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inorganic chemistry
Inorganic Chemistry 7th Edition Mark Weller, Tina Overton, Jonathan Rourke - Solutions
The existence of a maximum oxidation number of +6 for both uranium (Z = 92) and tungsten (Z = 74) prompted the placement of U under W in early periodic tables. When the element after uranium, neptunium (Z = 93), was discovered in 1940, its properties did not correspond to those of rhenium (Z = 75),
Discuss the assertion that the chemistry of the actinoids is closer to that of the d-block elements than to that of the lanthanoids.
Explain why UF3 and UF4 are high melting point solids whereas UF6 sublimes at 57°C.
Predict what species are formed when Pu metal is dissolved in dilute HCl and the nature of the solid product that forms when HF is subsequently added.
In their review on new commercial applications of Ln chemistry (Acc. Chem. Res., 2016, 49, 844), Guillou and coworkers explain how the coordination of different Ln(III) ions within metal–organic frameworks can be exploited to produce unique luminescent inks for anti-counterfeiting signatures.
Predict the average bond order for the An–O bonds in the following AnO22+(aq) cations: UO22+, NpO22+, PuO22+, AmO22+ and explain why a linear arrangement is found in all cases.
The processing of spent nuclear fuel and separation of the lighter actinoid elements, U, Np, and Pu, is an important industrial process. Discuss the chemistry involved in the various methods used to extract and separate these elements.
Derive the ground state term symbol for the following ions: Tb3+, Nd3+, Ho3+, Er3+, Lu3+.
The 24-membered U ring complex shown below is very unusual as it is rigid and contains both bridging azido and bridging nitrido ligands. Describe how this complex was synthesized and the significance of the bonding that is observed.
Comment on the following statements which may be correct, incorrect or partly correct. (a) The magnetic moment of Gd3+ is given by the spin-only formula; (b) Water substitution rates for Ln3+ (aq) ions are lower than those of M3+(aq) ions of 3d elements; (c) Nonlabile complexes of
A lanthanoid compound is reported in which Ln appears to be in the 5+ oxidation state. Explain why such a discovery (fictitious in this case) would be highly significant, and predict the most likely identity of the lanthanoid.
The elements Eu and Gd display certain similarities with Mn and Fe. Discuss this statement.
Explain why stable and readily isolable carbonyl complexes are unknown for the lanthanoids.
Suggest a synthesis of neptunocene from NpCl4.
Account for the similar electronic spectra of Eu3+ complexes with various ligands, compared to the variation of the electronic spectra of Am3+ complexes as the ligand is varied.
Predict a structure type for BkN based on the ionic radii r(Bk3+) = 96 pm and r(N3−) = 146 pm.
Discuss why the U–O bond length in the uranyl ion [UO2]2+ typically has a value around 180 pm, just slightly more than the Os–O bond length in [OsO2]2+ (174 pm), whereas the conventional ionic radius of U6+ (73 pm) is much larger than that of Os6+ (54 pm).
Outline how you could prepare samples of (a) MgCr2O4,(b) LaFeO3, (c) Ta3N5, (d) LiMgH3, (e) KCuF3, (f) The zeolite A analogue with Ga replacing Al, Na12[Si12Ga12O48]⋅nH2O.
Identify the likely products of the reactions (a) Li,CO,+CoO_800C,0_ (b) 2 Sr(OH)₂ +WO+MnO 900°C,0,
Describe the inorganic chemistry involved in the operation of a lambda sensor (an exhaust-gas oxygen sensor) in a vehicle engine.
To obtain high oxidation states for first row d metals in complex oxides, e.g. Sr2Fe(IV)O4, compounds are normally prepared at as low a temperature as possible commensurate with the reaction. Discuss the thermodynamic reasons for the use of these conditions and explain why the optimum temperature
When NiO is doped with small quantities of Li2O, the electronic conductivity of the solid increases. Provide a plausible chemical explanation for this observation.
Heating a complex oxide under ammonia can lead to nitridation (with nitrogen replacing oxygen) or reduction (with the production of nitrogen and water). Describe possible products that might be formed when SrWO4 is heated in ammonia. By consideration of the relative entropy changes for the two
The compound FexO generally has x < 1. Describe the probable metal ion defect that leads to x being less than 1.
Use ionic radii data (Resource section 1) to suggest possible dopants to increase anion conductivity in (a) PbF2(b) Bi2O3 (six-coordinate Bi3+).Resource section 1.Ionic radii are given (in picometres, pm) for the most common oxidation states and coordination geometries. The coordination number is
Describe the delafossite structure type adopted by some compounds of the stoichiometry MM′X2. Which elemental combinations are known to form this structure type? Discuss their electronic properties when X = O, and potential applications as photocatalysts.
How might you distinguish experimentally the existence of a solid solution from a series of crystallographic shearplane structures for a material that appears to have variable composition?
What are the advantages of sol–gel routes, in comparison with direct high-temperature reaction methods, in the synthesis of complex metal oxides? Why are sol–gel routes used to prepare finely divided or nanoparticulate material?
Superconductors are often classified as type I or II. Describe the physical characteristic that determines the classification of a superconductor into one or the other of these types. Classify the following materials in their superconducting state(a) Hg,(b) TaSi2, (c) YBCO, (d) Nb3Ge.
Draw one unit cell in the ReO3 structure, showing the M and O atoms. Does this structure appear to be sufficiently open to undergo Na+ ion intercalation? If so, where might the Na+ ions reside? Describe the likely structure type for a material where the Na:Re ratio is 1:1.
Discuss how various chemical substitutions led to the discovery, and subsequent optimization of the properties, of the superconducting materials with the LnFeOAs structure type. Describe the compositional and structural chemistry of other recently discovered iron-based superconducting materials.
‘Double perovskites’ of the composition AA′BB′O6 have been widely studied in respect of their magnetic properties. For A = Rb and A′ = Sr suggest some possible ions for the B and B′ sites in a double perovskite.
Discuss differences in the properties of zeolites, zeotypes (frameworks built from oxotetrahedral species other than AlO4 and SiO4), and metal–organic frameworks (MOFs).
The iodostannate perovskites, ASnI3, have been studied as potential semiconductors for applications as photovoltaics. By reference to the known APbI3 phases that adopt the perovskite structure suggest which cations, A+, might form a perovskite in the ASnI3 system.
Describe recent progress towards the commercialization of MOFs.
Predict the Néel temperature for CrO.
One target for a material of use for hydrogen storage in transport applications is that it should contain 10 weight per cent hydrogen. Which class of material is the most promising for this application? What are the different requirements of a static system that might be used to store hydrogen
Write possible formulas for a sulfide and a fluoride that might adopt the spinel structure.
What are the properties of an ideal inorganic pigment?
Which of the materials (a) YBa2Cu4O8, (b) Ca1.8Na0.2CuO2Cl2,(c) Gd2Ba2Ti2Cu2O11, (d) SrCuO2.12, which all contain layers of the stoichiometry CuO2, might be expected to be high-temperature superconductors?
Discuss the recent advances in perovskite solar cell chemistry that have driven device efficiencies to over 20 per cent.
Explain why the colour of Ta2O5 changes from white to red when it is heated under flowing NH3.
Summarize recent research efforts directed towards finding improved materials for the photocatalytic splitting of water.
State Zachariasen’s two generalizations that favour glass formation and apply them to the observation that cooling molten CaF2 leads to a crystalline solid whereas cooling molten SiO2 at a similar rate produces a glass.
Compare and contrast the chemistries of graphite and C60 with respect to their compounds in association with the alkali metals.
Classify the oxides (a) BeO, (b) TiO2, (c) La2O3, (d) B2O3,(e) GeO2 into glass-forming and non-glass-forming.
‘The increased reactivity that allows the design and synthesis of materials based on molecular units also means that these compounds are unsuitable for many applications that currently use inorganic materials.’ Discuss this remark.
Which metal fluorides might be glass-forming?
Explain whether vapour-phase or solution-based techniques typically lead to (a) Larger size distributions in nanoparticle synthesis, (b) Agglomerated particles that are strongly bonded to one another in so-called hard agglomerates.
Describe two methods that could be used to prepare the intercalation compound LixTiS2, x = 0.5.
(a) Discuss the difference between homogeneous and heterogeneous nucleation from the vapour phase. (b) Which type of nucleation is preferred for the growth of a thin film in this process?(c) Which type of nucleation is preferred for the growth of nanoparticles in this process?
Reaction of ZrS2 (c lattice parameter 583 pm) with [Co(η5-C5H5)2] gives a compound with a c lattice parameter of 1164 pm, and reaction with [Co(η5-C5Me5)2] gives a product with a corresponding lattice parameter of 1161 pm; ZrS2 does not react with [Fe(η5-C5H5)2]. Explain these observations.
Describe the difference between a physical vapour and a chemical vapour with respect to the type and stability of the vapour species.
Nanotubes are widely known for carbon. Find an example of an inorganic nanotube not based on carbon and describe its synthesis and properties as compared to the corresponding bulk material. Compare its structure to the carbon nanotubes.
Why isn’t BeH2 considered to be a suitable hydrogenstorage material?
Describe the interactions between Mo6S8 units in a Chevrel phase.
(a) Give a definition for scanning probe microscopy that makes clear both what it is and why it is called scanning probe microscopy. (b) Using a material of interest to you, pick any scanning probe microscopy method and describe how you might use it to characterize an important aspect of your
Which of the elements Be, Mg, Ga, Zn, P, and Cl might form structures in which the element is incorporated into a framework as an oxotetrahedral species?
Compare and contrast the band energies for a quantum dot nanocrystal and a bulk semiconductor.
Propose formulas for structures that would be isomorphous with SiO2 and zeolites of the same stoichiometry involving Al, P, B, and Zn, or mixtures thereof, replacing Si.
(a) Give two examples of applications of quantum wells.(b) Describe why quantum wells are used and if either molecular materials or traditional solid-state materials can exhibit similar properties. (c) How are quantum wells made?
Aluminosilicate surfaces in zeolites act as strong Brønsted acids, whereas silica gel is a very weak acid. (a) Give an explanation for the enhancement of acidity by the presence of Al3+ in a silica lattice. (b) Name three other ions that might enhance the acidity of silica.
(a) What is the relevance of self-assembly to the fabrication of nanomaterials?(b) What role will it play in nanotechnology?
Discuss shape selectivity with respect to catalytic processes involving zeolites including mechanisms involving reactant, transition state, and product selectivity.
(a) Describe the two classes of inorganic–organic nanocomposites based on their bonding types. (b) Give one example of a nanocomposite in each class.
Describe what sorts of ligands are needed to produce metal–organic frameworks (MOFs).
Discuss the synthesis, properties, and potential applications of ultrathin two-dimensional nanosheets of layered transition metal dichalcogenides.
Calculate the mass percentage of hydrogen in NaBH4 and state whether or not this material might be suitable for hydrogen storage.
The synthesis method described in this chapter for generating CdSe quantum dots involves the use of rather toxic compounds. Explore the chemical literature to find a more recent example that uses less toxic substances. Describe the solvation step, the nucleation step, and the growth step in each
Substitution of Mg by small amounts of Li and Al into MgH2 improves its hydrogen-storage properties. Write a formula for this lithium aluminium magnesium dihydride and explain how Li and Al would be incorporated into the structures.
The Grätzel cell has been described as a useful photoelectrochemical cell. Describe how the photoelectrochemical cell differs from the conventional photovoltaic cell. Describe why the nanostructure TiO2 is important for the improved performance. What other inorganic species play an important role
Discuss how the various physical properties of graphene may lead to the incorporation of this material into future technologies.
Egyptian blue, CaCuSi4O10, is pale blue and the spinel CuAl2O4 is an intense blue-green. Explain the difference.
Carbon nanotubes have been suggested for use as wires in molecular electronics. Describe the challenges of using nanotubes as wires in terms of connecting two functional electronic devices. Describe a possible technique to overcome some of these problems.
Dissolution of Na2S9 in polar solvents initially produces an intensely blue-coloured solution. In air the colour fades after a few minutes. Explain these observations by reference to the species responsible for the colour of ultramarine.
Describe the properties of an ideal photocatalyst for water-splitting.
Summarize the potential impact of heterogeneous oxidation catalysts in chemistry.
Place the semiconductors AlP, BN, InSb, and C (diamond) in order of the expected band gap.
Discuss the applications and mechanisms of oxidation and ammoxidation catalysts such as bismuth molybdate
Describe the structures of Na2C60 and Na3C60 in terms of hole-filling in a close-packed array of fulleride molecular ions.
Discuss the advantages of a solid support in catalysis by reference to the use of [Ni(POEt)3]4 in alkene isomerization.
(a) Compare the surface area for two spherical objects: one has a diameter of 10 nm and the other has a diameter of 1000 nm. (b) Describe whether these two objects are considered nanoparticles by using the size-based definition of a nanomaterial.(c) Using a surface-area-related property,
J.A. Botas et al. discuss the catalytic conversion of vegetable oils into hydrocarbons suitable for use as biofuels (Catal. Today, 2012, 195, 1, 59). What are the most important features of catalysts that are used for these reactions? How was the incorporation of transition metals expected to
(a) Explain the difference between the top-down and bottom-up methods of fabrication of materials. Be specific and provide one example of each. (b) Give one advantage and one disadvantage for each synthesis method.
(a) Describe the three basic steps in nanoparticle formation from solution. (b) Explain why two steps should occur independently to achieve a uniform size distribution. (c) What are stabilizer molecules used for in nanoparticle synthesis?
Describe the processes occurring during Ostwald ripening.
(a) Draw a schematic diagram of a core–shell nanoparticle.(b) Briefly describe how core–shell nanoparticles could be made using either vapour-phase or solution-based techniques. (c) For what purpose would core–shell nanoparticles be used?
Which inorganic materials, other than graphite, have structures with strong in-layer bonds but much weaker interactions between layers, and so might be exfoliated into single sheets?
Why is the platinum/rhodium catalyst in automobile catalytic converters dispersed on the surface of a ceramic rather than used in the form of a thin metal foil?
Alkanes are observed to exchange hydrogen atoms with deuterium gas over some platinum metal catalysts. When 3,3-dimethylpentane in the presence of D2 is exposed to a platinum catalyst and the gases are observed before the reaction has proceeded very far, the main product is CH3CH2C(CH3)2CD2CD3 plus
Tetramethyllead can be synthesized in the laboratory from lead(II) chloride and a Grignard reagent according to the following reaction:Assuming that the synthesis was attempted with 4.0 g of PbCl2 and an excess of the Grignard reagent, and that 1.54 g of the product were isolated, calculate the
The effectiveness of platinum in catalysing the reaction 2H+(aq) + 2 e− → H2(g) is greatly decreased in the presence of CO. Suggest an explanation.
Describe the role of electrocatalysts in reducing the overpotential in the oxygen reduction reaction in fuel cells.
The noncatalytic route to manufacture of ethylene oxide produces 3.5 kg of waste for every 1 kg of product. Calculate the E-factor for this process.
DDT was one of the first synthetic pesticides and was widely used as an effective control measure for malaria, typhoid, and other insect-borne diseases during World War II. During the 1950s–1960s it became very widely used for insect control on crops, in animals, and in the home. However, it was
The old Monsanto process for manufacturing disodium iminodiacetate produces 7 kg of waste for every 1 kg of product. Calculate the E-factor for this process.
In their article ‘Industrial research: drug companies must adopt green chemistry’ (Nature, 2016, 534, 27), J. Tucker and M. Faul describe how they transformed their approach to manufacturing to save their company time and money by making drugs more sustainably. Summarize the approaches they
Ferrocene can be acetylated by reacting with excess acetic anhydride according to the following reaction:If the reaction used 1.5 g of ferrocene and produced 1.15 g of acetylferrocene, calculate the yield and the atom economy of the reaction and comment on the values.
In the 1960s, the anti-nausea drug thalidomide caused severe birth defects in babies born to mothers who had taken the drug to relieve morning sickness. Discuss the reasons why this was a serious issue in Europe and yet not in the US. Describe why the drug is toxic and under what circumstances it
Discuss how recycling is different from green chemistry. Evaluate the advantages and disadvantages of each.
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