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inorganic chemistry

Inorganic Chemistry 5th Edition Catherine Housecroft - Solutions

Comment on the variation in oxidation states of the first row metals.
In the complex [Ti(BH4)3(MeOCH2CH2OMe)], the Ti(III) centre is 8-coordinate. Suggest modes of coordination for the ligands.
Comment on each of the following observations.(a) Li2TiO3 forms a continuous range of solid solutions with MgO. (b) When TiCl3 is heated with concentrated aqueous NaOH, H2 is evolved.
How would you (a) Distinguish between the formulations CuIIFeIIS2 and CuIFeIIIS2 for the mineral chalcopyrite, (b) Show that Fe3+ is a hard cation,(c) Show that the blue compound precipitated when a solution of [MnO4]− in concentrated aqueous KOH is reduced by [CN]− contains Mn(V)?
Give equations for the following reactions:(a) Heating Fe with Cl2; (b) Heating Fe with I2;(c) Solid FeSO4 with concentrated H2SO4;(d) Aqueous Fe3+ with [SCN]−; (e) Aqueous Fe3+ with K2C2O4; (f) FeO with dilute H2SO4;(g) Aqueous FeSO4 and NaOH.
The complex [V2L4], where HL is diphenylformamidine (see structure opposite-above), is diamagnetic. Each L− ligand acts as a bridging, N;N'-donor such that the complex is structurally similar to complexes of the type [Cr2(O2CR)4]. (a) Describe a bonding scheme for the [V2]4+ core and derive the
(a) The ligand 1,4,7-triazacyclononane, L, forms the nickel complexes [NiL2]2[S2O6]3·7H2O and [NiL2][NO3]Cl·H2O. X-ray diffraction data for these complexes reveal that in the cation in [NiL2][NO3]Cl·H2O, the Ni—N bond lengths lie in the range 209–212 pm, while in [NiL2]2[S2O6]3·7H2O, two
Suggest why Co3O4 adopts a normal rather than inverse spinel structure.
Give explanations for the following observations.(a) The complex [Co(en)2Cl2]2[CoCl4] has a room temperature magnetic moment of 3.71 μeff. (b) The room temperature magnetic moment of [CoI4]2− (e.g. 5.01 μB for the [Et4N]+ salt) is larger than that of salts of [CoCl4]2−.
(a) The value of μeff for [CoF6]3− is 5.63 μB. Explain why this value does not agree with the value for μ calculated from the spin-only formula.(b) By using a simple MO approach, rationalize why one-electron oxidation of the bridging ligand in [(CN)5CoOOCo(CN)5]6− leads to a shortening of
(a) When [CN]− is added to aqueous Ni2+ ions, a green precipitate forms; if excess KCN is added, the precipitate dissolves to give a yellow solution and at high concentrations of [CN]−, the solution becomes red. Suggest an explanation for these observations. (b) If the yellow compound from
Treatment of an aqueous solution of NiCl2 with H2NCHPhCHPhNH2 gives a blue complex (μeff = 3:30 μB) which loses H2O on heating to form a yellow, diamagnetic compound. Suggest explanations for these observations and comment on possible isomerism in the yellow species.
Give equations for the following reactions:(a) Aqueous NaOH with CuSO4; (b) CuO with Cu in concentrated HCl at reflux; (c) Cu with concentrated HNO3;(d) Addition of aqueous NH3 to a precipitate of Cu(OH)2; (e) ZnSO4 with aqueous NaOH followed by addition of excess NaOH; (f) ZnS
(a) Compare the solid state structures of [M(Hdmg)2] for M=Ni and Cu and comment on the fact that [Cu(Hdmg)2] is more soluble in water than is [Ni(Hdmg)2]. (b) Suggest the likely structural features of [Pd(Hdmg)2].
Copper(II) chloride is not completely reduced by SO2 in concentrated HCl solution. Suggest an explanation for this observation and state how you would try to establish if the explanation is correct.
The tanning process in the manufacture of leather relies upon the interaction of Cr3+ with the fibrous protein collagen. Although glycine and L-proline are the most important amino acids (see Table 29.2) in collagen, glutamic acid (pKa = 3.8) and aspartic acid (pKa = 4.2) are also present. During
When the ligands do not sterically control the coordination geometry, do 4-coordinate complexes of (a) Pd(II), (b) Cu(I)(c) Zn(II) prefer to be square planar or tetrahedral? Explain your answer. In the absence of crystallographic data, how could you distinguish between a square
When iron(II) oxalate (oxalate=ox2−) is treated with H2O2, H2ox and K2ox, a green compound X is obtained. X reacts with aqueous NaOH to give hydrated Fe2O3, and is decomposed by light with production of iron(II) oxalate, K2ox and CO2. Analysis of X shows it contains 11.4% Fe and 53.7% ox2−.
Give an overview of the formation of halido complexes of type [MXn]m− by the first row d-block metal ions, noting in particular whether discrete ions are present in the solid state.
Give a brief account of the variation in properties of binary oxides of the first row d-block metals on going from Sc to Zn.
Dimethyl sulfoxide (DMSO) reacts with cobalt(II) perchlorate in EtOH to give a pink compound A which is a 1 : 2 electrolyte and has a magnetic moment of 4.9 μB. Cobalt(II) chloride also reacts with DMSO, but in this case the dark blue product, B, is a 1 : 1 electrolyte, and the magnetic moment of
When H2S is passed into a solution of copper(II) sulfate acidified with H2SO4, copper(II) sulfide precipitates. When concentrated H2SO4 is heated with metallic Cu, the principal sulfur-containing product is SO2 but a residue of copper(II) sulfide is also formed. Account for these reactions.
(a) Write an equation to represent the discharge of an alkaline electrolyte cell containing a Zn anode and BaFeO4 cathode.(b) The first charge transfer band for [MnO4]− occurs at 18320cm−1, and that for [MnO4]2− at 22940 cm−1. Explain the origin of these absorptions, and comment on the
(a) The electronic absorption spectrum of [Ni(DMSO)6]2+ (DMSO=Me2SO) exhibits three absorptions at 7728, 12970 and 24 038 cm−1. Assign these absorptions.(b) CuF2 has a distorted rutile structure (four Cu—F = 193 pm and two Cu—F = 227 pm per Cu centre); [CuF6]2− and [NiF6]3− are distorted
Vanadium(IV) complexes act as mimics for insulin, a hormone secreted by the pancreas. Among the complexes being studied is [VOL2] in which HL is maltol:Figure 21.45 shows the pH dependence of the species in aqueous solution containing [VO]2+ and HL in a 1 : 2 ratio. (a) Suggest a structure for
The compound shown below is a formazan dye usually referred to as ‘zincon’. It is used to detect Zn2+ and Cu2+ ions:(a) Suggest how the ligand binds to Zn2+ or Cu2+, and comment on the role of pH in determining the overall charge of the complex. (b) Why does the ligand include a SO3H
(a) Write out the first row d-block metals in sequence and then complete each triad of metals. (b) Between which two metals is the series of lanthanoid metals?
Briefly discuss trends in (a) Metallic radii and(b) Values of ΔaH°(298 K) for the d-block metals.
(a) Estimate the value of ΔfH°(WCl2) assuming it to be an ionic compound. Comment on any assumptions made. [Data needed in addition to those in Tables 21.1, 22.1 and the Appendices: ΔfH°(CrCl2) = −397 kJ mol−1]. (b) What does your answer to (a) tell you about the likelihood of WCl2 being
An acidified solution of 0.1000mol dm−3 ammonium vanadate (25.00cm3) was reduced by SO2 and, after boiling off excess reductant, the blue solution remaining was found to require addition of 25.00 cm3 0.0200 mol dm−3 KMnO4 to give a pink colour to the solution. Another 25.00 cm3 portion of the
An acidified solution of 0.1000mol dm−3 ammonium vanadate (25.00cm3) was reduced by SO2 and, after boiling off excess reductant, the blue solution remaining was found to require addition of 25.00 cm3 0.0200 mol dm−3 KMnO4 to give a pink colour to the solution. Another 25.00 cm3 portion of the
Give equations to describe what happens to VBr3 on heating.
The magnetic moment of [NH4]V(SO4)2 · 12H2O is 2.8 μB and the electronic absorption spectrum of an aqueous solution contains absorptions at 17,800, 25,700 and 34,500 cm−1. Explain these observations.
Give equations to describe what happens to VBr3 on heating.
The magnetic moment of [NH4]V(SO4)2·12H2O is 2.8 μB and the electronic absorption spectrum of an aqueous solution contains absorptions at 17 800, 25 700 and 34 500 cm−1. Explain these observations.
The magnetic moment of [NH4]V(SO4)2·12H2O is 2.8 μB and the electronic absorption spectrum of an aqueous solution contains absorptions at 17 800, 25 700 and 34 500 cm−1. Explain these observations.
The magnetic moment of [NH4]V(SO4)2·12H2O is 2.8 μB and the electronic absorption spectrum of an aqueous solution contains absorptions at 17 800, 25 700 and 34 500 cm−1. Explain these observations.
(a) Structures 16.67 and 16.68 show hypervalent sulfur in NSF and NSF3. Draw resonance structures for each molecule that retains an octet of electrons around the S atoms, and account for the three equivalent S—F bonds in NSF3.(b) The enthalpies of vaporization (at the boiling point) of H2O, H2S,
The electronic spectra of mixtures of CH2Cl2 solutions (each 0.993 mmol dm−3) of I2 and the donor D shown in the diagram after the table were recorded for different volume ratios of the two solutions. Values of the absorbance for the absorption at λmax = 308 nm are as follows:(a) Suggest how
(a) Give descriptions of the bonding in ClO2 and [ClO2]− (17.24 and 17.35), and rationalize the differences in Cl—O bond lengths.(b) Rationalize why KClO4 and BaSO4 are isomorphous. O Cl-0= 147 pm; 20-C1-0 = 117° (17.24)
Figure 17.15 shows a Frost–Ebsworth diagram for chlorine.(a) How is this diagram related to the potential diagram for chlorine in Fig. 17.14?(b) Which is the most thermodynamically favoured species in Fig. 17.15? Explain how you reach your conclusion.(c) State, with reasons, which species in the
Describe in outline how you would attempt:(a) To determine the equilibrium constant and standard enthalpy change for the aqueous solution reaction:(b) To show that the oxide I4O9 (reported to be formed by reaction between I2 and O3) reacts with water according to the reaction:(c) To show that when
(a) The reaction of CsF, I2O5 and IF5 at 435K leads to Cs2IOF5. When the amount of CsF is halved, the product is CsIOF4. Write balanced equations for the reactions. Are they redox reactions?(b) Using data in Fig. 17.14, calculate ΔG°(298 K) for the reaction:Comment on the fact that the reaction
Suggest products for the following (which are not balanced): (a) [CIO3] + Fe²+ + H+ (b) [103] + [SO3)²- (c) [103] + Br¯ + H+
(a) Figure 17.7 showed the structure of [(AgI2)n]n+ and an MO scheme for the bonding. The bonding may also be represented using the valence bond approach. The diagram below illustrates the positive charge localized on Ag+ centres. Use this as a starting point to draw a set of resonance structures
Which description in the second list below can be correctly matched to each element or compound in the first list? There is only one match for each pair. List 1 HCIO4 CaF₂ 1₂05 CIO₂ [BrF] [IF] HOCI C6H6 Br₂ CIF 3 RbCl I₂C16 List 2 Weak acid in aqueous solution Charge transfer
Discuss the interpretation of each of the following observations:(a) Al2Cl6 and I2Cl6 are not isostructural.(b) Thermal decomposition of [Bu4N][ClHI] yields [Me4N]I and HCl.(c) 0.01 M solutions of I2 in n-hexane, benzene, ethanol and pyridine are violet, purple, brown and yellow respectively. When
The UV–VIS spectrum of a solution of I2 and hexamethylbenzene in hexane exhibits absorptions at 368 and 515 nm. Assign these absorptions to electronic transitions, and explain how each transition arises.
Fluoride ions are added to drinking water, toothpaste and drugs used to treat osteoporosis. However, an excess of F− is toxic to the body. The design of water-soluble, selective fluoride ion receptors is therefore topical. One group of receptors that has been investigated consists of the
Suggest likely structures for (a) [F2ClO2]−,(b) FBrO3, (c) [ClO2]+, (d) [F4ClO]−.
(a) Give equations to show the effect of temperature on the reaction between Cl2 and aqueous NaOH.(b) In neutral solution 1 mol [IO4]− reacts with excess I− to produce 1 mol I2. On acidification of the resulting solution, a further 3 mol I2 is liberated. Derive equations for the reactions which
Both HBr and BrO (see problem 17.23) are present in volcanic plumes. A model for reactions in the plume involves the following sequence:(a) Briefly discuss the types of reactions shown above.(b) Discuss the roles of ClO and Cl in ozone depletion over Antarctica. Comment on any similarities between
Discuss the interpretation of each of the following observations:(a) Although the hydrogen bonding in HF is stronger than that in H2O, water has much the higher boiling point.(b) Silver chloride and silver iodide are soluble in saturated aqueous KI, but insoluble in saturated aqueous KCl.
Explain why:(a) [NH4]F has the wurtzite structure, unlike other ammonium halides which possess the CsCl or NaCl lattice depending on temperature;(b) [PH4]I is the most stable of the [PH4]+ X− halides with respect to decomposition to PH3 and HX.
Which description in the second list below can be correctly matched to each element or compound in the first list? There is only one match for each pair. List 1 So [S₂08]²- [S₂] S₂F₂ Na₂O [S₂06]² PbS H₂O₂ HSO 3 CI [S₂O3]²- H₂S SeO3 List 2 A toxic gas Readily disproportionates
(a) Comment on the fact that HOI disproportionates in aqueous solution at pH 0, but in aqueous HCl at pH 0, iodine(I) is stable with respect to disproportionation.(b) The solid state structure of [ClF4][SbF6] reveals the presence of ions, but asymmetrical Cl—F—Sb bridges result in infinite
Suggest products for the following reactions; the equations are not necessarily balanced on the left hand sides. Draw the structures of the sulfur containing products. (a) SF4 + SbF5 (b) SO3 + HF. liq HF (c) Na₂S4 + HCI (d) [HSO3] + I₂ + H₂O → (e) [SN] [AsF6] + CsF- (f) HSO3Cl + anhydrous
(a) How many degrees of vibrational freedom does each of ClF3 and BF3 possess? The IR spectrum of ClF3 in an argon matrix exhibits six absorptions, whereas that of BF3 has only three. Explain why the spectra differ in this way.(b) Which of the following compounds are potentially explosive and must
Use values of rcov (Table 17.1) to estimate the X—Y bond lengths of ClF, BrF, BrCl, ICl and IBr. Compare the answers with values in Fig. 17.8 and Table 17.3, and comment on the validity of the method of calculation.Table 17.1Table 17.3.Figure 17.8 Property Atomic number, Z Ground state electronic
Comment on the following statements, giving equations to illustrate relevant reactions:(a) Iodine supplements for the human body comprise I2/KI.(b) HF is used commercially to etch silica glass.(c) Mixtures of solid ammonium perchlorate and powdered aluminium are used as rocket propellants.
(a) What is the collective name for the group 18 elements? (b) Write down, in order, the names and symbols of these elements; check your answer by reference to the first page of this chapter. (c) What common feature does the ground state electronic configuration of each element possess?
(a) Draw the structures of S7NH, S6N2H2, S5N3H3 and S4N4H4, illustrating isomerism where appropriate. (The structures of hypothetical isomers with two or more adjacent NH groups should be ignored.) (b) Write a brief account of the preparation and reactivity of S4N4, giving the structures of
Discuss the interpretation of each of the following observations.(a) When metallic Cu is heated with concentrated H2SO4, in addition to CuSO4 and SO2, some CuS is formed.(b) The [TeF5]− ion is square pyramidal.(c) Silver nitrate gives a white precipitate with aqueous sodium thiosulfate; the
(a) S8O can be prepared by treating S8 with CF3CO3H. The structure of S8O is shown below. Explain why the addition of one O atom to the S8 ring reduces the molecular symmetry from D4d to C1.(b) The reaction between TeF4 and Me3SiCN leads to the formation of Me3SiF and substitution products
Interpret the following experimental results.(a) Sodium dithionite, Na2S2O4 (0.0261 g) was added to an excess of ammoniacal AgNO3 solution; the precipitated silver was removed by filtration, and dissolved in nitric acid. The resulting solution was found to be equivalent to 30.0 cm3 0.10 M
The action of concentrated H2SO4 on urea, (H2N)2CO, results in the production of a white crystalline solid X of formula H3NO3S. This is a monobasic acid. On treatment with sodium nitrite and dilute hydrochloric acid at 273 K, one mole of X liberates one mole of N2, and on addition of aqueous BaCl2,
Write a brief account of the oxoacids of sulfur, paying attention to which species are isolable.
Give the structures of S2O, [S2O3]2−, NSF, NSF3, [NS2]+ and S2N2 and rationalize their shapes.
[NS2][SbF6] reacts with nitriles, RC≡N, to give [X] [SbF6] where [X]+ is a cycloaddition product. Propose a structure for [X]+ and show that it is a 6-electron system. Do you expect the ring to be planar or puckered? Give reasons for your answer.
For a given atom Y, the Y—F bond is usually stronger than the corresponding Y—Cl bond. An exception is when Y is oxygen (Table 16.2). Suggest a reason for this observation.Table 16.2.
Briefly discuss the trends in boiling points and values of ΔvapH° listed in Table 17.2 for the hydrogen halides.Table 17.2. Property Physical appearance at 298 K Melting point /K Boiling point/K AfusH (mp)/kJ mol-¹ AvapH (bp)/kJ mol-¹ A,Hº (298 K)/kJ mol-¹ A,Gº (298 K)/kJ mol Bond
The [Se4]2+ ion has D4h symmetry and the Se—Se bond lengths are equal (228 pm).(a) Is the ring in [Se4]2+ planar or puckered?(b) Look up a value of rcov for Se. What can you deduce about the Se—Se bonding?(c) Draw a set of resonance structures for [Se4]2+.(d) Construct an MO diagram that
The reaction of TeCl4 with PPh3 in THF solution in air leads to the formation of the salt (Ph3PO)2H]2[Te2Cl10]. Structural data reveal that each Te centre in the anion is in an approximately octahedral environment. (a) Suggest a structure for [Te2Cl10]2−. (b) The cation [(Ph3PO)2H]+ is
Suggest products for the following reactions (which are not balanced): (a) AgCI+ CIF3 (b) CIF + BF3 (c) CsF+IFs - (d) SbF5 + CIF5 (e) Me NF + IF₂ A (f) K[BrF4]
HSO is an intermediate in the atmospheric oxidation of H2S, and it has been implicated in ozone depletion. Calculated wavenumbers for the fundamental modes of vibration of HSO are 2335, 1077 and 1002 cm−1. These are assigned to stretching, bending and stretching modes, respectively. Deuteration
(a) North African desert dusts contain particles of calcite and dolomite. Why are these dusts important in counteracting acid rain in the Eastern Mediterranean? Give equations to illustrate your answer.(b) Crystalline CaC2O4·H2O (log Ksp = −8.6) and CaC2O4·2H2O (log Ksp ≈ −8.2) accumulate
Comment on the relevance of homonuclear bond formation between group 16 elements to the following:(a) Ozone and dioxygen;(b) Iron pyrites (fool’s gold);(c) The blue gemstone lapis lazuli;(d) Elemental Te, used as an additive in low-carbon steels.
(a) What is the collective name for the group 17 elements? (b) Write down, in order, the names and symbols of these elements; check your answer by reference to the first two pages of this chapter. (c) Give a general notation showing the ground state electronic configuration of each
(a) Write equations to show the reactions involved in the extraction of Br2 and I2 from brines.(b) What reactions occur in the Downs process, and why must the products of the process be kept apart?(c) In the electrolysis cell used for the industrial preparation of F2, a diaphragm is used to
Give explanations for the following observations.(a) pKa values for CF3CO2H and CH3CO2H are 0.23 and 4.75, respectively.(b) The dipole moment of a gas phase NH3 molecule is 1.47 D, but that of NF3 is 0.24 D.(c) In electrophilic substitution reactions in monosubstituted aryl compounds C6H4X, X = Me
Discuss the role of halide acceptors in the formation of interhalogen cations and anions.
Predict the structures of (a) [ICl4]−, (b) [BrF2]+,(c) [ClF4]+, (d) IF7, (e) I2Cl6, (f) [IF6]+, (g) BrF5.
(a) Assuming static structures and no observed coupling to the central atom, what would you expect to see in the 19F NMR spectra of BrF5 and [IF6]? (b) Do you expect these spectra to be temperature-dependent?
(a) Use data in Appendix 11 to give a quantitative explanation why H2 can be prepared from the reaction of Zn with dilute mineral acid, but not from Cu with a dilute acid.(b) The ion [H13O6]+ can exist in more than one isomeric form. One that has been structurally characterized is described in
Discuss the trends in data in Table 12.4.Data from Table 12.4. Metal, M Mg Ca Sr Ba MF2 -1113 -1214 -1213 -1200 AH°/kJ mol MC1₂ -642 -795 -828 -860 MBr₂ -517 -674 -715 -754 MI₂ -360 -535 -567 -602
Figure 14.10 shows a unit cell of K3C60. From the structural information given, confirm the stoichiometry of this fulleride.Figure 14.10.
Comment on each of the following observations.(a) The carbides Mg2C3 and CaC2 liberate propyne and ethyne respectively when treated with water, reaction between ThC2 and water produces mixtures composed mainly of C2H2, C2H6 and H2, but no reaction occurs when water is added to TiC.(b) Mg2Si reacts
Predict the shapes of the following molecules or ions: (a) CICN; (b) OCS; (c) [SiH3]; (d) [SnCl,]; (e) Si₂OCl; (f) [Ge(C₂O4)3]; (g) [PbCl²; (h) [SnS4].
In 1H NMR spectra in which the solvent is acetonitrile-d3, labelled to an extent of 99.6%, a multiplet is observed at δ 1.94 ppm. How does this multiplet arise, and what is its appearance? [D, I = 1; H, I = 1/2]
Suggest a structure for the [H9O4]+ ion.
(a) Write down, in order, the names and symbols of the elements in group 14. (b) Classify the elements in terms of metallic, semi-metallic or non-metallic behaviour.(c) Give a general notation showing the ground state electronic configuration of each element.
By referring to Fig. 8.6, deduce whether carbon could be used to extract Sn from SnO2 at (a) 500 K;(b) 750 K; (c) 1000 K.Justify your answer.Figure 8.6. A,Go/kJ per half-mole of O₂ (see text) -100 -200 -300 -400 -500 -600 0 CO NiO SnO₂ FeO ZnO Al₂O3 SrO CaO 250 500 750 M(s)→M(1) >=
Comment on the trends in values of (a) Melting points, (b) ΔatomH°(298 K) (c) ΔfusH°(mp) for the elements on descending group 14.
How does the structure of graphite account for (a) Its use as a lubricant, (b) The design of graphite electrodes, (c) The fact that diamond is the more stable allotrope at very high pressures?
Give four examples of reactions of C60 that are consistent with the presence of C = C bond character.
Table 14.7 gives values of the symmetric and asymmetric stretches of the heteronuclear bonds in CO2, CS2 and (CN)2, although the molecules are indicated only by the labels I, II and III. (a) Assign an identity to each of I, II and III. (b) State whether the stretching modes listed in Table 14.7
(a) Suggest why the NSi3 skeleton in N(SiMe3)3 is planar. (b) Suggest reasons why, at 298 K, CO2 and SiO2 are not isostructural. Under what conditions can phases of CO2 with silica-like structures be made?
The observed structure of [Sn9Tl]3− is a bicapped square-antiprism. (a) Confirm that this is consistent with Wade’s rules. (b) How many isomers (retaining the bicapped square-antiprism core) of [Sn9Tl]3− are possible?
Compare and contrast the structures and chemistries of the hydrides of the group 14 elements, and give pertinent examples to illustrate structural and chemical differences between BH3 and CH4, and between AlH3 and SiH4.
Write equations for: (a) The hydrolysis of GeCl4; (b) The reaction of SiCl4 with aqueous NaOH; (c) The 1:1 reaction of CsF with GeF2; (d) The hydrolysis of SiH3Cl; (e) The hydrolysis of SiF4; (f) The 2:1 reaction of [Bu4P]Cl with SnCl4. In each case suggest the

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