شبه فلز
أشباه الفلزات (الأصل الإغريقي للكلمة يعنى شبيه الفلز) مثل الفلزات واللافلزات هي إحدى السلاسل الكيميائية، وتتميز بخصائص معينة من ناحية التأين والترابط. تتميز أشباه الفلزات بخصائص متوسطة بين الفلزات واللا فلزات، ولا توجد طريقة محددة للتفريق بين أشباه الفلزات والفلزات الحقيقية، ولكنها عمومًا تكون شبه موصلة أكثر من كونها عازلة.
تقع أشباه الفلزات في الجدول الدوري على هيئة خط مائل من البورون إلى البولونيوم وتكون العناصر الموجودة في أعلى يسار الخط هي الفلزات، بينما تقع العناصر الموجودة أسفل يمين الخط ضمن اللافلزات.
لا تقتصر أشباه الفلزات فقط على هذه العناصر ولكنها توجد أيضًا في السبائك والمركبات .
التعريفات
التعريف القائم على الحكم
المادة الفوقية هي عنصر له خصائص في الوسط، أو خليط من المعادن واللافلزات، والتي يصعب تصنيفها إما كمعدن أو مادة غير معدنية. يعتمد هذا التعريف عام على الصفات الفاصلة التي يتم الاستشهاد بها باستمرار في المؤلفات العلمية.[n 1] تُعتبر صعوبة التصنيف سمة رئيسية في تلك الموادّ. تحتوي معظم العناصر على مزيج من الخواص المعدنية وغير المعدنية،[7] ويمكن تصنيفها وفقًا لمجموعة الخصائص التي تكون أكثر وضوحًا.[7][n 2] تفتقر العناصر الموجودة في الهوامش أو بالقرب منها إلى غموض واضح بدرجة كافية لتحديد خصائصها المعدنية أو غير المعدنية ، وتُصنف على أنها أشباه فلزات.[7]
يتم التعرف على البورون والسيليكون والجرمانيوم والزرنيخ والإثمد والتيلوريوم بشكل شائع كأشباه فلزات.[11][n 3] يُضاف في بعض الأحيان واحدٌ أو أكثر من السيلنيوم أو البولونيوم أو الأستاتين إلى القائمة باختلاف العالم المؤلف للمرجع العلمي.[11] قد يُستبعد البورون في بعض الأحيان بمفرده في أو يُستبعد معه السيليكون.[13] لا يُعتبر التيلوريوم ضمن قائمة أشباه الفلزات في بعض الأحيان أيضًا.[11] كما تم التشكيك في إدراج الأنتيمون، والبولونيوم، والأستاتين ضمن أشباه الفلزانالميتالويدات.[7]
يتم تصنيف العناصر الأخرى في بعض الأحيان على أنها أشباه فلزات. تشمل هذه العناصر[14] الهيدروجين،[11] والبريليوم،[7] والنيتروجين،[7] والفسفور،[11] والكبريت،[11] والزنك،[7] والغاليوم،[7] والقصدير، واليود،[13] والرصاص،[7] والبزموت، والرادون.[11] كما يُستخدم مصطلح أشباه الفلزات للعناصر التي تُظهر بريق معدني وموصلية كهربائية، وهي العناصر المترددة، مثل الزرنيخ والأنتيمون والفاناديوم والكروم والموليبدنوم والتنغستن والقصدير والرصاص والألمنيوم.[13] تُعتبر الفلزات بعد الانتقالية (مثل الكربون أو النيتروجين) التي يمكن أن تشكل سبائك بالمعادن[7] أو تُعدّل خصائصها[7] في بعض الأحيان كأنواع من أشباه الفلزات.
التعريف القائم على المعايير
لا يوجد تعريف مقبول على نطاق واسع لأشباه الفلزات، ولا يوجد أي تقسيم للجدول الدوري إلى المعادن والفلزات واللافلزات؛[13] تساءل هوكس[7] عن جدوى وضع تعريف محدد، مشيرًا إلى أنه يمكن العثور على حالات شاذة في عدة محاولات. ووصفت شارب[7] تصنيف عنصر على أنه شيء "تعسفي".
تعتمد خصائص أشباه الفلزات على معايير التصنيف المستخدمة.[7] اعترف ايمسلي بأربعة أنواع من أشباه الفلزات (الجرمانيوم والزرنيخ والأنتيمون والتيلوريوم)، وصنّف جيمس وآخرون[7] اثنا عشر عنصرًا ( الأربعة الذين اعترف بهم ايمسلي بالإضافة إلى البورون، والكربون، والسيليكون، والسيلينيوم، والبزموت، والبولونيوم، والموسكوفيوم والليفرموريوم. يتم تضمين سبعة عناصر في المتوسط ضمن هذه القوائم؛ كما تميل ترتيبات التصنيف الفردية إلى مشاركة أرضية مشتركة وتختلف في الهوامش غير المحددة.[15][n 4][n 5]
يشيع استخدام معيار كمي واحد مثل الكهرسلبية،[7] تتمتع أشباه الفلزات بقيم كهرومغناطيسية تتراوح من 1.8 أو 1.9 إلى 2.2.[13] تشمل الأمثلة الأخرى كفاءة التعبئة (جزء الحجم في البنية البلورية التي تشغلها الذرات) ومعيار نسبة جولدهامر-هيرتسفيلد.[7] تحتوي أشباه الفلزات المعروفة بشكل عام على كفاءة التعبئة تتراوح بين 34٪ و 41٪.[n 6] وتساوي نسبة جولدهامر-هرتسفيلد تقريبًا مكعب نصف القطر الذري مقسومًا على الحجم المولي،[n 7] وتُعتبر مقياس بسيط لكيفية وجود عنصر معدني، وتتمتع أشباه الفلزات الُمعترف بها وجود نسب من حوالي 0.85 إلى 1.1 ومتوسط 1.0.[7][n 8] اعتمد المؤلفون الآخرون عل معايير أخرى مثل السلوك الذري[n 9] أو العدد التناسقي.[25]
كتب جونز عن دور التصنيف في العلوم، ولاحظ أن "(التصانيف) عادةً ما يتم تحديدها بأكثر من سمتين".[7] استخدم ماسترتون وسولينسكي[26] ثلاثة معايير لوصف العناصر الستة المعترف بها بشكل شائع كأشباه للفلزات: فأشباه الفلزات لها طاقات تأين تساوي حوالي 200 كيلوكالوري / مول (837 كيلوجول / مول) وقيم تيار كهربية قريبة من 2.0. كما قالوا أن أشباه الفلزات تُعتبر أشباه موصلات بشكل نموذجي، على الرغم من أن الأنتيمون والزرنيخ (شبه الجسيم من منظور فيزياء) لهما توصيلات كهربائية تقترب من المعادن. ويُعتقد في أن السلينيوم والبولونيوم لا يندرجا في هذا التصنيف، في حين تظل حالة الأستاتين غير مؤكدة.[n 10]
الاستخدامات الشائعة
تكون الفلزات هشة للغاية بحيث لا توجد استخدامات هيكلية لها في أشكالها النقية.[13] وتستخدم هذه المركبات ومكوناتها كمكونات للسبائك، والعوامل البيولوجية (المٌبيدة والغذائية والطبية)، والمُحفزات، ومثبطات اللهب، والنظارات، ووسائط التخزين البصرية والإلكترونيات البصرية، والألعاب النارية، وأشباه الموصلات والإلكترونيات.[n 11]
السبائك
لاحظ عالم المعادن البريطاني سيسيل ديش في كتابة في وقت مبكر من تاريخ المركبات بين الفلزية، أن "بعض العناصر غير المعدنية قادرة على تشكيل مركبات ذات طبيعة معدنية مميزة بالمعادن، وبالتالي قد تدخل هذه العناصر في تكوين السبائك ". ارتبط السيليكون والزرنيخ والتيلوريوم، على وجه الخصوص، مع العناصر المكونة للسبيكة.[7] اقترح فيليبس وويليامز[7] أن مركبات السيليكون والجرمانيوم والزرنيخ والأنتيمون مع الفلزات بعد الانتقالية "من المحتمل أن تصنف على أنها سبائك".
ومن بين المركبات الفلزّية الخفيفة، تكون السبائك التي تحتوي على فلزات انتقالية ممثلة تمثيلاً جيدًا. يمكن أن يشكل البورون مركبات السبائك وسبائك مع هذه المعادن ، إذا كانت n> 2.[7] يستخدم الفيروبورن ( المُحتوي على 15 ٪ من البورون) لإدخال البورون إلى سبائك الصلب؛ وتدخل سبائك النيكل والبورون في مكونات سبائك اللحام وتركيبات الصناعات الهندسية. تستخدم سبائك السيليكون مع الحديد والألومنيوم على نطاق واسع في صناعات الصلب والسيارات، على التوالي. كما يشكل الجرمانيوم العديد من السبائك، وتُعتبر سبائكه مع عناصر المجموعة الحادية عشرة الأكثر أهمية.[7]
تستخدم أشباه الفلزات الأثقل في صُنع السبائك أيضًا. يمكن للزرنيخ أن يشكل سبائك مع المعادن، بما في ذلك البلاتين والنحاس؛[7] كما يُضاف إلى النحاس وسبائكه لتحسين مقاومة التآكل[7] ويبدو أنه يمنح نفس الفائدة عند إضافته إلى الماغنيسيوم.[7] يشتهر الإثمد بأنه سبيكة ممتازة في الصناعات ، بما في ذلك مع معادن العملات. وتشتمل سبائكه على البيوتر (بيوتر) (وهي سبيكة من القصدير مع ما يصل إلى 20٪ من الإثمد) ونوع معدني (سبيكة رصاص بها ما يصل إلى 25٪ من الإثمد).[7] يُشكل التيلوريوم بسهولة سبائك مع الحديد، مثل سبائك القيروتيليريوم (تحتوي على 50-58 ٪ التيلوريوم)، والنحاس، في شكل سبائك التيلوريوم النحاس (تحتوي على 40-50 ٪ التيلوريوم).[7] يستخدم الفيروتيليريوم كمثبت للكربون في صب الصلب.[7] من العناصر غير المعدنية التي غالبًا ما يتم التعرف عليها غالبًا على أنها من مركبات أشباه الفلزات، يُستخدم السيلينيوم في شكل الفيروزيلنيوم (50-58٪ من السيلينيوم) - لتحسين قابلية استخدام الصلب المقاوم للصدأ.[13]
ملاحظات
- Definitions and extracts by different authors, illustrating aspects of the generic definition, follow:
- "In chemistry a metalloid is an element with properties intermediate between those of metals and nonmetals."[1]
- "Between the metals and nonmetals in the periodic table we find elements ... [that] share some of the characteristic properties of both the metals and nonmetals, making it difficult to place them in either of these two main categories"[2]
- "Chemists sometimes use the name metalloid ... for these elements which are difficult to classify one way or the other."[3]
- "Because the traits distinguishing metals and nonmetals are qualitative in nature, some elements do not fall unambiguously in either category. These elements ... are called metalloids ..."[4]
- ذهب, for example, has mixed properties but is still recognised as "king of metals". Besides metallic behaviour (such as high electrical conductivity, and أيون formation), gold shows nonmetallic behaviour:
- It has the highest electrode potential
- It has the third-highest طاقة تأين among the metals (after زنك and زئبق)
- It has the lowest ألفة إلكترونية
- Its كهرسلبية of 2.54 is highest among the metals and exceeds that of some nonmetals (هيدروجين 2.2; فسفور 2.19; and رادون 2.2)
- It forms the Au− auride أيون, acting in this way like a هالوجين
- It sometimes has a tendency, known as "محب للذهب", to bond to itself;[8]
- Mann et al.[12] refer to these elements as "the recognized metalloids".
- Jones[16] writes: "Though classification is an essential feature in all branches of science, there are always hard cases at the boundaries. Indeed, the boundary of a class is rarely sharp."
- The lack of a standard division of the elements into metals, metalloids and nonmetals is not necessarily an issue. There is more or less, a continuous progression from the metallic to the nonmetallic. Potentially, a specified subset of this continuum can serve its particular purpose as well as any other.[17]
- The packing efficiency of boron is 38%; silicon and germanium 34; arsenic 38.5; antimony 41; and tellurium 36.4.[18] These values are lower than in most metals (80% of which have a packing efficiency of at least 68%),[19] but higher than those of elements usually classified as nonmetals. (Gallium is unusual, for a metal, in having a packing efficiency of just 39%.[20] Other notable values for metals are 42.9 for bismuth[21] and 58.5 for liquid mercury.[22]) Packing efficiencies for nonmetals are: graphite 17%,[23] sulfur 19.2,[24] iodine 23.9,[24] selenium 24.2,[24] and black phosphorus 28.5.[21]
- Atomic conductance is the electrical conductivity of one mole of a substance. It is equal to electrical conductivity divided by molar volume.[3]
- Selenium has an ionization energy (IE) of 225 kcal/mol (941 kJ/mol) and is sometimes described as a semiconductor. It has a relatively high 2.55 electronegativity (EN). Polonium has an IE of 194 kcal/mol (812 kJ/mol) and a 2.0 EN, but has a metallic band structure.[27] Astatine has an IE of 215 kJ/mol (899 kJ/mol) and an EN of 2.2.[28] Its electronic band structure is not known with any certainty.
- Olmsted and Williams[29] commented that, "Until quite recently, chemical interest in the metalloids consisted mainly of isolated curiosities, such as the poisonous nature of arsenic and the mildly therapeutic value of borax. With the development of metalloid semiconductors, however, these elements have become among the most intensely studied".
مراجع
- Cusack 1987, p. 360
- Kelter, Mosher & Scott 2009, p. 268
- Hill & Holman 2000, p. 41
- King 1979, p. 13
- Moore 2011, p. 81
- Gray 2010
- شبه فلز
- Wiberg 2001, p. 1279 "نسخة مؤرشفة". Archived from the original on 8 مايو 2020. اطلع عليه بتاريخ 20 يوليو 2018. الوسيط
|CitationClass=
تم تجاهله (مساعدة)صيانة CS1: BOT: original-url status unknown (link) - Belpassi et al. 2006, pp. 4543–4
- Schmidbaur & Schier 2008, pp. 1931–51
- شبه فلز; شبه فلز; شبه فلز
- Mann et al. 2000, p. 2783
- شبه فلز; شبه فلز
- شبه فلز. Dunstan lists Be, Al, Ge (maybe), As, Se (maybe), Sn, Sb, Te, Pb, Bi, and Po as metalloids (pp. 310, 323, 409, 419).
- شبه فلز "The boundary between metals and metalloids is indefinite ..."; شبه فلز: "Although the elements are conveniently described as metals, metalloids, and nonmetals, the transitions are not exact ..."
- Jones 2010, p. 170
- Kneen, Rogers & Simpson 1972, pp. 218–220
- Van Setten et al. 2007, pp. 2460–1; Russell & Lee 2005, p. 7 (Si, Ge); Pearson 1972, p. 264 (As, Sb, Te; also black P)
- Russell & Lee 2005, p. 1
- Russell & Lee 2005, pp. 6–7, 387
- Pearson 1972, p. 264
- Okajima & Shomoji 1972, p. 258
- Kitaĭgorodskiĭ 1961, p. 108
- Neuburger 1936
- شبه فلز: "One criterion for distinguishing semi-metals from true metals under normal conditions is that the عدد تناسقي of the former is never greater than eight, while for metals it is usually twelve (or more, if for the body-centred cubic structure one counts next-nearest neighbours as well)."
- شبه فلز list B, Si, Ge, As, Sb and Te as metalloids, and comment that Po and At are ordinarily classified as metalloids but add that this is arbitrary as so little is known about them.
- Kraig, Roundy & Cohen 2004, p. 412; Alloul 2010, p. 83
- Vernon 2013, pp. 1704
- Olmsted & Williams 1997, p. 975
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