أحادي كبريتيد النحاس

(تم التحويل من Copper monosulfide)
أحادي كبريتيد النحاس
Sulfid měďnatý.PNG
الأسماء
اسم أيوپاك
Copper sulfide
أسماء أخرى
المُعرِّفات
رقم CAS
3D model (JSmol)
ChemSpider
رقم EC
  • 215-271-2
رقم RTECS
  • GL8912000
UNII
الخصائص
الصيغة الجزيئية CuS
كتلة مولية 95.611 g/mol
المظهر black powder or lumps
الكثافة 4.76 g/cm3
نقطة الانصهار
قابلية الذوبان في الماء 3.3×10−5 g/100 ml (18 °C)[بحاجة لمصدر]
نتاج قابلية الذوبان، Ksp 5×10−37[1]قالب:Quotation needed
قابلية الذوبان في nitric acid soluble[بحاجة لمصدر][كمية]
قابلية الذوبان في ammonium hydroxide soluble[بحاجة لمصدر][كمية]
القابلية المغناطيسية −2.0×10−6 cm3/mol
معامل الانكسار (nD) 1.45
البنية
البنية البلورية hexagonal
المخاطر
ن.م.ع. مخطط تصويري رمز البيئة في النظام المنسق عالمياً لتصنيف وعنونة الكيماويات (GHS)
H413
P273, P501
حدود التعرض الصحية بالولايات المتحدة (NIOSH):[2]
PEL (المسموح)
 TWA 1 mg/m3 (as Cu)
REL (الموصى به)
 TWA 1 mg/m3 (as Cu)
IDLH (خطر عاجل)
 TWA 100 mg/m3 (as Cu)
مركبات ذا علاقة
Copper(II) oxide
zinc sulfide
ما لم يُذكر غير ذلك، البيانات المعطاة للمواد في حالاتهم العيارية (عند 25 °س [77 °ف]، 100 kPa).
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مراجع الجدول

Copper monosulfide is a chemical compound of copper and sulfur. It was initially thought to occur in nature as the dark indigo blue mineral covellite. However, it was later shown to be a cuprous compound, formula Cu
3S(S
2).[3][مطلوب توضيح] CuS is a moderate conductor of electricity.[4][صفحة مطلوبة] A black colloidal precipitate of CuS is formed when hydrogen sulfide, H
2S, is bubbled through solutions of Cu(II) salts.[5][صفحة مطلوبة] It is one of a number of binary compounds of copper and sulfur (see copper sulfide for an overview of this subject), and has attracted interest because of its potential uses in catalysis[6] and photovoltaics.[7]

التصنيع

Copper monosulfide can be prepared by passing hydrogen sulfide gas into a solution of copper(II) salt.

Alternatively, it can be prepared by melting an excess of sulfur with copper(I) sulfide or by precipitation with hydrogen sulfide from a solution of anhydrous copper(II) chloride in anhydrous ethanol.

The reaction of copper with molten sulfur followed by boiling sodium hydroxide and the reaction of sodium sulfide with aqueous copper sulfate will also produce copper sulfide.

CuS structure and bonding

Copper sulfide crystallizes in the hexagonal crystal system, and this is the form of the mineral covellite. There is also an amorphous high pressure form[8] which on the basis of the Raman spectrum has been described as having a distorted covellite structure. An amorphous room temperature semiconducting form produced by the reaction of a Cu(II) ethylenediamine complex with thiourea has been reported, which transforms to the crystalline covellite form at 30 °C (86 °F).[9]
The crystal structure of covellite has been reported several times,[10][11][12] and whilst these studies are in general agreement on assigning the space group P63/mmc there are small discrepancies in bond lengths and angles between them. The structure was described as "extraordinary" by Wells[13][صفحة مطلوبة] and is quite different from Copper(II) oxide, but similar to Copper(II) selenide (or referred to as Klockmannite). The covellite unit cell contains 6 formula units (12 atoms) in which:

  • 4 Cu atoms have tetrahedral coordination (see illustration).
  • 2 Cu atoms have trigonal planar coordination (see illustration).
  • 2 pairs of S atoms are only 207.1 picometers apart[12] indicating the existence of an S-S bond (a disulfide unit).
  • the 2 remaining S atoms form trigonal planar triangles around the copper atoms, and are surrounded by five Cu atoms in a pentagonal bipyramid (see illustration).
  • The S atoms at each end of a disulfide unit are tetrahedrally coordinated to 3 tetrahedrally coordinated Cu atoms and the other S atom in the disulfide unit (see illustration).

The formulation of copper sulfide as CuII
S (i.e. containing no sulfur-sulfur bond) is clearly incompatible with the crystal structure, and also at variance with the observed diamagnetism[14][صفحة مطلوبة] as a Cu(II) compound would have a d9 configuration and be expected to be paramagnetic.[5][صفحة مطلوبة]

Studies using XPS[15][16][17][18] indicate that all of the copper atoms have an oxidation state of +1. This contradicts a formulation based on the crystal structure and obeying the octet rule that is found in many textbooks (e.g.[5][صفحة مطلوبة][19][صفحة مطلوبة]) describing CuS as containing both CuI
 and CuII
 i.e. (Cu+
)
2Cu2+(S
2)2−S2−. An alternative formulation as (Cu+
)
3(S2−)(S
2)−
 was proposed and supported by calculations. The formulation should not be interpreted as containing radical anion, but rather that there is a delocalized valence "hole".[3][20] Electron paramagnetic resonance studies on the precipitation of Cu(II) salts indicates that the reduction of Cu(II) to Cu(I) occurs in solution.[21]

Covellite-xtal-CM-3D-balls.png

Covellite-Cu1-coordination-3D-balls.png Covellite-Cu2-coordination-3D-balls.png Covellite-S1-coordination-3D-balls.png Covellite-S2-coordination-3D-balls.png
ball-and-stick model of part of
the crystal structure of covellite		 trigonal planar
coordination of copper		 tetrahedral
coordination of copper		 trigonal bipyramidal
coordination of sulfur		 tetrahedral
coordination of sulfur-note[مطلوب توضيح] disulfide unit

انظر أيضاً

المراجع

  1. ^ Rollie J. Myers (1986). "The new low value for the second dissociation constant for H2S: Its history, its best value, and its impact on the teaching of sulfide equilibria". J. Chem. Educ. 63 (8): 687. Bibcode:1986JChEd..63..687M. doi:10.1021/ed063p687.
  2. ^ "NIOSH Pocket Guide to Chemical Hazards".
  3. ^ أ ب Liang, W.; Whangbo, M.-H. (February 1993). "Conductivity anisotropy and structural phase transition in Covellite CuS". Solid State Communications. 85 (5): 405–408. Bibcode:1993SSCom..85..405L. doi:10.1016/0038-1098(93)90689-K.
  4. ^ Wells, A. F. (1962). Structural Inorganic Chemistry (3rd ed.). Oxford University Press. ISBN 0198553218.
  5. ^ أ ب ت Greenwood, N. N. (1997). Chemistry of the Elements (2nd Edition ed.). Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4. {{cite book}}: |edition= has extra text (help); Unknown parameter |coauthors= ignored (|author= suggested) (help)
  6. ^ Kuchmii, S.Y.; Korzhak A.V.; Raevskaya A.E.; Kryukov A.I. (2001). "Catalysis of the Sodium Sulfide Reduction of Methylviologene by CuS Nanoparticles". Theoretical and Experimental Chemistry. New York: Springer. 37 (1): 36–41. doi:10.1023/A:1010465823376. S2CID 91893521.
  7. ^ Mane, R.S.; Lokhande C.D. (June 2000). "Chemical deposition method for metal chalcogenide thin films". Materials Chemistry and Physics. 65 (1): 1–31. doi:10.1016/S0254-0584(00)00217-0.
  8. ^ Peiris, M; Sweeney, J.S.; Campbell, A.J.; Heinz D. L. (1996). "Pressure-induced amorphization of covellite, CuS". J. Chem. Phys. 104 (1): 11–16. Bibcode:1996JChPh.104...11P. doi:10.1063/1.470870.
  9. ^ Grijalva, H.; Inoue, M.; Boggavarapu, S.; Calvert, P. (1996). "Amorphous and crystalline copper sulfides, CuS". J. Mater. Chem. 6 (7): 1157–1160. doi:10.1039/JM9960601157.
  10. ^ Oftedal, I. (1932). "Die Kristallstruktur des Covellins (CuS)". Z. Kristallogr. 83 (1–6): 9–25. doi:10.1524/zkri.1932.83.1.9. S2CID 101164006.
  11. ^ Berry, L. G. (1954). "The crystal structure of covellite CuS and klockmannite CuSe". American Mineralogist. 39: 504.
  12. ^ أ ب Evans, H.T. Jr.; Konnert J. (1976). "Crystal structure refinement of covellite". American Mineralogist. 61: 996–1000.
  13. ^ Wells, A. F. (1984). Structural inorganic chemistry (5th ed.). Oxford [Oxfordshire] : New York: Clarendon Press ; Oxford University Press. ISBN 0-19-855370-6.
  14. ^ Magnetic susceptibility of the elements and inorganic compounds Archived 2012-01-12 at the Wayback Machine
  15. ^ Nakai, I.; Sugitani, Y.; Nagashima, K.; Niwa, Y. (1978). "X-ray photoelectron spectroscopic study of copper minerals". Journal of Inorganic and Nuclear Chemistry. 40 (5): 789–791. doi:10.1016/0022-1902(78)80152-3.
  16. ^ Folmer, J.C.W.; Jellinek F. (1980). "The valence of copper in sulfides and selenides: An X-ray photoelectron spectroscopy study". Journal of the Less Common Metals. 76 (1–2): 789–791. doi:10.1016/0022-5088(80)90019-3.
  17. ^ Folmer, J.C.W.; Jellinek F.; Calis G.H.M (1988). "The electronic structure of pyrites, particularly CuS2 and Fe1−xCuxSe2: An XPS and Mössbauer study". Journal of Solid State Chemistry. 72 (1): 137–144. Bibcode:1988JSSCh..72..137F. doi:10.1016/0022-4596(88)90017-5.
  18. ^ Goh, S.W.; Buckley A.N.; Lamb R.N. (February 2006). "Copper(II) sulfide?". Minerals Engineering. 19 (2): 204–208. Bibcode:2006MiEng..19..204G. doi:10.1016/j.mineng.2005.09.003.
  19. ^ قالب:Cotton&Wilkinson6th
  20. ^ Nozaki, H; Shibata, K; Ohhashi,N. (April 1991). "Metallic hole conduction in CuS". Journal of Solid State Chemistry. 91 (2): 306–311. Bibcode:1991JSSCh..91..306N. doi:10.1016/0022-4596(91)90085-V.
  21. ^ Luther, GW; Theberge SM; Rozan TF; Rickard D; Rowlands CC; Oldroyd A. (February 2002). "Aqueous copper sulfide clusters as intermediates during copper sulfide formation". Environ. Sci. Technol. 36 (3): 394–402. Bibcode:2002EnST...36..394L. doi:10.1021/es010906k. PMID 11871554.

قالب:Disulfides

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