Understanding The Chemistry Of Nickel

Understanding The Chemistry Of atomic number 28 note atomic number 28 is sil actually white 1 and lustrous metal. It is the 7th near abundant transition metal and 24th some abundant element in the crust of earth. It has an atomic number of 28, atomic mass of 58.71 gmol-1 and atomic volume of 6.59 cm3mol-1 2. It belongs to group 10 (8B) and 4th period of neo periodic table. atomic number 28 has electronic configuration Ar 4s2 3d8 3. It has property of malleability and ductility. 300 kilometers long wire can be drawn from a single kilogram of plate. It has uplifted electrical and thermal conductivities of 0.146 x 106 Scm-1 and 90.9 Wm-1K-1. It is hard, odorless and corrosion resistant metal that takes a high polish. atomic number 28 crystallizes with face centered cubic structure. The social unit cell has lattice parameter of 0.352 nm with atomic radius of 0.124 nm. plate is naturally occuring ferro magnetic and magnetostrictive material 4 at or near room temperature. Its c urie temperature is 355 C 5.Nickel is mined from two types of ore deposits. These include laterites and sulphides. Laterites atomic number 18 silicate or oxide ores. It occurs most usually in combination with sulphur and iron in pentlandite (NiS.2FeS) which contains 1.5% atomic number 28, with sulfur in millerite (NiS), with arsenic in mineral plate noteine (NiAs) as a red nickel ore, containing 43.9% nickel and 56.1% arsenic, and with arsenic and sulfur in nickel glance 6.1.2 chemic Properties of NickelNickel is relatively unre sprightly element. Under ambient conditions, it does not react with wet, oxygen or dissolve in most acids.1.2.1 Standard reduction PotentialsIn aqueous solution, the standard reduction potentials for various oxidisation states of nickel argon shown in Scheme 1.1 7, 8.Scheme 1.1 Standard Electrode Potentials of Various Nickel Species1.2.2 reaction of Nickel with HalogensNickel dichloride, NiCl2, nickel dibromide, NiBr2, and nickel diiodide, NiI2, ar e formed by the reactions of nickel with chlorine, Cl2, bromine, Br2, and iodine, I2.Ni(s) + Cl2(g) NiCl2(s) (yellow)Ni(s) + Br2(g) NiBr2(s) (yellow)Ni(s) + I2(g) NiI2(s) (black)1.2.3 Reaction of Nickel with AcidsNickel metal dissolves slowly in thin sulphuric acid to form solution containing the aquated Ni(II) ion together with hydrogen gas, H2.Ni(s) + H2SO4(aq) Ni2+(aq) + SO42-(aq) + H2(g)Ni(s) + HCl(aq) Ni2+(aq) + Cl- (aq) + H2(g)It does not dissolve in concentrated nitric acid, HNO3, because it is rendered passive by this reagent 9.1.2.4 Reaction of Nickel with AirNickel in finely divided form reacts readily with air. At higher temperatures, it burns in oxygen to form nickel oxide.2Ni(s) + O2(g) 2NiO(s)1.3 oxidization StatesThe oxidation states of nickel include -1, 0, +1, +2, +3 or +4. The most prevalent oxidation state is +2, but compounds of Ni0, Ni+1, and Ni3+ are well known. Ni4+ has also been exhibit 10.1.4 Nickel(II) CompoundsNickel is known primarily for its div alent compounds with all common anions, i.e. halides, hydroxide, sulfate, carbonate, carboxylates, sulfide and hydroxide. Green and blue are the characteristic people of colors of its compounds. Important nickel(II) compounds include1.4.1 OxidesNickel oxide, NiO is a powdery green solid that becomes yellow on heating 11. It can be vigilant easily by heating nickel carbonate, nitrate or hydroxide.1.4.2 SulfidesNickel sulfides occur in different forms such as NiS, nickel sulphide, NiS2, nickel persulphide and Ni3S2, trinickel disulphide.1.4.3 HalidesNiCl2 is yellow but NiCl2.6H2O is of green colour. NiCl2 is prepared byNiCl2.6H2O + 6SOCl2 NiCl2 + 6SO2 + 12HClNiF2 is prepared by treatment of anhydrous nickel(II) chlHYPERLINK http//en.wikipedia.org/wiki/Nickel(II)_chlorideoride with fluorine at 350 C 12.NiClHYPERLINK http//en.wikipedia.org/wiki/Nickel(II)_chloride2 + FHYPERLINK http//en.wikipedia.org/wiki/Fluorine2 NiF2 + ClHYPERLINK http//en.wikipedia.org/wiki/Chlorine21.4.4 Nitrat esNickel(II) nitrate hexahydrate, Ni(NO3)2.6H2O is highly disintegrable in wet, giving emerald green solutions.1.4.5 CarbonatesNickel(II) carbonate is a ill green polymeric solid consisting of Ni2+ cations and COHYPERLINK http//en.wikipedia.org/wiki/Carbonate3HYPERLINK http//en.wikipedia.org/wiki/CarbonateHYPERLINK http//en.wikipedia.org/wiki/Carbonate2- anions. It is readily decomposed by aqueous acids to give solutions containing the ion Ni(H2O)62+, liberating water and carbon dioxide.1.4.6 SulfatesThe anhydrous form has a yellow to green color firearm NiSO4.7H2O and NiSO4.6H2O appears green and blue to pale green, respectively.1.4.7 HydroxidesNi(OH)2 occurs as green crystals that can be precipitated when aqueous alkali is added to a solution of nickel (II) salt. Its decomposition on heating above 230 C produces toxic gases.1.5 Nickel (III), Nickel (IV) Nickel (VI) CompoundsThe +3 oxidation state is found in dinickel trioxide, Ni2O3. NiO4-2 is an example of +6 oxidation state while NiO2 and NiF6-2 correspond to +4 oxidation states. Nickel(IV) also occurs in BaNiO3 and in the periodate salts, MNiIO6 (M = alkali cation, NH4).1.6 Water Soluble, Poorly Soluble Insoluble NickelCompoundsIn contrast to water soluble nickel salts (chloride, nitrate, acetate and sulfate), metallic nickel, nickel sulfides, and nickel oxides are poorly soluble in water 13. NiCO3 is partly water soluble.1.7 Nickel(II) ComplexesNickel in its most common +2 oxidation state displays a wider range of geometries in its multifactoriales than any other metal ion with coordination numbers 3 to 6.Nickel(II) forms some complexes with octahedral 14, 15, square coplanar 16, 17, 18 and tetrahedral 19, 20 geometries and a smaller number of five coordinate compounds 21, 22 with square pyramidal and trigonal bipyramidal arrangements. Nickel(II) octahedral, trigonal bipyramidal, square pyramidal and tetrahedral complexes are paramagnetic and vex in the bulk of cases a green or blue colour. The square planar nickel complexes are diamagnetic and mostly take a yellow, red or brown colour.The ligand exchange processes for nickel(II) tend to be associative, while with palladium(II) and platinum(II), dissociative pathways predominate which tends to adopt only square planar complexes.1.7.1 half dozen get up Octahedral Nickel(II) ComplexesNickel(II) forms octahedral complexes with neutral ligands such as H2O and NH3. Amines displace some or all of water molecules in the octahedral Ni(H2O)62+ ion to form complexes such as trans Ni(H2O)2(NH3)42+, Ni(NH3)62+ and Ni(en)32+. These complexes are characteristically purple or blue in contrast to the bright green hexaaquanickel(II) ion, Ni(H2O)62+ 23.These octahedral complexes have two unpaired electrons and are paramagnetic with magnetic moments 2.9 to 3.4 BM. former(a) examples include dichlorobis(ethylenediamine)nickel(II), a blue solid, soluble in water and polar organic solvents 24 and Ni(acac)2.2H2O 25.2+ 2+Ni(H2O)62+ Ni(NH3)62+ Ni(en)2Cl2 Ni(acac)2.2H2O1.7.2 Five Coordinate Square Pyramidal rhombohedral BipyramidalNickel(II) ComplexesSeveral phosphine and arsine ligands form five coordinate trigonal bipyramidal complexes because tetradentate tripod ligands such as NC2H4N(CH3)23 and NC2H4PPh23 cannot span the apices of a regular tetrahedron. One face is left open for fifth ligand, e.g halide ion to form trigonal bipyramidal complex. Though hydride, thiolate, alkyl and other anionic ligands are also known the complexes are therefore +1 cations.Tris(1,3-diaminopropane) chromium(III) pentacyanonickelate(II), Cr(tn)3Ni(CN)5 has square pyramidal Ni(CN)53- anions. In contrast, crystalline tris(ethylenediamine) chromium(III) pentacyanonickelate(II) sesquihydrate, Cr(en)3Ni(CN)5.1.5H2O contains both square pyramidal anions and slightly distorted trigonal bipyramidal anions 26.The trigonal bipyramidal structure is favored on the basis of ligand repulsion alone. For this reason, almost both five coordinate compound having non metallic central element such as PF5 has trigonal bipyramidal structure unless there are lone pairs.1.7.3 Four Coordinate Nickel(II) ComplexesNickel(II) in its four coordination mode exhibits either tetrahedral or square planar geometry.1.7.3.1 Tetrahedral Nickel(II) ComplexesNickel(II) tetrahedral complexes of stoichiometric types NiX42-, NiX3L-, NiL2X2 and Ni(L-L)2 are known where X represents halogen, L is neutral ligand such as phosphine, phosphine oxide or arsine, and L-L is bidentate ligand such as ethylenediamine. Tetrahedral arrangement for Ni2+ will be preferred if the ligands are large and weak field.Ni(PPh3)3Cl NiCl42-Ni(acac)21.7.3.2 Square Planar Nickel(II) ComplexesFor the vast majority of four coordinate nickel(II) complexes, planar geometry is preferred for small and strong field ligands. Tetracyanonickelate(II) will probably be orange red colored square planar complex. Almost all planar complexes of nickel(II) with d8 configuration are diamagnetic. Impor tant examples of square planar complexes are red bis(dimethylglyoximato) nickel(II) 27 and dichloro1,3-bis(diphenylphosphino)propanenickel, NiCl2(dppp).Ni(dmgH)2 NiCl2(dppp)Ni(C2O4)22- Ni(CN)42-1.7.4 Three Coordinate Nickel(II) ComplexesThere are many examples of trigonal complexes for nickel(0), however, they are rare for Ni(II). The examples include dialkylamides Ni(NR2)31- and Ni2( -NR2)2(NR2)2 as well as blue mesityl complex Ni(mes)31- which has approximately T shaped geometry 28, 29.1.8 Nickel(III) ComplexesNi(tdt)2- is nickel(III) square planar complex anion having coordination number four where tdt = 3,4-toluenedithiole. Other examples include Ni(tacn)23+ with 1,4,7-triazacyclononane 30 and dark green air stable Ni(III) complex having sponsor NO2S2 chromophore 31.Ni(NO2S)2(C6H4)4 Me(tdt)2-, Me = NiNi(tacn)23+1.9 Nickel(IV) ComplexesA well schematic bis chelated complex of nickel(IV) is the diacetylpyridine dioximato complex 32. Other examples include dicarbollide complex, Ni(closo-1,2-C2B9H11)2 33 and the polyselenide anion Ni4Se4(Se3)(Se4)4- with a cubic Ni4Se4 core 34. The hexadentate ligand 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene 2,15-dione dioxime forms pseudooctahedral NiN6 complex with nickel(IV) 35.1.10 Nickel(-I, 0, +I) ComplexesThe low valent oxides, K3NiO2 and KNa2NiO2 contain linear O-Ni(I)-O3- units 36. The majority of nickel(I) complexes contain phosphine ligands and have tetrahedral or trigonal bipyramidal structure. They are paramagnetic as expected for d9 configurations. In Ni(CO)4, nickel is in zero oxidation state 37. Bis(cyclooctadiene)nickel(0), Ni(C8H12)2 is a diamagnetic featuring tetrahedral nickel(0) 38.Ni(cod)2 Ni(CO)41.11 biologic RoleNickel is a part of urease. NiFe-hydrogenases selectively oxidise H2. Carbon monoxide dehydrogenase enzymes consists of Fe-Ni-S cluster 39. Other nickel containing enzymes include class of superoxide dismutase and glyoxalase 40.Enzymatic reactions attend on redox activity of nicke l atoms in enzymes active site. In fact, proposed mechanisms of NiFe hydrogenase 41, methyl-CoM reductase 42, 43 and NiSOD 44, 45 involves reduced (Nio, Ni+) and or oxidized (Ni3+) forms of nickel. Nickel along with iron plays lively role in transport of oxygen in blood. Nickel also acts as co-factor in absorption of iron from intestine.1.12 Sources and Potential Exposure of NickelNickel is a ubiquitous natural trace element and it occurs in air, water and s oil colour of the biosphere 46.1.12.1 DietFood and drinking water 47, 48 are the major germs of nickel word picture 49. Fats, chocolates 50, nuts, candies 51, tomatoes, bananas, onions, spinach, legumes, tea 52, white flour and all canned foods 53 are rich in nickel content.1.12.2 Ambient AirNickel oxide, nickel chloride, nickel carbonyl and nickel subsulphide are inhaled pollutants. Nickel levels in ambient air are in range 1 10 ng/m3 in urban areas, although much higher levels 110 180 ng/m3 have been recorded in heavily i ndustrialized areas and larger cities 54.1.12.3 Tobacco SmokingIt is major source of nickel in indoor air. A cigarette contains 1 3 g of nickel. Nickel in a burning cigarette form nickel tetracarbonyl that is volatile and gaseous compound and badly affects respiratory tract 55.1.12.4 Occupational Exposure of NickelPulmonary absorption is major route of nickel mental picture in industries 56. The general population is also assailable to nickel in nickel alloys and nickel plated materials such as coins 57, jewellery 58, electric guitar strings 59, unsullied steel cutlery, soaps and detergents.1.13 Exposure Limits of NickelThe American Conference of Governmental and Industrial Hygienists (ACGIH) has assigned threshold limit value time weighted average for exposure to nickel compounds is 1.5 mg/m3 for elemental nickel, 0.1 mg/m3 for soluble inorganic nickel compounds and nickel subsulfide, 0.2 mg/m3 for insoluble inorganic compounds and 0.05 ppm for nickel carbonyl 60.1.14 Toxicity of NickelNickel is known as haemato, immunoto, neuro, geno, reproductive, pulmonary toxic and carcinogenic agent.1.14.1 Acute Toxicity (01 day)The accidental inhalation of nickel carbonyl causes acute toxic personal effects in two stages, immediate and delayed. The immediate symptoms include headache, vertigo, irritability, which usually last a few hours, followed by an asymptomatic interval of 12 h to 5 days. The delayed symptoms are1.14.1.1 Nickel ItchSoluble nickel compounds on scratch up contact may result in nickel itch 61, most frequently when skin is moist.1.14.1.2 Gastrointestinal DistressNausea, vomiting and diarrhea were reported in workers who drank water, contaminated with nickel sulfate and nickel chloride.1.14.1.3 Neurological Effects fatuousness and weariness were reported in individuals accidentally exposed to nickel sulphate and nickel chloride (1.63 g Ni/liter) with boric acid in drinking water 62.1.14.1.4 Pulmonary FibrosisIn humans and animals, nickel carbonyl c auses pulmonary fibrosis. Nickel fumes are respiratory irritants and may also cause pneumonitis.1.14.1.5 Kidney DamageKidney ill-treat and frank haematuria were observed 63.1.14.2 Subchronic Toxicity (10 100 day)A 6 weeks exposure of nickel fumes (0.07 1.1 mg nickel/m3) in humans caused an addition in air way and eye irritations, headaches and tiredness 64.1.14.3 Chronic Toxicity ( 100 days)1.14.3.1 DermatitisIn sensitized individuals, it is most common effect out-of-pocket to nickel use in jewellery intended for pierced body parts and is often marked by itchy and red skin followed by skin ulceration 65.1.14.3.2 Respiratory DisordersInhalation of nickel dusts and aerosols contributes to respiratory disorders such as asthma 66, pneumoconiosis and can also interfere with krebs cycle.1.14.3.3 Heart strokeExposure of nickel tetracarbonyl to levels 50,000 100,000 times greater than levels normally encountered in food or drinking water can cause heart failure and changeable degree s of cardiovascular system poisoning 67.1.14.3.4 TumorsNickel powder can induce both epithelial and connective tissue tumors e.g. pelvic, renal cortical and liver tumors when precondition by subcutaneous, intramuscular or intraperitoneal injection 68.1.14.3.5 Kidney PoisoningNickel in blood is mostly protein bound and accumulates primarily in kidneys resulting in kidney poisoning 69.1.14.3.6 expect DefectsLow birth weight infants with sensory abnormalities, such as hearing or sight loss and cardiac malformations are born with nickel exposed mothers 70, 71.1.14.3.7 Oxidative StressNickel(II) induces oxidative stress in humans 72, 73 by producing either reactive oxygen species, ROS or reactive nitrogen species, RNS. NiCl2 induces lipid peroxidation while ROS generated damage DNA. Nickel binds to DNA repair enzymes and generates oxygen free radicals causing protein degradation 74.1.14.3.8 GenotoxicityNi(CO)4 inhibts DNA dependent RNA synthesis activity by dressing to chromatin or DN A and thereby preventing action of RNA polymerase, causing suppresion of messenger RNA dependent induction of enzyme synthesis 75.1.14.3.9 CarcinogenicityNickel subsulphide, nickel oxide, nickel sulphate as well as nickel sulfide fume and dust is believed to be carcinogenic 76, 77. Independent international scientific bodies have class mixed sulphidic and oxidic nickel compounds 78 as carcinogens to humans, inclusive of water soluble nickel compounds. There are higher chances of development of lung cancer, nasal cancer, and Prostate cancer in nickel exposed workers 79.1.15 Uses of Nickel1.15.1 Nickel AlloysNickel in alloyed form has made significant contributions to our present day society. German silver containing 10 30 % nickel is used for ornamental and domestic objects. Monel contains 68% nickel ands is used in apparatus for handling corrosive materials. Invar is important due to very small coefficient of expansion 80.Nickel is principle alloying element in stainless steel tha t enhances its heat, corrosion, and stress rupture resistance 81. Majority of stainless steels contain 8 10 % nickel. Its limitless uses include home and industrial products.1.15.2 Nickel ElectroplatingNickel electroplating is used for both protective and decorative finishes. Nickel chloride, NiCl2, nickel acetate Ni(OCOCH3)2, nickel nitrate, Ni(NO3)2.6H2O and nickel sulphate, NiSO4.7H2O are employed chiefly in nickel electroplating baths 82 while nickel oxide is used as electrolyte. Nickel electroplating changes the chemical, physical and mechanical properties of the workpiece 83.1.15.3 Catalytic HydrogenationRaney nickel is used in a large number of industrial processes because of its stability and high catalytic activity at room temperature. It catalyses hydrogenation of vegetable oils. Soybean oil has been hydrogenated electrocatalytically on raney nickel with 90 100 % efficiencies 84.Benzene is commonly reduced to cyclohexane using raney nickel for production of nylon.Reducti on of Benzene to Cyclohexane Using Raney NickelRaney nickel is used in reduction of compounds that have multiple bonds.Reduction of Thiophene by Raney NickelDe-Sulfurization of Thioacetals using Raney Nickel1.15.4 Industrial Applications of Nickel1.15.4.1 Heavy IndustriesNickel found super alloys have high temperature applications in jet engines, gas turbines and rocket engines 85. Monel can resist corrosion by sea water and is ideal for propellor shaft in boats and desalination plants.1.15.4.2 Food Chemical processing IndustriesMonel and stainless steel are used in chemical and food processing industries due to better corrosion resistance at high temperature steam 86.1.15.4.3 Ceramics, Paints, Dyes Cosmetic IndustriesNickel(II) phthalocyanine, C32H16N8Ni is used as bluish green pigment in the coloring industries 87. The nickel titanium yellow pigments find great use in polymer and paint applications 88.Nickel dimethylglyoxime (C8 H14 N4 NiO4) is routinely used as coloring agent in paints, cosmetics and authorized kinds of plastics. NiO is used in making glass having ability to absorb visible light but transmits ultraviolet light 89. In cosmetic products of many brands, the highest level of nickel in eye shadows is about 49 ppm 90.1.15.4.4 Textile Rubber IndustryNickel acetate is used as mordant in material industry. Di-n-butyldithiocarbamate nickel(II) complex, NiCS2N(C4H4)22 is used as an antioxidant in tires.1.15.5 BatteriesNickel batteries are dominant in the field of re surgeable electrochemical power sources due to their long cycle life, high power and a reliable performance. Ni(OH)2 is used as positive electrode to significantly boost energy densities in nickel alkaline batteries 91. Nickel cadmium cells set up 1.2 V and are used in aeroplanes and emergency lighting systems. In industries, these batteries provide high voltage of 250 V with capacities about 5 Ah 100 Ah 92.Nickel hydrogen (NiH2) battery cells with nickel oxide positive electrode a re developed due to high power density and good thermal performance which make them beautiful for use in electric vehicles, satellite and space power systems 93.1.16 Chemistry of Ligands1.16.1 Thiourea (Tu)Thiourea, SHYPERLINK http//en.wikipedia.org/wiki/CarbonC(NHYPERLINK http//en.wikipedia.org/wiki/HydrogenH2)2 is lustrous white crystalline compound. It is useful sulfur donor thioamide and planar molecule, soluble in water and polar organic solvents but insoluble in non polar solvents.It has two tautomeric forms but in aqueous solution, thione form predominates.1.16.2 N,N-Dimethylthiourea (Dmtu)N,N-Dimethylthiourea, C3H8N2S has appearance of pale to white crystals. It shows coordination through sulfur.Fig. 1.10 Structure of N,N-Dimethylthiourea1.16.3 1,1,3,3-Tetramethyl-2-thiourea (Tmtu)This substituted thiourea is white crystalline solid. It is sulfur donor ligand.1.16.4 1,3-Diazinane-2-thione (Diaz)This six membered heterocyclic thione is sulfur donor ligand.1.16.5 Imidazolidi ne-2-thione (Imt)It is a sulfur donor five membered heterocyclic thione 94 and has brown crystals. The peculiarity of Imidazolidine-2-thione is presence of a thiouredine fragment. It is planar with non-uniform distribution of electron density and shows presence of maximum negative charge on exocyclic sulfur.Dipolar form B predominates in resonance hybrid.1.17 ObjectiveThe primary objective of this study is to understand basic chemistry of nickel(II) and its complexes and gain an acuteness into metal ligand interactions in biological systems with following main objectives.To explore coordination chemistry of nickel(II) with various sulfur donor ligands and develop useful model for biologically active nickel complexes by determining structures of synthesized nickel complexes.Synthesis of nickel(II) complexes with thioamide and thione ligands.Crystallization of as many complexes as possible and determination of their structures by X-ray crystallography.Characterization of complexes b y IR and UV-VIS spectroscopy.A comparative study of complexes based on spectroscopic and structural data.