أوروبيوم

Europium, ₀₀Eu

Europium
المظهر	silvery white, with a pale yellow tint; but rarely seen without oxide discoloration
الوزن الذري العياري Ar°(Eu)
Europium في الجدول الدوري
– ↑ Eu ↓ Am samarium ← europium → gadolinium
الرقم الذري (Z)	63
المجموعة	n/a
الدورة	period 6
المستوى الفرعي	f-block
التوزيع الإلكتروني	[Xe] 4f7 6s2
الإلكترونات بالغلاف	2, 8, 18, 25, 8, 2
الخصائص الطبيعية
الطور at د.ح.ض.ق	solid
نقطة الانصهار	1099 K ​(826 °س، ​1519 °F)
نقطة الغليان	1802 K ​(1529 °س، ​2784 °ف)
الكثافة (بالقرب من د.ح.غ.)	5.244 ج/سم³
حين يكون سائلاً (عند ن.إ.)	5.13 ج/سم³
حرارة الانصهار	9.21 kJ/mol
حرارة التبخر	176 kJ/mol
السعة الحرارية المولية	27.66 J/(mol·K)
ضغط البخار P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 863 957 1072 1234 1452 1796
الخصائص الذرية
الكهرسلبية	مقياس پاولنگ: 1.2
طاقات التأين	الأول: 547.1 kJ/mol الثاني: 1085 kJ/mol الثالث: 2404 kJ/mol
نصف القطر الذري	empirical: 180 pm
نصف قطر التكافؤ	198±6 pm
الخطوط الطيفية
خصائص أخرى
البنية البلورية	​body-centered cubic (bcc)
سرعة الصوت قضيب رفيع	est. 13.9 W/(m·K)
التمدد الحراري	poly: 35.0 µm/(m⋅K) (at r.t.)
المقاومة الكهربائية	poly: 0.900 µΩ⋅m (at r.t.)
الترتيب المغناطيسي	paramagnetic
القابلية المغناطيسية	+34000.0×10−6 cm3/mol
معامل يونگ	18.2 GPa
معامل القص	7.9 GPa
معاير الحجم	8.3 GPa
نسبة پواسون	0.152
صلادة ڤيكرز	165–200 MPa
رقم كاس	7440-53-1
التاريخ
التسمية	after Europe
الاكتشاف وأول عزل	Eugène-Anatole Demarçay (1896, 1901)
نظائر الeuropium

يروپيوم أو أوروپيوم أو اليوروپيوم Europium هو عنصر كيميائي رمزه Eu ورقمه الذري 63. وسـُمي على اسم قارة اوروپا.

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 الخصائص المميزة

الاوروپيوم هو أكثر العناصر الأرضية النادرة تفاعلاً; فهو يتأكسد بسرعة في الهواء, ويشبه الكالسيوم في تفاعله مع الماء; وشحنات العنصر الفلزي في صيغة صلبة, حتى عند تغطيتها بطبقة واقية من الزيت المعدني, فهي نادراً ما تكون براقة. ويشتعل الالاوروپيوم في الهواء عند درجة حرارة 150 °م إلى 180 °م. وله تقريباً نفس صلادة الرصاص وهو مطيل بدرجة كبيرة.

 الاستخدامات

هناك القليل من الاستخدامات التجارية لفلز الالاوروپيوم, إلا أنه قد استـُعمل to dope بعض أنواع الزجاج لصناعة ليزرات, كما يـُستخدم في الكشف عن متلازمة داون وبعض الأمراض الجينية الأخرى. وبسبب قدرته على امتصاص النيوترونات, فيجري دراسة استخدامه في المفاعلات النووية. اكسيد الالاوروپيوم (Eu₂O₃) يـُستعمل على نطاق واسع كفوسفور أحمر في أجهزة التلفزيون و مصابيح الفلوسنت, وكمنشط للفوسفورات المصنوعة من الإتريوم. وبينما الاوروپيوم ثلاثي التكافؤ يعطي فوسفورات حمراء, فالاوروپيوم ثنائي التكافؤ يعطي فوسفورات زرقاء. مجموعتا فوسفور الاوروبيوم, مجموعتان مع فوسفورات التربيوم الصفراء/الخضراء, يعطون أضواءً "ثلاثية الألوان trichromatic" وهي التي أصبحت هامة جداً للحصول على إضاءة اقتصادية. ويـُستخدم أيضاً كعامل في صناعة زجاج الفلورسنت. ويستخدم استشعاع الاوروپيوم لفحص التفاعلات الجزيئية الحيوية في غرابيل اكتشاف العقاقير. ويستخدم كذلك في فوسفورات مكافحة التزوير في الأوراق النقدية لليورو.

ويستخدم الاوروپيوم بنسب ضئيلة جداً في دراسات الكيمياء الأرضية و الپترولوجيا فهم العمليات المكونة للصخور النارية (الصخور التي بردت من magma أو الحمم). وطبيعة europium anomaly found تستخدم للمساعدة في اعادة بناء العلاقات داخل مجموعة من الصخور النارية.

 التاريخ

Europium was first found by Paul Émile Lecoq de Boisbaudran in 1890, who obtained basic fraction from samarium-gadolinium concentrates which had spectral lines not accounted for by samarium or gadolinium; however, the discovery of europium is generally credited to French chemist Eugène-Anatole Demarçay, who suspected samples of the recently discovered element samarium were contaminated with an unknown element in 1896 and who was able to isolate europium in 1901. When the europium-doped yttrium orthovanadate red phosphor was discovered in the early 1960s, and understood to be about to cause a revolution in the color television industry, there was a mad scramble for the limited supply of europium on hand among the monazite processors. (Typical europium content in monazite was about 0.05%.) Luckily, Molycorp, with its bastnäsite deposit at Mountain Pass California, whose lanthanides had an unusually "rich" europium content of 0.1%, was about to come on-line and provide sufficient europium to sustain the industry. Prior to europium, the color-TV red phosphor was very weak, and the other phosphor colors had to be muted, to maintain color balance. With the brilliant red europium phosphor, it was no longer necessary to mute the other colors, and a much brighter color TV picture was the result. Europium has continued in use in the TV industry ever since, and, of course, also in computer monitors. California bastnäsite now faces stiff competition from Bayan Obo, China, with an even "richer" europium content of 0.2%. Frank Spedding, celebrated for his development of the ion-exchange technology that revolutionized the rare earth industry in the mid-1950s once related the story of how, in the 1930s, he was lecturing on the rare earths when an elderly gentleman approached him with an offer of a gift of several pounds of europium oxide. This was an unheard-of quantity at the time, and Spedding did not take the man seriously. However, a package duly arrived in the mail, containing several pounds of genuine europium oxide. The elderly gentleman had turned out to be the Dr. McCoy who had developed a famous method of europium purification involving redox chemistry.

 التواجد

ولا يتواجد الاوروپيوم في الطبيعة كعنصر حر; إلا أن هناك العديد من المعادن التي تحتوي على الاوروپيوم, وأهم المصادر هي باستناسيت و مونازيت. Europium has also been identified in the spectra of the sun and certain stars. Depletion or enrichment of europium in minerals relative to other rare earth elements is known as the europium anomaly.

الاوروپيوم ثنائي التكافؤ بكميات صغيرة وُجد أنه المنشط للاستشعاع الأزرق الساطع لبعض العينات من فلوريتات المعادن (ثنائي فلوريد الكالسيوم). The most outstanding examples of this originated around Weardale, and adjacent parts of northern England, and indeed it was this fluorite that gave its name to the phenomenon of fluorescence, although it was not until much later that europium was discovered or determined to be the cause.

 المركبات

مركبات الاوروپيوم تتضمن:

• فلوريدات: EuF₂ EuF₃
• كلوريدات: EuCl₂ EuCl₃
• بروميدات: EuBr₂ EuBr₃
• يوديدات: EuI₂ EuI₃
• اكسيدات: EuO Eu₂O₃ Eu₃O₄
• كبريتيدات: EuS
• سلنيدات: EuSe
• تليوريدات: EuTe
• نيتريدات: EuN

Europium(II) compounds tend to predominate, in contrast to most lanthanides: (which generally form compounds with an oxidation state of +3). Europium(II) chemistry is very similar to barium(II) chemistry, as they have similar ionic radii. Divalent europium is a mild reducing agent, such that under atmospheric conditions, it is the trivalent form that predominates. Under anaerobic, and particularly under geothermal conditions, the divalent form is sufficiently stable such that it tends to be incorporated into minerals of calcium and the other alkaline earths. This is the cause of the "negative europium anomaly", that depletes europium from being incorporated into the most usual light lanthanide minerals such as monazite, relative to the chondritic abundance. Bastnaesite tends to show less of a negative europium anomaly than monazite does, and hence is the major source of europium today. The accessible divalency of europium has always made it one of the easiest lanthanides to extract and purify, even when present, as it usually is, in low concentration. See also europium compounds.

 النظائر

•  مقالة مفصلة: نظائر الاوروپيوم

Naturally occurring europium is composed of 2 isotopes, ¹⁵¹Eu and ¹⁵³Eu, with ¹⁵³Eu being the most abundant (52.2% natural abundance). While ¹⁵³Eu is stable, ¹⁵¹Eu was recently found to be unstable to alpha decay with half-life of $5_{-3}^{+11}\times 10^{18}$ yr, in reasonable agreement with theoretical predictions. Besides natural radioisotope ¹⁵¹Eu, 35 artificial radioisotopes have been characterized, with the most stable being ¹⁵⁰Eu with a half-life of 36.9 years, ¹⁵²Eu with a half-life of 13.516 years, and ¹⁵⁴Eu with a half-life of 8.593 years. All of the remaining radioactive isotopes have half-lives that are less than 4.7612 years, and the majority of these have half-lives that are less than 12.2 seconds. This element also has 8 meta states, with the most stable being ^150mEu (t_½ 12.8 hours), ^152m1Eu (t_½ 9.3116 hours) and ^152m2Eu (t_½ 96 minutes).

The primary decay mode before the most abundant stable isotope, ¹⁵³Eu, is electron capture, and the primary mode after is beta minus decay. The primary decay products before ¹⁵³Eu are isotopes of samarium (Sm) and the primary products after are isotopes of gadolinium (Gd).

 اوروپيوم كناتج عن الانشطار النووي

مقاطع عرضية للإمساك الحراري للنيوترونات

النظير	151Eu	152Eu	153Eu	154Eu	155Eu
Yield	~10	low	1580	>2.5	330
Barns	5900	12800	312	1340	3950

Medium-lived
fission products

Prop: Unit:	t½ a	Yield %	Q * keV	βγ *
155Eu	4.76	.0803	252	βγ
85Kr	10.76	.2180	687	βγ
113mCd	14.1	.0008	316	β
90Sr	28.9	4.505	2826	β
137Cs	30.23	6.337	1176	βγ
121mSn	43.9	.00005	390	βγ
151Sm	96.6	.5314	77	β

الاوروپيوم يتم انتاجه في الانشطار النووي, ولكن fission product yields of europium isotopes are low near the top of the mass range for fission products.

Like other lanthanides, many isotopes, especially isotopes with odd mass numbers and neutron-poor isotopes like ¹⁵²Eu, have high cross sections for neutron capture, often high enough to be neutron poisons.

¹⁵¹Eu is the beta decay product of Sm-151, but since this has a long decay half-life and short mean time to neutron absorption, most ¹⁵¹Sm instead winds up as ¹⁵²Sm.

¹⁵²Eu (half-life 13.516 years) and ¹⁵⁴Eu (halflife 8.593 years) cannot be beta decay products because ¹⁵²Sm and ¹⁵⁴Sm are nonradioactive, but ¹⁵⁴Eu is the only long-lived "shielded" nuclide, other than ¹³⁴Cs, to have a fission yield of more than 2.5 parts per million fissions. A larger amount of ¹⁵⁴Eu will be produced by neutron activation of a significant portion of the nonradioactive¹⁵³Eu; however, much of this will be further converted to ¹⁵⁵Eu.

¹⁵⁵Eu (halflife 4.7612 years) has a fission yield of 330 ppm for U-235 and thermal neutrons. Most will be transmuted to nonradioactive and nonabsorptive Gadolinium-156 by the end of fuel burnup.

Overall, europium is overshadowed by Cs-137 and Sr-90 as a radiation hazard, and by samarium and others as a neutron poison.

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 المحاذير

سمية مركبات الاوروپيوم لم تـُدرس بالكامل بعد, but there are no clear indications that europium is highly toxic compared to other heavy metals. The metal dust presents a fire and explosion hazard. Europium has no known biological role.

 عزل الاوروپيوم

Europium metal is available commercially so it is not normally necessary to make it in the laboratory, which is just as well as it is difficult to isolate as the pure metal. This is largely because of the way it is found in nature. The lanthanoids are found in nature in a number of minerals. The most important are xenotime, monazite, and bastnaesite. The first two are orthophosphate minerals LnPO₄ (Ln denotes a mixture of all the lanthanoids except promethium which is vanishingly rare) and the third is a fluoride carbonate LnCO₃F. Lanthanoids with even atomic numbers are more common. The most common lanthanoids in these minerals are, in order, cerium, lanthanum, neodymium, and praseodymium. Monazite also contains thorium and yttrium which makes handling difficult since thorium and its decomposition products are radioactive.

For many purposes it is not particularly necessary to separate the metals, but if separation into individual metals is required, the process is complex. Initially, the metals are extracted as salts from the ores by extraction with sulfuric acid (H₂SO₄), hydrochloric acid (HCl), and sodium hydroxide (NaOH). Modern purification techniques for these lanthanoid salt mixtures are ingenious and involve selective complexation techniques, solvent extractions, and ion exchange chromatography.

Pure europium is available through the electrolysis of a mixture of molten EuCl₃ and NaCl (or CaCl₂) in a graphite cell which acts as cathode using graphite as anode. The other product is chlorine gas.

 المصادر

• Los Alamos National Laboratory - Europium

 وصلات خارجية

• WebElements.com - Europium
• It's Elemental - Europium