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inorganic chemistry

Questions and Answers of Inorganic Chemistry

Define the terms (a) Turnover frequency, (b) Selectivity, (c) Catalyst, (d) Catalytic cycle, (e) Catalyst support.
Chlorofluorocarbons (CFCs) were developed as novel, safe refrigerants. What refrigerants were they designed to replace and what were their hazards? What were the problems associated with CFCs? Review
Show how reaction of MeCOOMe with CO under conditions of the Monsanto ethanoic acid process can lead to ethanoic anhydride.
The addition of promoters can further enhance the rate of a catalysed reaction. Describe how the promoters allowed the iridium-based Cativa process to compete with the rhodium-based process in the
Define the terms risk and hazard.
Briefly outline the different industrial processes that have been used to manufacture acetic anhydride. Discuss the green credentials of each process.
What is the green chemistry safety principle?
Apart from direct O-atom transfer (Fig. 26.50), another mechanism proposed for Mo enzymes is indirect O-atom transfer, also known as coupled electron-proton transfer. In this mechanism, shown in Fig.
J.A. Botas et al. discuss the catalytic conversion of vegetable oils into hydrocarbons suitable for use as biofuels (Catal. Today, 2012, 195, 59). What are the most important features of catalysts
Figure 26.68 shows Mössbauer spectra of a sample of ferredoxin from chloroplasts at 77 K. Interpret the data with regard to the oxidation states an spin states of the two Fe atoms and comment on the
Why is real-time, in-process monitoring beneficial to green chemical processes?
Ionic liquids can be used as catalysts as well as solvents. Write a review on the use of ionic liquids as catalysts.
Sensors are increasingly being used in situ to monitor reactions and effluent streams in industry. What are the advantages and disadvantages of using in situ sensors compared to traditional
Ultimately, the overall ‘green’ credentials of any process can only be evaluated through life cycle analysis (LCA). Identify what components would be considered in the LCA of the synthesis of
Predict the properties of Na+, Ca2+, and Cl– binding sites that would be important for providing selectivity in their respective transmembrane ion transporters.
In an article on the detection of Zn(II) that is released from neuronal tissue (brain, nerves) following trauma, E. Tomat and S.J. Lippard describe the development of special ligands that are highly
Calcium-binding proteins can be studied by using lanthanoid ions (Ln3+). Compare and contrast the coordination preferences of the two types of metal ion and suggest techniques in which lanthanoid
In justifying research into small molecule catalysts for producing NH3 from N2, it is sometimes stated that nitrogenase is an ‘efficient’ enzyme: how true is this statement? Comment critically on
In zinc enzymes, ‘spectroscopically silent’ Zn(II) can often be replaced by Co(II) with high retention of activity. Explain the principles by which this substitution can be exploited to obtain
‘In Mo enzymes, the bond between a terminal oxo anion and Mo(VI) is usually written as a double bond, whereas it is more correctly assigned as a triple bond.’ Discuss this statement. Suggest how
Compare and contrast the acid–base catalytic activities of Zn(II), Fe(III), and Mg(II).
Propose physical methods that would allow you to determine whether a reactive intermediate isolated by rapid freeze quenching contains Fe(V).
The structure of the P-cluster in nitrogenase differs significantly between oxidized and reduced states. Comment on this observation in the light of proposals that it participates in long-range
Microorganisms can synthesize the acetyl group (CH3CO–) by direct combination of methyl groups with CO. Make some predictions about the metals that are involved.
Comment on the implications of discovering, by microwave detection, substantial levels of O2 on a planet in another solar system.
Reductive dehalogenases are cobalamin-containing enzymes which catalyse the replacement of a halogen atom by a hydrogen atom in organic molecules (X is typically Cl). With reference to the principles
Compounds of Au(III) are under investigation as anticancer drugs. Predict some of the similarities and contrasts with Pt(II) compounds.
In their article ‘Targeting and delivery of platinum-based anticancer drugs’ (Chem. Soc. Rev. 2012, 42, 202), X. Wang and Z. Guo review the expanding field of nanoparticle-based drug delivery.
Copper bracelets have long been thought to have beneficial effects for rheumatism sufferers. Without surmising on the possible molecular mechanism of action at the target site, describe the chemical
Write an essay on the different ways that metallocenes are being used in medicine.
Boranocarbonate ([H3BCO2]2–) is a promising CORM which is stable in alkali but decomposes slowly to release CO once introduced to neutral or mildly acidic solutions such as the bloodstream. Predict
Write a short essay on selected elements of the periodic table with regard to their medical uses.
Comment, from a chemistry angle, on the ways that Ga(III) compounds might act as drugs through the inhibition of certain types of Fe-containing enzyme.
Identify particular chemical properties of bismuth that suit it for its special role in treating gastric ailments, noting that the stomach environment is highly acidic.
In Problem 7.12 we looked at the successive formation constants for 1,2-diaminoethane complexes of three different metals. Using the same data, discuss the effect of the metal on the formation
Starting with Fig. 20.12, show how, using a crystal-field approach, an extreme tetragonal distortion leads to the orbital energy-level diagram in Fig. 20.10. Perform a similar analysis for
Determine the configuration (in the form t2gx egy or ext2y , as appropriate), the number of unpaired electrons, and the ligandfield stabilization energy in terms of ΔO or ΔT and P for each of the
In a fused magma liquid from which silicate minerals crystallize, the metal ions can be four-coordinate. In olivine crystals, the M(II) co-ordination sites are octahedral. Partition coefficients,
Both H− and P(C6H5)3 are ligands of similar field strength, high in the spectrochemical series. Recalling that phosphines act as π acceptors, is π-acceptor character required for strong-field
Write the d-orbital configurations and use the Tanabe–Sugano diagrams (Resource section 6) to identify the ground term of (a) Low-spin [Rh(NH3)6]3+, (b) [Ti(OH2)6]3+, (c) High-spin
Estimate the spin-only contribution to the magnetic moment for each complex in Exercise 20.1.Data from Exercises 20.1Determine the configuration (in the form t2gx egy or ext2y , as appropriate), the
Using the Tanabe–Sugano diagrams in Resource section 6, estimate ΔO and B for (a) [Ni(OH2)6]2+ (absorptions at 8500, 15400, and 26000 cm−1) (b) [Ni(NH3)6]2+ (absorptions at 10750, 17500, and
By considering the splitting of the octahedral orbitals as the symmetry is lowered, draw the symmetry-adapted linear combinations and the molecular orbital energy-level diagram for σ bonding in a
Match each of the magnetic moments, 3.8, 0, 1.8, 5.9 (in μB), with one of the species: [Fe(CN)6]3−, [Fe(H2O)6]3+, [CrO4]2−, [Cr(H2O)6]3+.
Draw the appropriate symmetry-adapted linear combinations and the molecular orbital diagram for σ bonding in a square-planar complex. The point group is D4h. Take note of the small overlap of the
Consider a trigonal prismatic six-coordinate ML6 complex with D3h symmetry. Use the D3h character table (Resources section 4) to divide the d orbitals of the metal into sets of defined symmetry type.
Enthalpies of hydration and values of the ligand-field splitting parameter, ΔO, are given for some octahedrally coordinated ions. (a) Plot the enthalpies of hydration against the number of d
MLCT bands can be recognized by the fact that the energy is a sensitive function of the polarity of the solvent (because the excited state is more polar than the ground state). Two simplified
The spectrum of d1 Ti3+(aq) is attributed to a single electronic transition eg ← t2g. The band shown in Fig. 20.3 is not symmetric and suggests that more than one state is involved. Suggest how to
Solutions of the complexes [Co(NH3)6]2+, [Co(OH2)6]2+ (both Oh), and [CoCl4]2− are coloured. One is pink (absorbs blue light), another is yellow (absorbs violet light), and the third is blue
For each of the following pairs of complexes, identify the one that has the larger LFSE:(a) [Cr(OH2)6]2+ or [Mn(OH2)6]2+(b) [Fe(OH2)6]2+ or [Fe(OH2)6]3+(c) [Fe(OH2)6]3+ or [Fe(CN)6]3–(d)
Interpret the variation, including the overall trend across the 3d series, of the following values of oxide lattice enthalpies (in kJ mol−1). All the compounds have the rock-salt structure: CaO
In a trigonal bipyramidal complex the axial and equatorial sites have different steric and electronic interactions with the central metal ion. Consider a range of some common ligands and decide which
Vanadium(IV) species that have the V=O group have quite distinct spectra. What is the d-electron configuration of V(IV)? The most symmetrical of such complexes are [VOL5] with C4v symmetry, with the
A neutral macrocyclic ligand with four donor atoms produces a red diamagnetic low-spin d8 complex of Ni(II) if the anion is the weakly coordinating perchlorate ion. When perchlorate is replaced by
Bearing in mind the Jahn–Teller effect, predict the structure of [Cr(OH2)6]2+.
Consider spin-crossover complexes and identify the features that a complex would need for it to be used in (a) A practical pressure sensor (b) A practical information-storage device.
Consider the molecular orbital diagram for a tetrahedral complex (based on Fig. 20.8) and the relevant d-orbital configuration, and show that the purple colour of [MnO4]− ions cannot arise from a
Consider the octahedral [NiF6]3− ion. What spin state and magnetic moment could it have? How would the Jahn-Teller effect affect the two spin states, and how might this complicate an interpretation
Write the Russell–Saunders term symbols for states with the angular momentum quantum numbers (L,S): (a) (0, 5/2),(b) (3, 3/2), (c) (2, 1/2), (d) (1,1).
Identify the ground term from each set of terms: (a) 1P, 3P, 3F, 1G; (b) 3P, 5D, 3H, 1I, 1G; (c) 6S, 4P, 4G, 2I.
Give the Russell–Saunders terms of the configurations: (a) 4s1, (b) 3p2. Identify the ground term.
The gas-phase ion V3+ has a 3F ground term. The 1D and 3P terms lie, respectively, 10642 and 12920 cm−1 above it. The energies of the terms are given in terms of Racah parameters as E(3F) = A −
Match each of the extinction coefficients, εmax, <1, 10, 100, >104 (in dm3 mol−1 cm−1), with one of the species: [MnO4]− in H2O; Fe3+(aq) in 1.0 M HClO4; Co2+(aq) in 1.0 M HClO4;
The spectrum of [Co(NH3)6]3+ has a very weak band in the red and two moderate intensity bands in the visible to near-UV. How should these transitions be assigned?
The Racah parameter B is 460 cm−1 in [Co(CN)6]3− and 615 cm−1 in [Co(NH3)6]3+. Consider the nature of bonding with the two ligands and explain the difference in nephelauxetic effect.
An approximately ‘octahedral’ complex of Co(III) with ammine and chlorido ligands gives two bands with εmax between 60 and 80 dm3 mol−1 cm−1, one weak peak with εmax = 2 dm3 mol−1 cm−1,
Ordinary bottle glass appears nearly colourless when viewed through the wall of the bottle but visibly coloured (green) when viewed from the end so that the light has a long path through the glass.
Solutions of [Cr(OH2)6]3+ ions are pale greeny-blue but the chromate ion, [CrO4]2−, is an intense yellow. Characterize the origins of the transitions and explain the relative intensities.
Classify the symmetry type of the d orbitals in a tetragonal C4v symmetry complex, such as [CoCl(NH3)5]2+, where the Cl lies on the z-axis.(a) Which orbitals will be displaced from their position in
The rate constants for the formation of [CoX(NH3)5]2+ from [Co(NH3)5(OH2)]3+ for X = Cl− ,Br− ,N−3, and SCN− differ by no more than a factor of 2. What is the mechanism of the substitution?
Given NaBH4, a hydrocarbon of your choice, and appropriate ancillary reagents and solvents, give formulas and conditions for the synthesis of (a) B(C2H5)3, (b) Et3NBH3.
Identify the B-containing compounds A, B, and C. BF3 CaF2 C LiAlH4 heat A H₂O B
The relative positons of tetrahedral and octahedral holes between close-packed layers may be described using the PTOT system, where P represents a close-packed layer, and T and O the tetrahedral and
Discuss the similarities in the chemistry of Tl(I) to those of the alkali metals and particularly that of potassium.
Give a balanced chemical equation and conditions for the recovery of boron.
Use suitable molecular-orbital software to calculate the wavefunctions and energy levels for closo-[B6H6]2−. From that output, draw a molecular orbital energy diagram for the orbitals primarily
How would you expect the Group 13 element to hydrogen bond enthalpy to change as the group is descended? Hence explain the nonexistence of TlH3. The most important oxo salts of Group 13 are the
Explain the important role of cryolite, Na3AlF6, in the extraction of aluminium metal.
In his paper ‘Covalent and ionic molecules: why are BeF2 and AlF3 high melting point solids whereas BF3 and SiF4 are gases?’ (J. Chem. Educ., 1998, 75, 923), R.J. Gillespie makes a case for the
Why does a droplet of mercury cause aluminium to react rapidly with air?
Nanotubes of C and BN have been synthesized by C. Colliex et al. (Science, 1997, 278, 653). (a) What are the advantageous properties of these nanotubes over carbon analogues?(b) Outline the
Diborane has been used as a rocket propellant. Calculate the energy released from 1.00 kg of diborane given the following values of The combustion reaction is B2H6(g) + 3O2(g) → 3H2O(g) + B2O3(s).
Describe the bonding in (a) BF3, (b) AlCl3, (c) B2H6, (d) TlF.
M. Montiverde discusses ‘Pressure dependence of the superconducting temperature of MgB2’ (Science, 2001, 292, 75). (a) Describe the bases of the two theories that have been postulated to
Arrange the following in order of increasing Lewis acidity: BF3, BCl3, AlCl3. In the light of this order, write balanced chemical reactions (or no reaction) for:(a) BF3N(CH3)3 + BCl3 →(b) BH3CO +
Thallium tribromide (1.11 g) reacts quantitatively with 0.257 g of NaBr to form a product A. Deduce the formula of A. Identify the cation and anion.
Shuji Nakamura was awarded the 2014 Nobel Prize for Physics in part for his invention of blue LEDs based on gallium nitride. Discuss the chemistry of gallium nitride including its synthesis,
In their paper ‘New structural motifs in metallaborane chemistry: synthesis, characterization, and solid-state structures of [(Cp*W)3(μ-H)B8H8], [(Cp*W)2B7H9], and [(Cp*Re)2B7H7] (Cp* =
Does B2H6 survive in air? If not, write the equation for the reaction.
Predict how many different boron environments would be present in the proton-decoupled 11B-NMR of (a) B5H11, (b) B4H10.
Predict the products from the hydroboration of (a) (CH3)2 C=CH2, (b) CH=CH.
Using BCl3 as a starting material and other reagents of your choice, devise a synthesis for the Lewis acid chelating agent, F2B–C2H4–BF2.
Determine the point group of a B2Cl4 molecule in (a) The gas phase (staggered) (b) The solid (planar) structures.
Give the IUPAC names of (a) B10H14,(b) [B12H12]2−, (c) Arachno-[B12H14]2−.
Give balanced chemical equations for the synthesis of 1,2-B10C2H10(Si(CH3)3)2 starting with decaborane(14) and other reagents of your choice.
Draw the B12 unit that is a common motif of boron structures; take a viewpoint along a C2 axis.
Which boron hydride would you expect to be more thermally stable, B6H10 or B6H12? Give a generalization by which the thermal stability of a borane can be judged.
How many skeletal electrons are present in B5H9?
(a) From its formula, classify B10H14 as closo, nido, or arachno. (b) Use Wade’s rules to determine the number of framework electron pairs for decaborane(14). (c) Verify by detailed

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