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inorganic chemistry

Questions and Answers of Inorganic Chemistry

Figure 13.21 shows four hydrogen-bonded molecules of B2(OH)4. To what point group does a single molecule of B2(OH)4 belong?Figure 13.21. .....
Figure 13.11c shows the solid state structure of the [Al(BH4)4]‾ ion, present in [Ph3MeP][Al(BH4)4]. In the light of these structural data, account for the following observations, recorded for the
Explain how, during dimerization, each BH3 molecule acts as both a Lewis base and a Lewis acid.
(a) Suggest products for the following reactions.(b) PhB(OH)2 forms dimers in the solid state. Dimers further associate into a 3-dimensional network. Describe how this assembly is likely to arise.
The ordering of the relative stabilities of adducts L · BH3 for some common adducts is, according to L: Me2O < THF < Me2S < Me3N < Me3P < H‾. In addition to answering each of the
The reaction ofK[B(CN)4] withClF3 in liquid HF leads to the formation of K[B(CF3)4]. Explain why, in the 11B NMR spectrum of this salt, a 13-line pattern is observed. What will be the relative
The solvolysis of K[B(CF3)4] in concentrated H2SO4 generates (F3C)3BCO. (a) Write a balanced equation for the solvolysis process. (b) In the gas phase, (F3C)3BCO possesses C3 rather than
(a) Write down the formula of cryolite. (b) Write down the formula of perovskite. (c) Cryolite is described as possessing a 3-dimensional structure closely related to that of perovskite.
(a) The behaviour of H3BO3 in aqueous solution is not typical of a mineral acid such as HCl or H2SO4. Illustrate, using appropriate examples, these differing behaviours. (b) The formula of borax
Compare the physical and chemical properties of α- and γ-alumina, choosing examples that highlight why it is important not to call Al2O3 simply ‘alumina’.
Write a brief account of the bonding and reactivity of borazine which emphasizes the ways in which this compound is similar or dissimilar to benzene.
GaCl3 reacts with KP(H)SitBu3 (equimolar amounts) to give KCl and two isomers of a 4-membered, cyclic compound which contains 38.74% C, 7.59% H and 19.06% Cl. Suggest the identity of the product, and
Use Wade’s rules to suggest likely structures for B5H9, [B8H8]2−, C2B10H12 and [B6H9]−. Are any cage-isomers possible?
(a) Comment why, in Fig. 13.1, the data are presented on a logarithmic scale. What are the relative abundances of Al (Fig. 13.1) and Mg (Fig. 12.2) in the Earth’s crust?(b) Show that the changes in
Suggest likely products for the following reactions, with the stoichiometries stated: (a) B5 H₂ + Br₂ (b) B4 H10 + PF3 (c) 1-BrB5H8 (d) 2-MeB5Hg 298 K KH, 195 K ROH
(a) Write balanced equations for the reactions of aqueous Ga+ with [I3]‾ , Br2, [Fe(CN)6]3+ and [Fe(bpy)3]3+.(b) The 205Tl NMR spectrum of an acidic solution that contains Tl3+ and 13C-enriched
(a) What type of semiconductors are formed by doping silicon with boron or gallium? Using simple band theory, explain how the semiconducting properties of Si are altered by doping with B or Ga.(b) An
Crystalline Ag2[B12Cl12] may be described as having a structure based on an anti-fluorite-type arrangement. By approximating each [B12Cl12]2− ion to a sphere, draw a diagram to represent a unit
(a) NMR spectroscopic data for [HAl(BH4)2]n are consistent with the compound existing in two forms in solution. One form is probably a dimer and the other, a higher oligomer. Each species possesses
(a) At 297 K, the 11B NMR spectrum of a CD2Cl2 solution of [Ph4As][B6H7] shows one doublet (δ–18.0 ppm, J = 147 Hz). In the 1H NMR spectrum, two signals are observed (δ–5.5 ppm, broad; δ +1.1
Comment on the following statements:(a) World gallium production increased from 37 t in 1990 to 435 t in 2013.(b) Rubies are composed of α-Al2O3 (corundum) but are red in colour.(c) The adduct
Glass is manufactured by cooling a melt to produce a rigid structure without crystallization. The binary oxides B2O3 and SiO2 are the primary components of borosilicate glass. Possible structural
The commercial applications of boron nitride include those as an electrical insulator, a lubricant, an abrasive, a material for making crucibles for high temperature work (e.g. moulds for molten
(a) Two-electron reduction of B5H9 followed by protonation is a convenient route to B5H11. What structural change (and why) do you expect the B5 cage to undergo during this reaction?(b) Account for
(a) Write equations to show how you expect compounds 7.24 to 7.28 to dissociate in aqueous solution. (b) Suggest how compound 7.29 will react with NaOH in aqueous solution. What salts would it be
The values of pKa(1) and pKa(2) for chromic acid (H2CrO4) are 0.74 and 6.49 respectively.(a) Determine values of Ka for each dissociation step. (b) Write equations to represent the dissociation
The values of log K for the following two equilibria are 7.23 and 12.27, respectively:Determine (a) Ksp for AgBr,(b) K for the reaction: Ag+ (aq) + 2NH3(aq) [Ag(NH3)2]+ (aq) Ag*(aq) + Br (aq) =
In aqueous solution, boric acid behaves as a weak acid (pKa = 9:1) and the following equilibrium is established:(a) Draw the structures of B(OH)3 and [B(OH)4]‾.(b) How would you classify the acidic
The structure of H5DTPA (see Box 4.3) is shown below:(a) Write equilibria to show the stepwise acid dissociation of H5DTPA. Which step do you expect to have the largest value of Ka?(b) In the complex
Four pKa values (1.0, 2.0, 7.0, 9.0) are tabulated for the acid H4P2O7. Write equations to show the dissociation steps in aqueous solution and assign, with reasoning, a pKa value to each step.
The values of pKa for CH3CO2H and CF3CO2H are 4.75 and 0.23, both of which are very nearly independent of temperature. Suggest reasons for this difference.
(a) To what equilibria do the values of pKa(1) = 10:71 and pKa(2) = 7:56 for the conjugate acid of H2NCH2CH2NH2 refer? (b) Calculate the corresponding values of pKb and write equations to show
Potassium chromate is used as an indicator in titrations for the determination of chloride ion. At the end-point of a titration of an aqueous solution of a metal chloride salt (e.g. NaCl) against
(a) Discuss the factors that contribute towards KCl being a readily soluble salt (35 g per 100 g H2O at 298 K). (b) Develop your answer to part (a) by using the following data: ΔhydHº(K+, g) =
When NaCN dissolves in water, the resulting solution is basic. Account for this observation given that pKa for HCN is 9.31.
Construct a thermochemical cycle for the decomposition of the phosphonium halides according to the equation:and use it to account for the fact that the most stable phosphonium halide is the iodide.
Write equations to illustrate the amphoteric behaviour of [HCO3]‾ in aqueous solution.
Which of the following oxides are likely to be acidic, basic or amphoteric in aqueous solution: (a) MgO;(b) SnO; (c) CO2; (d) P2O5; (e) Sb2O3; (f) SO2;(g) Al2O3; (h) BeO
Explain what is meant by the terms (a) Saturated solution; (b) Solubility; (c) Sparingly soluble salt;(d) Solubility product (solubility constant).
Comment on the following observations.(a) In its complexes, Co(III) forms strong bonds to O- and N-donor ligands, moderately strong bonds to P-donor ligands, but only weak bonds to As-donor
Write down expressions for Ksp for the following ionic salts: (a) AgCl; (b) CaCO3; (c) CaF2.
Calculate the solubility of BaSO4 at 298K in g per 100 g of water given that Ksp = 1:07 × 10−10.
Outline the changes that occur (a) To the salt, (b) To the water molecules, when solid NaF dissolves in water. How do these changes affect (qualitatively) the entropy of the system?
(a) Explain why water is described as being amphoteric.(b) Draw the structures of the conjugate acid of each of the following:(c) The value of Ksp(298 K) for Ag2CrO4 is 1:12 × 10–12. What mass of
(a) Comment on the fact that, of the group 1 cations, Li+ is the most strongly solvated in aqueous solution, even though the first coordination shell only contains four H2O molecules compared with
(a) What are the conjugate bases of the acids HF, [HSO4]‾, [Fe(OH2)6]3+ and [NH4]+? (b) What are the conjugate acids of the bases [HSO4]‾, PH3, [NH2]‾ and [OBr]‾? (c) What is the
The formation of a buffer solution is an example of the common-ion effect. Explain how a buffer works with reference to a solution containing acetic acid and sodium acetate.
Calculate the solubility of AgBr (Ksp = 5:35 × 10−13)(a) In aqueous solution and (b) In 0.5M KBr solution.
Magnesium oxide is more soluble in aqueous magnesium chloride than in pure water. Discuss this observation.
Soda-water is made by saturating H2O with CO2. If you titrate soda-water with alkali using phenolphthalein as indicator, you obtain a fading end-point. What does this suggest?
What explanation can you give for the decrease in solubility of the alkaline earth metal sulfates in the sequence CaSO4 > SrSO4 > BaSO4?
(a) Give expressions to define the stepwise stability constants for equilibria 7.66 and 7.68. (b) For each of the complex ions formed in steps 7.66 and 7.68, gives expressions to define the
How many chelate rings are present in each of the following complexes? Assume that all the donor atoms are involved in coordination. (a) [Cu(trien)]2+;(b) [Fe(ox)3]3−; (c)
Suggest reasons for the following observations. (a) Although Pd(II) complexes with monodentate O-donor ligands are not as plentiful as those with P-, S- and As-donor ligands, Pd(II) forms many
(a) For [Pd(CN)4]2‾, a value of log β4 of 62.3 (at 298K in aqueous medium) has been determined. To what equilibrium process does this value refer?(b) For the equilibrium:the value of log K is
(a) Aqueous solutions of copper(II) sulfate contain the [Cu(OH2)6]2+ ion. The pH of a 0.10moldm−3 aqueous CuSO4 solution is 4.17. Explain the reason why the solution is acidic, and determine Ka for
Iron overload is a medical condition where the body cannot cope with abnormally high levels of iron in the system. Chelation therapy by administering desferrioxamine, 7.31, is used to treat the
Among the naturally occurring minerals of Al are diaspore (α-AlO(OH)), boehmite (γ-AlO(OH)) and gibbsite (γ-Al(OH)3). At low pH, reactions with H+ give rise to water-soluble [Al(OH2)6]3+,
The extraction of metals from primary (naturally occurring ores) and secondary (recycled materials) sources is of huge industrial importance. The manipulation of equilibria in, for example, solvent
The natural sulfur cycle involves many sulfur reducing and sulfur-oxidizing bacteria. For example, S2‾ is oxidized to elemental sulfur and to [SO4]2–, and the reverse processes convert mobile
Using data in Appendix 11, determine which of the following species is thermodynamically unstable with respect to disproportionation (and under what conditions) in aqueous solution: (a) Fe2+; (b)
(a) Using appropriate data from Appendix 11, determine E°cell for the disproportionation of H2O2.(b) Calculate ΔGo for this process. (c) Comment on the fact that H2O2 can be stored without
Write balanced half-equations corresponding to the steps shown in the potential diagrams in Fig. 8.2.Figure 8.2 Acidic solution (pH 0) [MnO4] Alkaline solution (pH 14)
Using data from Table 8.1 and from Section 8.3, explain why H2 is evolved when powdered Ag is heated with a concentrated solution of HI.Data from Table 8.1 Table 8.1 Selected standard reduction
Determine ΔGo(298 K) for the reaction:given the following data:What does the value of ΔGo tell you about the tendency of precipitated CuCl to disproportionate? 2+ 2CuCl(s) Cu²+ (aq) + 2Cl(aq) +
Give the oxidation state of each element in the following compounds and ions; Pauling electronegativity values in Appendix 7 may be useful:(a) CaO; (b) H2O; (c) HF; (d) FeCl2; (e) XeF6;(f)
Using appropriate data from eqs. 8.43 to 8.47, confirm the value of Eo given for eq. 8.48.Equations 12+ (aq) + 2e Mn(s) Mn²+ [MnO4] (aq) + e[MnO4)² E = -1.19 V (aq) E = +0.56 V 2+ MnO₂ (s) + 4H+
Calculate the overall formation constant for [Fe(CN)6]3−, given that the overall formation constant for [Fe(CN)6]4− is ≈ 1032, and that: Fe³+ (aq) + e Fe²+ (aq) [Fe(CN)6]³(aq) E = +0.77
Using data from Table 8.1, write down the spontaneous cell process, and calculate Eocell and ΔGo for the following combinations of half-cells:Data from Table 8.1 (a) Ag+ (aq) +e=Ag(s) (b) Br₂ (aq)
Given that Ksp for AgI is 8:51 × 10−17, and EoAg+/Ag = +0:80 V, calculate Eo for the reduction step:Hence confirm the statement in Section 8.3 that reduction of silver(I) when in the form of solid
Use the following experimental data to determine EoCu2+/Cu, and comment on the need (or not) to make use of all the data given. [Cu²+]/mol dm E/V 0.001 0.005 0.010 0.252 0.272 0.281 0.050 0.302
Consider the half-reaction:If the ratio of concentrations of [MnO4]− : Mn2+ is 100:1, determine E at pH values of (a) 0.5; (b) 2.0;(c) 3.5 (T = 298 K). Over this pH range, how does the ability
In each redox reaction in problem 8.3, confirm that the net increases and decreases in oxidation states balance each other.Data from Problem 8.3Which of the following reactions are redox reactions?
(a) Calculate EAg+/Ag for a half-cell in which the concentration of silver(I) ions is 0.1moldm−3 (T = 298 K). (b) Are silver(I) ions more or less easily reduced by zinc in this solution than
Which of the following reactions are redox reactions? In those that are, identify the oxidation and reduction processes. (a) N₂ + 3Mg Mg3N₂ (b) N₂ + O₂- 2NO (c) 2NO₂ → N₂04 (d) SbF3 +
What oxidation state change does each metal undergo in the following reactions or half-reactions? (a) [Cr₂O7²- + 14H+ +6e2Cr³+ (b) 2K + 2H₂O2KOH + H₂ (c) Fe₂O3 + 2A1 2Fe + Al₂O3 A (d)
(a) Use data from Appendix 11 to construct a potential diagram showing the redox chemistry of vanadium in aqueous solution at pH0. (b) Use your diagram to establish whether any vanadium species is
Use the data in the potential diagram shown in Fig. 8.7 to construct a Frost–Ebsworth diagram for chlorine. Hence show that Cl− is the most thermodynamically favoured species of those in the
The following potential diagram summarizes the results of electrochemical studies of the aqueous solution (pH 0) chemistry of uranium:Use the information to deduce as much as possible about the
Use the data in Appendix 11 to rationalize the following observations in a quantitative manner. What assumption(s) have you made in answering this question?(a) The dithionate ion, [S2O6]2−, can be
(a) Using the potential diagram below (at pH 14), calculate E°O3−2/O2(b) Comment on the following data:(c) How valid is Fig. 8.4a for aqueous solutions at pH 2?Figure 8.4a.
In hydrochloric acid, HOI reacts to give [ICl2]−. Use the potential diagrams below to explain why HOI disproportionates in aqueous acidic solution, but does not when the acid is aqueous HCl.
Using data from Appendix 11, and the value for the standard Gibbs energy of formation for PbS of −99 kJ mol–1, determine a value for Ksp for this salt.Data from Appendix 11The concentration of
By constructing thermodynamic cycles analogous to those shown in Fig. 8.5, discuss the factors that contribute to the trend in values of Eo for the group 1 metals Li to Cs. Figure 8.5Table 7.7 Step
The following potential diagram is part of that illustrating the redox chemistry of chlorine in aqueous solution at pH0. (a) Calculate the value of E° for the reduction of [ClO3]‾ to HClO2. (b)
A tarnished silver knife is placed in a beaker containing hot aqueous NaHCO3. A piece of Al foil is placed in the solution so that it touches the knife. The deposit of Ag2S disappears and the clean
Zinc/silver oxide button batteries are used in calculators and watches. Although the silver component makes them expensive, this is outweighed by their high performance. The battery uses KOH as the
In each of the following reactions, relate starting materials and products by the processes of reduction, oxidation, disproportionation or no redox change. In some reactions, more than one process is
The commercial purification of copper metal is carried out in electrolytic cells. The anode is composed of impure (‘blister’) copper, and the electrolyte is a mixture of aqueous CuSO4 and H2SO4.
Consider the following two scenarios: (i) Aluminium rivets used to connect two steel plates, (ii) Steel rivets used to connect two Aluminium plates.Discuss whether these choices would be
A plumber directly connects a galvanized steel pipe to a copper pipe in a system that carries running water. Suggest what will happen over a period of time.
Provide explanations for the following observations.(a) In moist air, corrosion of iron is spontaneous. However, under anaerobic (O2 free), wet conditions, corrosion of iron is only marginally
The industrial manufacture of NH3 from N2 and H2 is carried out on a huge scale using heterogeneous catalysis, i.e. the reaction between gaseous N2 and H2 is carried out over a solid catalyst. (a)
In problems 4.28 to 4.51, refer to Table 4.3 for isotopic abundances where needed.NaBH4 contains the tetrahedral [BH4]– ion. Although NaBH4 hydrolyses slowly in water, it is possible to obtain a
Using Figs. 5.22, 5.23 and 5.25 to help you, compare the MO pictures of the bonding in BF3 and [NO3]‾. What approximations have you made in your bonding analyses?Figure 5.22.Figure 5.23Figure 5.25.
Table 5.6 gives the results of a self-consistent field (SCF) quantum chemical calculation for H2O using an orbital basis set of the atomic orbitals of O and the LGOs of an H---H fragment. The axis
Refer to Fig. 5.17 and the accompanying discussion.(a) Why does the B 2pz atomic orbital become a non-bonding MO in BH3? (b) Draw schematic representations of each bonding and antibonding MO in
‘Titanium dissolves nitrogen to give a solid solution of composition TiN0.2; the metal lattice defines an hcp arrangement.’ Explain what is meant by this statement, and suggest whether, on the
The diagrams at the right-hand side of Fig. 5.19 show three of the MOs in NH3. Sketch representations of the other four MOs.Figure 5.19. Energy 2p₂(a₂) 2p, 2p, (e) 2s
By referring to Section 10.6, suggest how the following solid state structures (i.e. the organization of the molecules in the solid state) may be affected by hydrogen bonding: (a)

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