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Nickel and its compounds

 

Nickel is a malleable ductile silvery metallic transition element. Its atomic number is 28. Its relative atomic mass is 58.70. Its relative density is 8.9. its melting point is 1450°C. its boiling point is 2732°C. It is found in the minerals pentlandite (NiS), pyrrhoite ((Fe, Ni)S), and garnierite ((Ni,Mg)6(OH)6Si4O11.H2O). Nickel is also present in certain iron meteorites (up to 20%). The metal is extracted by roasting the ore to give the oxide, followed by reduction with carbon monoxide and purification by the Mond process. Alternatively electolysis is used. Nickel metal is used in special steels, in Invar, and, being ferromagnetic, in magnetic alloys, such as Mumetal. It is also an effective catalyst, particularly for hydrogenation reactions.The main compounds are formed with nickel in the +2 oxidation state; the +3 state also exists (e.g. the black oxide, Ni2O3). Nickel was discovered by Axel Cronstedt (1722-65) in 1751.

Nickel carbonyl is a colourless volatile liquid, Ni(CO)4. Its melting point is 25°C and boiling point is 43°C. It is formed by direct combination of nickel metal with carbon monoxide at 50-60°C. The reaction is reversed at higher temperatures and the reactions are the basis of the Mond process for purifying nickel. The nickel in the compound has an oxidation state of zero and the compound is a typical example of a complex with pi-bonding ligands, in which filled d-orbitals on the nickel overlap with empty p-orbitals on the carbon.

Nickelic compounds are the compounds of nickel in its +3 oxidation state; e.g. nickelic oxide is nickel (III) oxide.

Nickelous compounds are the compounds of nickel in its +2 oxidation state; e.g. nickelous oxide is nickel (II) oxide .

Nickel (II) oxide is a green powder with a relative density of 6.6. It can be made by heating nickel (II) nitrate or carbonate with air excluded.

Nickel(III) oxide is a black or grey powder with relative density of 4.8. It is made by heating nickel (II) oxide in air and used in nickel-iron accumulators.

 

 


Transition elements

 

Transition elements are the set of elements in the periodic table in which filling of electrons in an inner d- or f-level occurs. With increasing proton number, electrons fill atomic levels up to argon, which has the electron configuration ls22s22p63s23p6. In this shell, there are 5 d-orbitals, which can each contain 2 electrons. However, at this point the subshell of lowest energy is not the 3d but the 4s. The next two elements, potassium and calcium, have the configurations [Ar] 4s1 and [Ar]4s2 respectively. For the next element, scandium, the 3d level is of lower energy than the 4p level, and scandium has the configuration [Ar]3d1 4s2. This filling of the inner d-level continues up to zinc [Ar]3d104s2, giving the first transition series. There is a further series of this type in the next period of the table: between yttrium ([Kr]4d 5s2) and cadmium ([Kr]4d105s2). This is the second transition series. In the next period of the table the situation is rather more complicated. Lanthanum has the configuration [Xe]5d1 6s2. The level of lowest energy then becomes the 4 f level and the next element, cerium, has the configuration [Xe]4f15d1 6s2. There are 7 of these f- orbitals, each of which can contain 2 electrons, and filling of the f -levels continues up to lutetium ([Xe]4f145d16s2). Then the filling of the 5d levels continues from hafnium to mercury. The series of 14 elements from cerium to lutetium is a series within a series called an inner transition series. This one is the lanthanoid series. In the next period there is a similar inner transition series, the actinoid series, from thorium to lawrencium. Then filling of the d-level continues from element 104 onwards.

In fact, the classification of chemical elements is valuable only in so far as it illustrates chemical behaviour and it is conventional to use the term transition elements in a more restricted sense. The elements in the inner transition series from cerium (58) to lutetium (71) are called the lanthanoids; those in the series from thorium (90) to lawrencium (103) are the actinoids. These two series together make up the f-block in the periodic table. It is also common to include scandium, yttrium and lanthanum with the lanthanoids (because of chemical similarity) and to include actinium with the actinoids. Of the remaining transition elements, it is usual to speak of three main transition series: from titanium to copper; from zirconium to silver; and from hafnium to gold. All these elements have similar chemical properties that result from the presence of unfilled d-orbitals in the element or (in the case of copper, silver and gold) in the ions. The elements from 104 to 109 and the undiscovered elements 110 and 111 make up a fourth transition series. The elements zinc, cadmium and mercury have filled d-orbitals both in the elements and in compounds, and are usually regarded as nontransition elements forming group 12 of the periodic table. The elements of the three main transition series are all typical metals (u the nonchemical sense), i.e. most are strong hard materials that are good conductors of heat and electricity and have high melting and boilingpoints. Chemically, their behaviour depends on the existence of unfilled d-orbitals. They exhibit variable valency, have coloured compounds, and form coordination compounds. Many of their compounds are paramagnetic as a result of the presence of unpaired electrons. Many of them are good catalysts. They are less reactive than the s- and p-block metals.




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