these compounds are available both in anhydrous and hydrated forms which are both hygroscopic. They are common sources of iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while the hydrate is a mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

كلوريد الحديد الثلاثي
Iron(III) chloride anhydrate.jpg
Iron(III) chloride (anhydrous)
Хлорид железа.jpg
Iron(III) chloride (hydrate)
Iron-trichloride-sheet-3D-polyhedra.png
Iron-trichloride-sheets-stacking-3D-polyhedra.png
الأسماء
اسم أيوپاكs
Iron(III) chloride
Iron trichloride
أسماء أخرى
  • Ferric chloride
  • Molysite
  • Flores martis
Identifiers
رقم CAS
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.028.846 Edit this at Wikidata
رقم EC
  • 231-729-4
رقم RTECS
  • LJ9100000
UNII
UN number
  • 1773 (anhydrous)
  • 2582 (aqueous solution)
InChI InChI={{{value}}}
SMILES
الخصائص
الصيغة الجزيئية FeCl
3
كتلة مولية
  • 162.204 g/mol (anhydrous)
  • 270.295 g/mol (hexahydrate)[1]
المظهر Green-black by reflected light; purple-red by transmitted light; yellow solid as hexahydrate; brown as aqueous solution
الرائحة Slight HCl
الكثافة
  • 2.90 g/cm3 (anhydrous)
  • 1.82 g/cm3 (hexahydrate)[1]
نقطة الانصهار
نقطة الغليان
قابلية الذوبان في الماء 912 g/L (anhydrous or hexahydrate, 25 °C)[1]
قابلية الذوبان في
  •  
  • 630 g/L (18 °C)
  • Highly soluble
  • 830 g/L
  • Highly soluble
القابلية المغناطيسية +13,450·10−6 cm3/mol[2]
اللزوجة 12 cP (40% solution)
المخاطر[4][5][Note 1]
صفحة بيانات السلامة ICSC 1499
ن.م.ع. مخطط تصويري Corr. Met. 1; Skin Corr. 1C; Eye Dam. 1Acute Tox. 4 (oral)
ن.م.ع. كلمة الاشارة DANGER
H290, H302, H314
P234, P260, P264, P270, P273, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P390, P405, P406, P501
NFPA 704 (معيـَّن النار)
Flammability code 0: لن يشتعل. مثل الماءHealth code 2: التعرض الشديد أو المتواصل ولكن ليس بمزمن قد يتسبب في عجز مؤقت أو جرح بُحتمل بقاؤه. مثل الكلوروفورمReactivity code 0: مستقر في العادة، حتى تحت ظروف التعرض للنار، ولا يتفاعل مع الماء. مثل النيتروجين السائلSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
2
0
نقطة الوميض Non-flammable
حدود التعرض الصحية بالولايات المتحدة (NIOSH):
REL (الموصى به)
 TWA 1 mg/m3[3]
مركبات ذا علاقة
coagulants ذات العلاقة
البنية
البنية البلورية Hexagonal, hR24
الزمرة الفراغية R3, No. 148[7]
ثابت العقد a = 0.6065 nm, b = 0.6065 nm, c = 1.742 nm
ثابت العقد α = 90°, β = 90°, γ = 120°
Octahedral
ما لم يُذكر غير ذلك، البيانات المعطاة للمواد في حالاتهم العيارية (عند 25 °س [77 °ف]، 100 kPa).
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مراجع الجدول

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البنية والخصائص

 
Anhydrous iron(III) chloride evaporates at relatively mild temperatures to give the bitetrahedral dimer.

All forms of ferric chloride are paramagnetic, owing to the presence of five unpaired electrons residing in 3d orbitals. This electronic configuration places electrons in molecular orbitals that are antibonding with respect to ligands. Thus, iron(III) chlorides are labile, undergoing rapid ligand exchange in solution. In contrast to their kinetic lability, iron(III) chlorides are thermodynamically robust, as reflected by the vigorous methods applied to their synthesis.[8][9]


اللامائي

The anhydrous compound is a hygroscopic crystalline solid with a melting point of 307.6 °C. The colour depends on the viewing angle: by reflected light, the crystals appear dark green, but by transmitted light, they appear purple-red. Anhydrous iron(III) chloride has the BiI
3 structure, with octahedral Fe(III) centres interconnected by two-coordinate chloride ligands.[7][10]

Iron(III) chloride has a relatively low melting point and boils at around 315 °C. The vapor consists of the dimer Fe
2Cl
6 (like aluminium chloride) which increasingly dissociates into the monomeric FeCl
3 (with D3h point group molecular symmetry) at higher temperatures, in competition with its reversible decomposition to give iron(II) chloride and chlorine gas.[11]

الهيدرات

In addition to the anhydrous material, ferric chloride aggressively forms hydrates upon exposure to water, reflecting its Lewis acidity. Four of these hydrates have been crystallized and examined by X-ray crystallography. They all exhibit deliquesce and feature trans-[FeCl
2(H
2O)
4]+
 cations, with either chloride or [FeCl
4]−
 as the anions.[8]

  • dihydrate: FeCl
    3    ·2H2O     has the structural formula trans-[FeCl
    2    (H
    2    O)
    4    ][FeCl
    4    ]    .
  • FeCl
    3    ·2.5H2O     has the structural formula cis-[FeCl
    2    (H
    2    O)
    4    ][FeCl
    4    ]·H2O    .
  • FeCl
    3    ·3.5H2O     has the structural formula cis-[FeCl
    2    (H
    2    O)
    4    ][FeCl
    4    ]·3H2O    .
  • hexahydrate: FeCl
    3    ·6H2O     has the structural formula trans-[FeCl
    2    (H
    2    O)
    4    ]Cl·2H2O    .[12]

المحلول

 
A brown, acidic solution of iron(III) chloride.

Aqueous solutions of ferric chloride are characteristically yellow, in contrast to the pale pink solutions of [Fe(H
2O)
6]3+. Thus, the chloride ligand significantly influences the optical properties of the iron center. According to spectroscopic measurements, the main species in aqueous solutions of ferric chloride are the octahedral [FeCl
2(H
2O)
4]+
 (stereochemistry unspecified) and the tetrahedral [FeCl
4]−
.[8] The cationic aquo complex is strongly acidic:[13][8]

[FeCl
2(H
2O)
4)]+
 ⇌ [FeCl
2(OH)(H
2O)
3] + H+

Anhydrous iron(III) chloride dissolves in diethyl ether and tetrahydrofuran forming 1:2 adducts of the formula FeCl3(ether)2. In these complexes, the iron is pentacoordinate.[14]

التحضير

Several hundred thousand kilograms of anhydrous iron(III) chloride are produced annually. The principal method called direct chlorination, uses scrap iron as a precursor:[10]

2 Fe + 3 Cl
2 → 2 FeCl
3

The reaction is conducted at several hundred degrees such that the product is gaseous. Using excess chlorine guarantees that the intermediate ferrous chloride is converted to the ferric state.[10] A similar but laboratory-scale process also has been described.[15][16]

Solutions of iron(III) chloride are produced industrially both from iron and from ore, in a closed-loop process.[10]

  1. Dissolving iron ore in hydrochloric acid
    Fe
    3    O
    4     + 8 HCl → FeCl
    2     + 2 FeCl
    3     + 4 H
    2    O
  2. Oxidation of iron(II) chloride with chlorine
    2 FeCl
    2     + Cl
    2     → 2 FeCl
    3
  3. Oxidation of iron(II) chloride with oxygen and hydrochloric acid
    4 FeCl
    2     + O
    2     + 4 HCl → 4 FeCl
    3     + 2 H
    2    O

Heating hydrated iron(III) chloride does not yield anhydrous ferric chloride. Instead, the solid decomposes into hydrochloric acid and iron oxychloride. Hydrated iron(III) chloride can be converted to the anhydrous form by treatment with thionyl chloride.[17] Similarly, dehydration can be done with trimethylsilyl chloride:[18]

FeCl
3·6H2O + 12 (CH
3)
3SiCl → FeCl
3 + 6 ((CH
3)
3Si)
2O + 12 HCl

التفاعلات

The reactivity of ferric chloride reveals two trends: It is a Lewis acid and an oxidizing agent.


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تفاعلات أحماض لويس

Reactions of iron(III) chlorides reflect the description of iron(III) as oxophilic and a hard Lewis acid. The rapidity of these reactions is consistent with the lability of the ferric ion, reflecting its typical high-spin electronic configuration. Thus, oxalate salts react rapidly with aqueous iron(III) chloride to give [Fe(C
2O
4)
3]3−, known as ferrioxalate. Other carboxylate sources, e.g., citrate and tartrate, bind as well to give carboxylate complexes. The affinity of iron(III) for oxygen ligands was the basis of qualitative tests for phenols. Although superseded by spectroscopic methods, the ferric chloride test is a traditional colorimetric test.[19] The affinity of iron(III) for phenols is exploited in the Trinder spot test.

Myriad other manifestations of the oxophiliicty of iron(III) chloride are available. When heated with iron(III) oxide at 350 °C it reactions to give iron oxychloride:[20]

FeCl
3 + Fe
2O
3 → 3FeOCl

Alkali metal alkoxides react to give the iron(III) alkoxide complexes. These products have more complicated structures than anhydrous iron(III) chloride.[21][22] In the solid phase a variety of multinuclear complexes have been described for the nominal stoichiometric reaction between FeCl
3 and sodium ethoxide:

FeCl
3 + 3 CH
3CH
2ONa → "Fe(OCH
2CH
3)
3" + 3 NaCl

Iron(III) chloride forms a 1:2 adduct with Lewis bases such as triphenylphosphine oxide; e.g., FeCl
3(OP(C
6H
5)
3)
2. The related 1:2 complex FeCl
3(OEt
2)
2, where Et = C
2H
5), has been crystallized from ether solution.[14]

Iron(III) chloride also reacts with tetraethylammonium chloride to give the yellow salt of the tetrachloroferrate ion ((Et
4N)[FeCl
4]). Similarly combining FeCl3 with NaCl and KCl gives Na[FeCl
4] and K[FeCl
4], respectively.[23]

In addition to these simple stoichiometric reactions, the Lewis acidity of ferric chloride enables its use in a variety of acid-catalyzed reactions as described below in the section on organic chemistry.[10]

تفاعلات الاختزال

Iron(III) chloride is a oxidizing agent. A simple illustration is its tendency to release chlorine when heated above 160 °C:[16]

2FeCl
3 → 2FeCl
2 + Cl
2

It also serves as a one-electron oxidant illustrated by its reaction with copper(I) chloride to give copper(II) chloride and iron(II) chloride.

FeCl
3 + CuCl → FeCl
2 + CuCl
2

In a comproportionation reaction, iron(III) chloride reacts with iron powder to form iron(II) chloride:[10]

2 FeCl
3 + Fe → 3 FeCl
2

A traditional synthesis of anhydrous ferrous chloride is the reduction of FeCl3 with chlorobenzene:[24]

2 FeCl
3 + C
6H
5Cl → 2 FeCl
2 + C
6H
4Cl
2 + HCl

كيمياء الفلزات العضوية

The interaction of anhydrous iron(III) chloride with organolithium and organomagnesium compounds has been examined often. These studies are enabled because of the solubility of FeCl3 in ethereal solvents, which are compatible with the nucleophilic alkylating agents. Such studies may be relevant to the mechanism of FeCl3-catalyzed cross-coupling reactions.[25] The isolation of organoiron(III) intermediates requires low-temperature reactions, lest the [FeR4]- intermediates degrade. Using methylmagnesium bromide as the alkylation agent, salts of Fe(CH3)4]- have been isolated.[26] Illustrating the sensitivity of these reactions, methyl lithium LiCH
3 reacts with iron(III) chloride to give lithium tetrachloroferrate(II) Li
2[FeCl
4]:[27]

2 FeCl
3 + LiCH
3 → FeCl
2 + Li[FeCl
4] + 0.5 CH
3CH
3
Li[FeCl
4] + LiCH
3 → Li
2[FeCl
4] + 0.5 CH
3CH
3

To a significant extent, iron(III) acetylacetonate and related beta-diketonate complexes are more widely used than FeCl3 as ether-soluble sources of ferric ion.[28] These diketonate complexes have the advantages that they do not form hydrates, unlike iron(III) chloride, and they are more soluble in relevant solvents.[25] Cyclopentadienyl magnesium bromide undergoes a complex reaction with iron(III) chloride, resulting in ferrocene:[29]

3 C
5H
5MgBr + FeCl
3 → Fe(C
5H
5)
2 + 1/n (C
5H
5)
n + 3 MgBrCl

This conversion, although not of practical value, was important in the history of organometallic chemistry where ferrocene is emblematic of the field.[30]

الاستخدامات

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المعالجة المائية

In the largest application iron(III) chloride is used in sewage treatment and drinking water production as a coagulant and flocculant.[31] In this application, an aqueous solution of FeCl
3 is treated with base to form a floc of iron(III) hydroxide (Fe(OH)
3), also formulated as FeO(OH) (ferrihydrite). This floc facilitates the separation of suspended materials, clarifying the water.[10]

Iron(III) chloride is also used to remove soluble phosphate from wastewater. Iron(III) phosphate is insoluble and thus precipitates as a solid.[32] One potential advantage to its use in water treatment, ferric ion oxidizes (deodorizes) hydrogen sulfide.[33]

النقش وتنظيم المعدن

It is also used as a leaching agent in chloride hydrometallurgy,[34] for example in the production of Si from FeSi (Silgrain process by Elkem).[35]

In another commercial application, a solution of iron(III) chloride is useful for etching copper according to the following equation:

2 FeCl
3 + Cu → 2 FeCl
2 + CuCl
2

The soluble copper(II) chloride is rinsed away, leaving a copper pattern. This chemistry is used in the production of printed circuit boards (PCB).[9]

Iron(III) chloride is used in many other hobbies involving metallic objects.[36][37][38][39][40]

الكيمياء العضوية

 
Structure of FeCl3(diethylether)2. Color code: Cl=green,Fe = blue, O = red.

In industry, iron(III) chloride is used as a catalyst for the reaction of ethylene with chlorine, forming ethylene dichloride (1,2-dichloroethane):[41]

H
2C=CH
2 + Cl
2 → ClCH
2CH
2Cl

Ethylene dichloride is a commodity chemical, which is mainly used for the industrial production of vinyl chloride, the monomer for making PVC.

Several reagents for organic synthesis have been developed based especially on anhydrous iron(III) chloride:

As a reagent in organic chemistry, iron(III) chloride has attracted interest for both its redox activity and its Lewis acidity. Furthermore, because they are inexpensive and relatively nontoxic, iron chlorides have been widely examined.[28] Illustrating it use as a Lewis acid, iron(III) chloride catalyses electrophilic aromatic substitution and chlorinations. In this role, its function is similar to that of aluminium chloride. In some cases, mixtures of the two are used.[46] Iron(III) chloride oxidizes naphthols to naphthoquinones:[28][47]

 

علم الأنسجة

Iron(III) chloride is a component of useful stains, such as Carnoy's solution, a histological fixative with many applications. Also, it is used to prepare Verhoeff's stain.[48]

السلامة

Anhydrous iron(III) chloride is harmful, highly corrosive, and acidic.[28] Soluble iron(III) salts irritate the eyes, skin, mucous membrane, and induce abdominal pain, diarrhea, and vomiting when ingested.[49]

التواجد الطبيعي

FeCl
3 naturally occurs as the rare mineral molysite, usually related to volcanic and other-type fumaroles.[50][51]

FeCl
3 is also produced as an atmospheric salt aerosol by a reaction between iron-rich dust and hydrochloric acid from sea salt. This iron salt aerosol causes about 5% of naturally-occurring oxidization of methane and is thought to have a range of cooling effects.[52]

The clouds of Venus are hypothesized to contain approximately 1% FeCl
3 dissolved in sulfuric acid.[53][54]

ملاحظات

  1. ^ An alternative GHS classification from the Japanese GHS Inter-ministerial Committee (2006)[6] notes the possibility of respiratory tract irritation from FeCl
    3     and differs slightly in other respects from the classification used here.

المراجع

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للاستزادة

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