پلاديوم

(تم التحويل من Palladium)
پلاديوم,  46Pd
Palladium (46 Pd).jpg
الخصائص العامة
النطق
المظهر أبيض فضي
الوزن الذري العياري (Ar, standard) 106.42(1)
پلاديوم في الجدول الدوري
Hydrogen (reactive nonmetal)
Helium (noble gas)
Lithium (alkali metal)
Beryllium (alkaline earth metal)
Boron (metalloid)
Carbon (reactive nonmetal)
Nitrogen (reactive nonmetal)
Oxygen (reactive nonmetal)
Fluorine (reactive nonmetal)
Neon (noble gas)
Sodium (alkali metal)
Magnesium (alkaline earth metal)
Aluminium (post-transition metal)
Silicon (metalloid)
Phosphorus (reactive nonmetal)
Sulfur (reactive nonmetal)
Chlorine (reactive nonmetal)
Argon (noble gas)
Potassium (alkali metal)
Calcium (alkaline earth metal)
Scandium (transition metal)
Titanium (transition metal)
Vanadium (transition metal)
Chromium (transition metal)
Manganese (transition metal)
Iron (transition metal)
Cobalt (transition metal)
Nickel (transition metal)
Copper (transition metal)
Zinc (post-transition metal)
Gallium (post-transition metal)
Germanium (metalloid)
Arsenic (metalloid)
Selenium (reactive nonmetal)
Bromine (reactive nonmetal)
Krypton (noble gas)
Rubidium (alkali metal)
Strontium (alkaline earth metal)
Yttrium (transition metal)
Zirconium (transition metal)
Niobium (transition metal)
Molybdenum (transition metal)
Technetium (transition metal)
Ruthenium (transition metal)
Rhodium (transition metal)
Palladium (transition metal)
Silver (transition metal)
Cadmium (post-transition metal)
Indium (post-transition metal)
Tin (post-transition metal)
Antimony (metalloid)
Tellurium (metalloid)
Iodine (reactive nonmetal)
Xenon (noble gas)
Caesium (alkali metal)
Barium (alkaline earth metal)
Lanthanum (lanthanide)
Cerium (lanthanide)
Praseodymium (lanthanide)
Neodymium (lanthanide)
Promethium (lanthanide)
Samarium (lanthanide)
Europium (lanthanide)
Gadolinium (lanthanide)
Terbium (lanthanide)
Dysprosium (lanthanide)
Holmium (lanthanide)
Erbium (lanthanide)
Thulium (lanthanide)
Ytterbium (lanthanide)
Lutetium (lanthanide)
Hafnium (transition metal)
Tantalum (transition metal)
Tungsten (transition metal)
Rhenium (transition metal)
Osmium (transition metal)
Iridium (transition metal)
Platinum (transition metal)
Gold (transition metal)
Mercury (post-transition metal)
Thallium (post-transition metal)
Lead (post-transition metal)
Bismuth (post-transition metal)
Polonium (post-transition metal)
Astatine (metalloid)
Radon (noble gas)
Francium (alkali metal)
Radium (alkaline earth metal)
Actinium (actinide)
Thorium (actinide)
Protactinium (actinide)
Uranium (actinide)
Neptunium (actinide)
Plutonium (actinide)
Americium (actinide)
Curium (actinide)
Berkelium (actinide)
Californium (actinide)
Einsteinium (actinide)
Fermium (actinide)
Mendelevium (actinide)
Nobelium (actinide)
Lawrencium (actinide)
Rutherfordium (transition metal)
Dubnium (transition metal)
Seaborgium (transition metal)
Bohrium (transition metal)
Hassium (transition metal)
Meitnerium (unknown chemical properties)
Darmstadtium (unknown chemical properties)
Roentgenium (unknown chemical properties)
Copernicium (post-transition metal)
Nihonium (unknown chemical properties)
Flerovium (unknown chemical properties)
Moscovium (unknown chemical properties)
Livermorium (unknown chemical properties)
Tennessine (unknown chemical properties)
Oganesson (unknown chemical properties)
Ni

Pd

Pt
روديومپلاديومفضة
الرقم الذري (Z) 46
المجموعة، الدورة المجموعة 10, الفترة 5
المستوى الفرعي المستوى الفرعي d
التوزيع الإلكتروني [Kr] 4d10
الإلكترونات بالغلاف
2, 8, 18, 18
الخصائص الطبيعية
الطور (عند STP) صلب
نقطة الانصهار 1828.05 K ​(1554.9 °س، ​2830.82 °F)
نقطة الغليان 3236 K ​(2963 °س، ​5365 °ف)
الكثافة (بالقرب من د.ح.غ.) 12.023 ج/سم³
حين يكون سائلاً (عند ن.إ.) 10.38 ج/سم³
حرارة الانصهار 16.74 kJ/mol
حرارة التبخر 358 kJ/mol
السعة الحرارية المولية 25.98 J/(mol·K)
ضغط البخار
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1721 1897 2117 2395 2753 3234
الخصائص الذرية
حالات الأكسدة 0, +1, +2, +3, +4, +5, +6 ​(a أكسيد قاعدي معتدل)
الكهرسلبية Pauling scale: 2.20
طاقات التأين
  • 1st: 804.4 kJ/mol
  • 2nd: 1870 kJ/mol
  • 3rd: 3177 kJ/mol
نصف القطر الذري empirical: 137 pm
نصف قطر التكافؤ 139±6 pm
نصف قطر ڤان در ڤالز 163 pm
Color lines in a spectral range
متفرقات
البنية البلورية ​مكعب متوسطن حول الوجه
[[File:مكعب متوسطن حول الوجه|50px|alt=مكعب متوسطن حول الوجه crystal structure for پلاديوم|مكعب متوسطن حول الوجه crystal structure for پلاديوم]]
سرعة الصوت thin rod 3070 m/s (at 20 °C)
التمدد الحراري 11.8 µm/(m·K) (at 25 °C)
التوصيل الحراري 71.8 W/(m·K)
المقاومة الكهربائية 105.4 nΩ·m (at 20 °C)
الترتيب المغناطيسي مغناطيسية مسايرة[1]
معامل يونگ 121 GPa
معامل القص 44 GPa
معاير الحجم 180 GPa
نسبة پواسون 0.39
صلادة موز 4.75
صلادة ڤيكرز 400–600 MPa
صلادة برينل 320–610 MPa
رقم كاس 7440-05-3
التاريخ
التسمية على اسم الكويكب پالاس، الذي هو نفسه مسمى على اسم پالاس أثينا
الاكتشاف وأول عزل وليام هايد ولاستون (1803)
نظائر پلاديوم الرئيسية
نظير التوافر عمر النصف (t1/2) نمط الاضمحلال النواتج
100Pd إصط 3.63 d ε 100Rh
γ 0.084, 0.074,
0.126
102Pd 1.02% (β+β+) 1.1720 102Ru
103Pd syn 16.991 d ε 103Rh
104Pd 11.14% (SF) <18.969
105Pd 22.33% (SF) <18.247
106Pd 27.33% (SF) <16.806
107Pd طفيف 6.5×106 y β 0.033 107Ag
108Pd 26.46% (SF) <16.102
110Pd 11.72% >6×1017 y ββ 1.9997 110Cd
أنماط الانحلال بين الأقواس هي متوقعة، إلا أنها لم تُرصد
| المراجع | [[:d:خطأ لوا في وحدة:Wikidata على السطر 863: attempt to index field 'wikibase' (a nil value).|في ويكي‌داتا]]

الپلاديوم Palladium عنصر كيميائي من الجدول الدوري، ورمزه Pd ، ورقمه الذري 46. وهو فلز انتقالي نادر، من مجموعة البلاتين. ويشبه البلاتين كيميائياً. ويستخرج من خامي النحاس والنيكل. ويستخدم كعامل مساعد وفي صناعة المجوهرات. الپلاديوم كان قد اكتشفه وليام هايد ولاستون William Hyde Wollaston عام 1803.[3][4] He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired by her when she slew Pallas. Palladium, platinum, rhodium, ruthenium, iridium and osmium form a group of elements referred to as the platinum group metals (PGMs). These have similar chemical properties, but palladium has the lowest melting point and is the least dense of them.

More than half the supply of palladium and its congener platinum is used in catalytic converters, which convert as much as 90% of the harmful gases in automobile exhaust (hydrocarbons, carbon monoxide, and nitrogen dioxide) into less noxious substances (nitrogen, carbon dioxide and water vapor). Palladium is also used in electronics, dentistry, medicine, hydrogen purification, chemical applications, groundwater treatment, and jewelry. Palladium is a key component of fuel cells, which react hydrogen with oxygen to produce electricity, heat, and water.

Ore deposits of palladium and other PGMs are rare. The most extensive deposits have been found in the norite belt of the Bushveld Igneous Complex covering the Transvaal Basin in South Africa; the Stillwater Complex in Montana, United States; the Sudbury Basin and Thunder Bay District of Ontario, Canada; and the Norilsk Complex in Russia. Recycling is also a source, mostly from scrapped catalytic converters. The numerous applications and limited supply sources result in considerable investment interest.

الطلب العالمي على الپلاديوم ارتفع من 100 طن في 1990 إلى نحو 300 طن في 2000. الانتاج العالمي من المناجم كان 222 طن متري في 2006 حسب بيانات USGS. معظم الپالاديوم يستخدم في catalytic converters صناعة السيارات.[5]

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الخصائص

الپالاديوم.

الپالاديوم هو معدن فضي أبيض طري يشبه الپلاتين. Palladium belongs to group 10 in the periodic table, but the configuration in the outermost electrons are in accordance with Hund's rule. Electrons in the s-shell migrate to fill the d orbitals because they have less energy.

Z العنصر No. of electrons/shell
28 نيكل 2, 8, 16, 2 (or 2, 8, 17, 1)
46 پلاديوم 2, 8, 18, 18
78 پلاتين 2, 8, 18, 32, 17, 1
110 دارمشتاتيوم 2, 8, 18, 32, 32, 16, 2 (متوقع)


التصوير

باستخدام طريقة الطباعة باستعمال platinotype فباستطاعة المصورين أن ينتجوا أعمالاً فنية راقية باستعمال أملاح الپلاتين أو الپالاديوم. ولما كان غالباً ما يستعمل مع الپلاتين, فإن الپالاديوم يمنح بديلاً للفضة.[6]

المركبات

انظر أيضا تصنيف: مركبات الپلاديوم

مركبات الپلاديوم تتواجد أساساً في حالات الأكسدة 0 و +2 oxidation state. Other less common states are also recognized. Generally the compounds of palladium are more similar to those of platinum than those of any other element.

Alpha-palladium(II)-chloride-xtal-3D-balls.png
Pd6Cl12-from-xtal-1996-CM-3D-ellipsoids.png
Structure of α-PdCl2
Structure of β-PdCl2

پلاديوم(II)

كلوريد الپلاديوم(II) هو المادة البادئة الرئيسية لمركبات الپلاديوم الأخرى. It arises by the reaction of palladium with chlorine. It is used to prepare heterogeneous palladium catalysts such as palladium on barium sulfate, palladium on carbon, and palladium chloride on carbon.[7] Solutions of PdCl2 in nitric acid react with acetic acid to give palladium(II) acetate, also a versatile reagent. PdCl2 reacts with ligands (L) to give square planar complexes of the type PdCl2L2. One example of such complexes is the benzonitrile derivative PdX2(PhCN)2.[8][9]

PdCl2 + 2 L → PdCl2L2 (L = PhCN, PPh3, NH3, etc)

The complex bis(triphenylphosphine)palladium(II) dichloride is a useful catalyst.[10]

پلاديوم(0)

Palladium forms a range of zerovalent complexes with the formula PdL4, PdL3 and PdL2. For example, reduction of a mixture of PdCl2(PPh3)2 and PPh3 gives tetrakis(triphenylphosphine)palladium(0):[11]

2 PdCl2(PPh3)2 + 4 PPh3 + 5 N2H4 → 2 Pd(PPh3)4 + N2 + 4 N2H5+Cl

Another major palladium(0) complex, tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), is prepared by reducing sodium tetrachloropalladate in the presence of dibenzylideneacetone.[12]

Palladium(0), as well as palladium(II), are catalysts in coupling reactions, as has been recognized by the 2010 Nobel Prize in Chemistry to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki. Such reactions are widely practiced for the synthesis of fine chemicals. Prominent coupling reactions include the Heck, Suzuki, Sonogashira coupling, Stille reactions, and the Kumada coupling. Palladium(II) acetate, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4, and tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) serve either as catalysts or precatalysts.[13]


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حالات أكسدة أخرى

بالرغم من أن مركبات Pd(IV) هم نسبياً نادرون، فأحد الأمثلة هو sodium hexachloropalladate(IV), Na2[PdCl6]. A few compounds of palladium(III) are also known.[14] Palladium(VI) was claimed in 2002,[15][16] but subsequently disproven.[17][18]

Mixed valence palladium complexes exist, e.g. Pd4(CO)4(OAc)4Pd(acac)2 forms an infinite Pd chain structure, with alternatively interconnected Pd4(CO)4(OAc)4 and Pd(acac)2 units.[19]

تاريخ

الپلاديوم كان قد اكتشفه وليام هايد ولاستون William Hyde Wollaston عام 1803.[20][21] وكان ولاستون قد سمّى هذا العنصر عام 1804 على اسم المذنّب پالاس Pallas, والذي كان قد اكتُشِف قبل عامين.[22]

التواجد

انتاج الپالاديوم في 2005

في 2005, روسيا كانت المنتج الأكبر للپالاديوم بحصة لا تقل عن 50% من الانتاج العالمي ويتبعها جنوب أفريقيا, الولايات المتحدة وكندا, حسب British Geological Survey.

Applications

Cross section of a metal-core catalytic converter
The Soviet 25-rouble commemorative palladium coin is a rare example of the monetary usage of palladium.

The largest use of palladium today is in catalytic converters.[23] Palladium is also used in jewelry, dentistry,[23][24] watch making, blood sugar test strips, aircraft spark plugs, surgical instruments, and electrical contacts.[25] Palladium is also used to make professional transverse (concert or classical) flutes.[26] As a commodity, palladium bullion has ISO currency codes of XPD and 964. Palladium is one of only four metals to have such codes, the others being gold, silver and platinum.[27] Because it absorbs hydrogen, palladium is a key component of the controversial cold fusion experiments that began in 1989.


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Catalysis

When it is finely divided, as with palladium on carbon, palladium forms a versatile catalyst; it speeds heterogeneous catalytic processes like hydrogenation, dehydrogenation, and petroleum cracking. Palladium is also essential to the Lindlar catalyst, also called Lindlar's Palladium.[28] A large number of carbon–carbon bonding reactions in organic chemistry are facilitated by palladium compound catalysts. For example:

(See palladium compounds and palladium-catalyzed coupling reactions.)

When dispersed on conductive materials, palladium is an excellent electrocatalyst for oxidation of primary alcohols in alkaline media.[29] Palladium is also a versatile metal for homogeneous catalysis, used in combination with a broad variety of ligands for highly selective chemical transformations.

In 2010, palladium-catalysed organic reactions were recognized by the Nobel Prize in Chemistry. A 2008 study showed that palladium is an effective catalyst for carbon-fluoride bonds.[30]

Catalytic cycle for Kumada cross coupling reaction, which is widely used in the synthesis of fine chemicals.

Palladium catalysis is primarily employed in organic chemistry and industrial applications, although its use is growing as a tool for synthetic biology; in 2017, effective in vivo catalytic activity of palladium nanoparticles was demonstrated in mammals to treat disease.[31]

Electronics

The second greatest application of palladium in electronics is in multilayer ceramic capacitors[32] in which palladium (and palladium-silver alloy) is used for electrodes.[23] Palladium (sometimes alloyed with nickel) is used for component and connector plating in consumer electronics[33][34] and in soldering materials. The electronic sector consumed 1.07 million troy ounces (33.2 tonnes) of palladium in 2006, according to a Johnson Matthey report.[35]

Technology

Hydrogen easily diffuses through heated palladium,[36] and membrane reactors with Pd membranes are used in the production of high purity hydrogen.[37] Palladium is used in palladium-hydrogen electrodes in electrochemical studies. Palladium(II) chloride readily catalyzes carbon monoxide gas to carbon dioxide and is useful in carbon monoxide detectors.[38]

Hydrogen storage

Palladium readily absorbs hydrogen at room temperatures, forming palladium hydride PdHx with x less than 1.[39] While this property is common to many transition metals, palladium has a uniquely high absorption capacity and does not lose its ductility until x approaches 1.[40] This property has been investigated in designing an efficient, inexpensive, and safe hydrogen fuel storage medium, though palladium itself is currently prohibitively expensive for this purpose.[41] The content of hydrogen in palladium can be linked to magnetic susceptibility, which decreases with the increase of hydrogen and becomes zero for PdH0.62. At any higher ratio, the solid solution becomes diamagnetic.[42]

Dentistry

Palladium is used in small amounts (about 0.5%) in some alloys of dental amalgam to decrease corrosion and increase the metallic lustre of the final restoration.[43]

Jewelry

Palladium has been used as a precious metal in jewelry since 1939 as an alternative to platinum in the alloys called "white gold", where the naturally white color of palladium does not require rhodium plating. Palladium is much less dense than platinum. Similar to gold, palladium can be beaten into leaf as thin as 100 nm (1250,000 in).[36] Unlike platinum, palladium may discolor at temperatures above 400 °C (752 °F);[44] it is relatively brittle.[مطلوب توضيح]

Prior to 2004, the principal use of palladium in jewelry was the manufacture of white gold. Palladium is one of the three most popular alloying metals in white gold (nickel and silver can also be used).[23] Palladium-gold is more expensive than nickel-gold, but seldom causes allergic reactions (though certain cross-allergies with nickel may occur).[45]

When platinum became a strategic resource during World War II, many jewelry bands were made out of palladium. Palladium was little used in jewelry because of the technical difficulty of casting. With the casting problem resolved[بحاجة لمصدر] the use of palladium in jewelry increased, originally because platinum increased in price while the price of palladium decreased.[46] In early 2004, when gold and platinum prices rose steeply, China began fabricating volumes of palladium jewelry, consuming 37 tonnes in 2005. Subsequent changes in the relative price of platinum lowered demand for palladium to 17.4 tonnes in 2009.[47][48] Demand for palladium as a catalyst has increased the price of palladium to about 50% higher than that of platinum in January 2019.[49]

In January 2010, hallmarks for palladium were introduced by assay offices in the United Kingdom, and hallmarking became mandatory for all jewelry advertising pure or alloyed palladium. Articles can be marked as 500, 950, or 999 parts of palladium per thousand of the alloy.

Fountain pen nibs made from gold are sometimes plated with palladium when a silver (rather than gold) appearance is desired. Sheaffer has used palladium plating for decades, either as an accent on otherwise gold nibs or covering the gold completely.

Photography

In the platinotype printing process, photographers make fine-art black-and-white prints using platinum or palladium salts. Often used with platinum, palladium provides an alternative to silver.[50]

Toxicity

پلاديوم
المخاطر
ن.م.ع. مخطط تصويري The exclamation-mark pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)
ن.م.ع. كلمة الاشارة Warning
H317
P261, P273, P280, P302+352, P321, P333+313, P363, P501[51]

Palladium is a metal with low toxicity. It is poorly absorbed by the human body when ingested. Plants such as the water hyacinth are killed by low levels of palladium salts, but most other plants tolerate it, although tests show that, at levels above 0.0003%, growth is affected. High doses of palladium could be poisonous; tests on rodents suggest it may be carcinogenic, though no clear evidence indicates the element harms humans.[52]

Precautions

Like other platinum-group metals, bulk Pd is quite inert. Although contact dermatitis has been reported, data on the effects are limited. It has been shown that people with an allergic reaction to palladium also react to nickel, making it advisable to avoid the use of dental alloys containing palladium on those so allergic.[53][54][55][56][57]

Some palladium is emitted with the exhaust gases of cars with catalytic converters. Between 4 and 108 ng/km of palladium particulate is released by such cars, while the total uptake from food is estimated to be less than 2 µg per person a day. The second possible source of palladium is dental restoration, from which the uptake of palladium is estimated to be less than 15 µg per person per day. People working with palladium or its compounds might have a considerably greater uptake. For soluble compounds such as palladium chloride, 99% is eliminated from the body within 3 days.[53]

The median lethal dose (LD50) of soluble palladium compounds in mice is 200 mg/kg for oral and 5 mg/kg for intravenous administration.[53]

انظر أيضاً

المصادر

  1. ^ Lide, D. R., ed. (2005). "Magnetic susceptibility of the elements and inorganic compounds". CRC Handbook of Chemistry and Physics (PDF) (86th ed.). Boca Raton (FL): CRC Press. ISBN  0-8493-0486-5 .
  2. ^ Standard Atomic Weights 2013. Commission on Isotopic Abundances and Atomic Weights
  3. ^ Platinum Metals Review, Rhodium and Palladium - Events Surrounding Its Discovery, accessed 5 Feb 2007.
  4. ^ W. H. Wollaston (1804). "On a New Metal, Found in Crude Platina". Philosophical Transactions of the Royal Society of London. 94: 419-430.
  5. ^ J. Kielhorn, C. Melber, D. Keller, I. Mangelsdorf (2002). "Palladium – A review of exposure and effects to human health". International Journal of Hygiene and Environmental Health. 205 (6). doi:10.1078/1438-4639-00180. Text " pages 417-432 " ignored (help)CS1 maint: Multiple names: authors list (link)
  6. ^ Mike Ware (2005). "Book Review of : Photography in Platinum and Palladium". Platinum Metals Review. 49 (4): 190–195. doi:10.1595/147106705X70291.
  7. ^ قالب:OrgSynth
  8. ^ Anderson, Gordon K.; Lin, Minren; Sen, Ayusman; Gretz, Efi (1990). "Bis(Benzonitrile)Dichloro Complexes of Palladium and Platinum". Inorganic Syntheses. Inorganic Syntheses. 28: 60–63. doi:10.1002/9780470132593.ch13. ISBN  978-0-470-13259-3 .
  9. ^ Zalevskaya, O. A; Vorob'eva, E. G; Dvornikova, I. A; Kuchin, A. V (2008). "Palladium complexes based on optically active terpene derivatives of ethylenediamine". Russian Journal of Coordination Chemistry. 34 (11): 855–857. doi:10.1134/S1070328408110110.
  10. ^ قالب:OrgSynth
  11. ^ Coulson, D. R.; Satek, L. C.; Grim, S. O. (1972). "23. Tetrakis(triphenylphosphine)palladium(0)". Inorg. Synth. Inorganic Syntheses. 13: 121–124. doi:10.1002/9780470132449.ch23. ISBN  978-0-470-13244-9 .
  12. ^ Takahashi, Y; Ito, Ts; Sakai, S; Ishii, Y (1970). "A novel palladium(0) complex; bis(dibenzylideneacetone)palladium(0)". Journal of the Chemical Society D: Chemical Communications (17): 1065. doi:10.1039/C29700001065.
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