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inorganic chemistry

Inorganic Chemistry 5th Edition Catherine Housecroft - Solutions

By using the diagram shown below, confirm that C60 belongs to the Ih point group.
Rationalize the following signal multiplicities in the 119Sn NMR spectra of some halo-anions and, where possible, use the data to distinguish between geometric isomers [19F 100% I = 1/2]: (a) [SnCl5F]2− doublet; (b) [SnCl4F2]2− isomer A, triplet; isomer B, triplet; (c)
What would you expect to form when:(a) Sn is heated with concentrated aqueous NaOH;(b) SO2 is passed over PbO2;(c) CS2 is shaken with aqueous NaOH;(d) SiHCl2 is hydrolysed by water;(e) Four molar equivalents of ClCH2SiCl3 react with three equivalents of Li[AlH4] in Et2O solution
Suggest one method for the estimation of each of the following quantities:(a) ΔrHº for the conversion: GeO2(quartz)→ GeO2(rutile);(b) The Pauling electronegativity value, χP, of Si;(c) The purity of a sample of Pb(MeCO2)4 prepared in a laboratory experiment.
(a) By using the description of the bonding in Sn2R4 as a guide (see Fig. 23.19), suggest a bonding scheme for a hypothetical HSi ≡ SiH molecule with the following geometry:(b) Do you expect the [FCO]+ ion to have a linear or bent structure? Give an explanation for your answer.(c) The α-form of
Comment on the following observations:(a) The pyroxenes CaMgSi2O6 and CaFeSi2O6 are isomorphous;(b) The feldspar NaAlSi3O8 may contain up to 10% of CaAl2Si2O8;(c) The mineral spodumene, LiAlSi2O6, is isostructural with diopside, CaMgSi2O6, but when it is heated it is transformed into a polymorph
Which description in the second list below can be correctly matched to each compound in the first list? There is only one match for each pair. List 1 SiF4 Si Cs3C60 SnO [Ge,]+ GeF₂ [SiO4]¹ PbO₂ Pb(NO3)2 SnF4 List 2 A semiconductor at 298 K with a diamond-type structure A Zintl ion Its Ca²+
Account for the fact that when aqueous solution of KCN is added to a solution of aluminium sulfate, a precipitate of Al(OH)3 forms.
Suggest products for the following reactions; the lefthand sides of the equations are not necessarily balanced. (a) GeH₂Cl + NaOCH3 →→ (b) CaC₂ + N₂ (c) Mg₂ Si + H₂O/H™ (d) K₂SiF6+KA (e) 1,2-(OH)₂C6H4 + GeO₂ (f) (H₂Si)₂O+I2₂ →→ (g) €60 (h) Sn NaOH/MeOH O3, 257 K in
What would you expect to be the hydrolysis products of (a) Cyanic acid, (b) Isocyanic acid and(c) Thiocyanic acid?
For solid Ba[CSe3], the vibrational wavenumbers and assignments for the [CSe3]2− ion are 802 (E', stretch), 420 (A2''), 290 (A1') and 185 (E', deformation) cm−1.(a) Based on these assignments, deduce the shape of the [CSe3]2− ion. (b) Draw diagrams to illustrate the modes of vibration of
The reaction between a 1,2-ethanediamine solution of K4[Pb9] and a toluene solution of [Pt(PPh3)4] in the presence of crypt-222 leads to the formation of the platinum-centred Zintl ion [Pt@Pb12]2−, the 207Pb NMR spectrum of which consists of a pseudo-triplet (J207Pb195Pt = 3440 Hz).(a) What is
Deduce the point groups of each of the following molecular species: (a) SiF4, (b) [CO3]2−, (c) CO2,(d) SiH2Cl2.
The glass industry manufactures millions of tonnes of glass per year.(a) Only certain element oxides form glasses. Explain why this is, giving examples of what are termed in the glass industry as ‘networkforming oxides’. Which oxide is the most important starting material in commercial glasses?
Using bond enthalpy terms from Tables 14.2 and 15.3, estimate values of ΔrHº for the following reactions(a) 2N2 → N4 (tetrahedral structure);(b) 2P2 → P4 (tetrahedral structure);(c) 2C2H2 → C4H4 (tetrahedrane, with a tetrahedral C4 core).Table 14.2.Table 15.3. C-C_C=CC=C_C-H C-F C-CI
Lead-acid batteries accounted for 69% of all lead consumed in the US in 2015. (a) Complete the cell reaction given below (not balanced on the left-hand side) and show that the oxidation state changes balance in the final equation:(b) What are the two half-cell reactions in a lead–acid
(a) [SnF5]− has a polymeric structure consisting of chains with cis-bridging F atoms. Draw a repeat unit of the polymer. State the coordination environment of each Sn atom, and explain how the overall stoichiometry of Sn : F = 1:5 is retained in the polymer.(b) Which of the salts PbI2, Pb(NO3)2,
Which of the following equations show redox reactions: eqs. 15.64, 15.70, 15.73, 15.111 and 15.123? For each redox reaction, indicate which species is being oxidized and which reduced. Confirm that the changes in oxidation states for the oxidation and reduction processes balance.Equations 2NF3 Cu,
(a) Describe the solid state structures of K3C60 and of KC8. Comment on any physical or chemical properties of the compounds that are of interest.(b) Comment on the use of lead(II) acetate in a qualitative test for H2S.(c) In the [Et4N]− salt, the [C2S4]2− ion is nonplanar; the dihedral angle
Carbon monoxide detectors are in widespread use in the workplace and home. Metal oxide (e.g. SnO2) semiconductor and electrochemical sensors are commonly used. (a) Explain how an SnO2 sensor for CO works. (b) An electrochemical sensor employs platinum electrodes with aqueous sulfuric acid
Zeolite A is used as a water softener in detergents and washing powders. Industrial production combines hydrated Al2O3, aqueous NaOH and Na4SiO4. After crystallization, the product (zeolite A) is subject to a number of washing and drying processes before use. (a) Describe the general
What are the formal oxidation states of N or P in the following species? (a) N2; (b) [NO3]−; (c) [NO2]−;(d) NO2; (e) NO; (f) NH3; (g) NH2OH;(h) P4;(i) [PO4]3−; (j) P4O6; (k) P4O10
What might you expect to observe (at 298 K) in the 19F NMR spectra of solutions containing (a) [PF6]−(b) [SbF6]−. Data needed are in Table 15.2.Table 15.2. Property Atomic number, Z Ground state electronic configuration Enthalpy of atomization, A.H°(298 K)/ kJ mol Melting point, mp/K Boiling
Refer to Fig. 15.12. (a) By considering a number of unit cells of NiAs connected together, confirm that the coordination number of each Ni atom is 6. (b) How does the information contained in the unit cell of NiAs confirm the stoichiometry of the compound? (a) (b)
Give a brief account of allotropy among the group 15 elements.
Write equations for the reactions of (a) Water with Ca3P2; (b) Aqueous NaOH with NH4Cl;(c) Aqueous NH3 with Mg(NO3)2; (d) AsH3 with an excess of I2 in neutral aqueous solution; (e) PH3 with KNH2 in liquid NH3.
In each of reactions 15.66, 15.67 and 15.68, NF2 · reacts with another radical. What is the second radical in each reaction, and how is it formed? Draw a Lewis structure of F2NNO (the product of reaction 15.68).Equation 15.68. NF₂ + NO F₂NNO (15.68)
Explain why (a) A dilute aqueous solution of NH3 smells of the gas whereas dilute HCl does not retain the acrid odour of gaseous HCl, (b) Ammonium carbamate is used in smelling salts.
If (at 298 K) pKb for NH3 is 4.75, show that pKa for [NH4]+ is 9.25.
Give the relevant half-equations for the oxidation of NH2OH to HNO3 by [BrO3]−, and write a balanced equation for the overall process.
(a) Write a balanced equation for the preparation of NaN3 from NaNH2 with NaNO3. (b) Suggest a route for preparing the precursor NaNH2. (c) How might NaN3 react with Pb(NO3)2 in aqueous solution?
(a) We noted that [N3]− is isoelectronic with CO2. Give three other species that are also isoelectronic with [N3]−. (b) Describe the bonding in [N3]− in terms of an MO picture.
Figure 15.23 shows a unit cell of FeSb2O6. (a) How is this unit cell related to the rutile-type structure?(b) Why can the solid state structure of FeSb2O6 not be described in terms of a single unit cell of the rutile-type structure? (c) What is the coordination environment of each atom type? (d)
Suggest how you might confirm the conformation of N2H4 in (a) The gas phase (b) The liquid phase.
(a) Discuss structural variation among the phosphorus(III) and phosphorus(V) halides, indicating where stereochemical non-rigidity is possible. (b) On what basis is it appropriate to compare the lattice of [PCl4][PCl6] with that of CsCl?
Suggest products for the following reactions; the equations are not necessarily balanced on the lefthand sides. (a) Pl3 + IBr + GaBr3 (b) POBr3 + HF + AsF5 A (c) Pb(NO3)2 liquid NH3 (d) PH3 + K (e) Li3N + H₂O → (f) H3ASO4 + SO₂ + H₂O →
Explain whether it is possible to distinguish between the following pairs of isomers based only on the coupling patterns in the 31P NMR spectra:(a) Cis- and trans-[PF4(CN)2]−, (b) Mer- and fac-[PF3(CN)3]−.
Draw the structures of the possible isomers of [PCl2F3(CN)]−, and state how many fluorine environments there are based on the structures you have drawn. At room temperature, the 19F NMR spectra of CH2Cl2 solutions of two of the isomers exhibit two signals, while the spectrum of the third isomer
Suggest products for the reactions between (a) SbCl5 and PCl5; (b) KF and AsF5; (c) NOF and SbF5;(d) HF and SbF5.
(a) The 31P and 11B NMR spectra of Pr3P·BBr3 (Pr = n-propyl) exhibit a 1 :1 :1 :1 quartet (J = 150 Hz) and a doublet (J = 150 Hz), respectively. Explain the origin of these signals.(b) Discuss the factors that contribute towards [NH4][PF6] being soluble in water.(c) The ionic compound
(a) Draw the structures of [Sb2F11]− and [Sb2F7]−, and rationalize them in terms of the VSEPR model.(b) Suggest likely structures for the [{BiX4}n]n− and [{BiX5}n]2n− oligomers mentioned in Section 15.7.
By using an MO approach, rationalize why, in going from NO to [NO]+, the bond order increases, bond distance decreases and NO vibrational wavenumber increases.
25.0 cm3 of a 0.0500 M solution of sodium oxalate (Na2C2O4) reacted with 24.8 cm3 of a solution of KMnO4, A, in the presence of excess H2SO4. 25.0 cm3 of a 0.0494 M solution of NH2OH in H2SO4 was boiled with an excess of iron(III) sulfate solution, and when the reaction was complete, the iron(II)
Box 15.9 deals with the nitrogen cycle and the removal of nitrates and nitrites from waste water.(a) Urea is used to reduce [NO2]− to N2. Write a balanced equation for the reaction of HNO2 with urea. (b) Sulfamic acid is also used to reduce [NO2]− to N2 during water treatment. Give an equation
Write a brief account that supports the statement that ‘all the oxygen chemistry of phosphorus(V) is based on the tetrahedral PO4 unit’.
How may NMR spectroscopy be used:(a) To distinguish between solutions of Na5P3O10 and Na6P4O13;(b) To determine whether F atoms exchange rapidly between non-equivalent sites in AsF5;(c) To determine the positions of the NMe2 groups in P3N3Cl3(NMe2)3?
(a) Predict the 31P NMR spectrum of [HPF5]− (assuming a static structure) given that JPH = 939 Hz, JPF(axial) = 731 Hz and JPF(equatorial) = 817 Hz.(b) The [BiF7]2− and [SbF6]3− ions have pentagonal bipyramidal and octahedral structures, respectively. Are these observations consistent with
Deduce what you can about the nature of the following reactions.(a) One mole of NH2OH reacts with two moles of Ti(III) in the presence of excess alkali, and the Ti(III) is converted to Ti(IV).(b) When Ag2HPO3 is warmed in water, all the silver is precipitated as metal.(c) When one mole of H3PO2 is
(a) Use Wade’s rules to rationalize the fact that in [Pd@Bi10]4+, the Bi atoms are arranged in a pentagonal antiprism. How is this structure related to that of [Pd@Pb12]2−?(b) At 298 K, ammonium perchlorate decomposes according to the equation:Determine ΔrG°(298 K) for this decomposition if
Predict the structures of (a) [NF4]+; (b) [N2F3]+;(c) NH2OH; (d) SPCl3; (e) PCl3F2.
Suggest syntheses for each of the following from K15NO3: (a) Na15NH2, (b) 15N2(c) [15NO][AlCl4].
Suggest syntheses for each of the following from Ca3(32PO4)2: (a) 32PH3, (b) H332PO3 (c) Na332PS4.
25.0 cm3 of a 0.0500 M solution of sodium oxalate reacted with 24.7 cm3 of a solution of KMnO4, C, in the presence of excess H2SO4. 25.0 cm3 of a 0.0250 M solution of N2H4 when treated with an excess of alkaline [Fe(CN)6]3− solution gave [Fe(CN)6]4 and a product D. The [Fe(CN)6]4− formed
Comment on the fact that AlPO4 exists in several forms, each of which has a structure which is also that of a form of silica.
(a) What would you predict would happen when equimolar amounts of NaN3 and NaNO2 react in acidic solution? How would you attempt to confirm your prediction?(b) POCl3 reacts with an excess of Me2NH to yield compound A as the only phosphorus-containing product; compound A is miscible with water. A
(a) Explain what is meant by hyperconjugation in a phosphazene such as [Cl3P=N–PCl2=N=PCl3]+.(b) Draw resonance structures for [Cl3P=N–PCl2=N=PCl3]+ which illustrate contributions to the bonding from charge-separated species.
(a) Draw the structure of P4S3 and describe an appropriate bonding scheme for this molecule. Compare the structures of P4S10, P4S3 and P4, and comment on the formal oxidation states of the P atoms in these species.(b) The electrical resistivity of Bi at 273K is 1:07 × 10−6Ωm. How do you expect
(a) Sn3N4, γ-Si3N4 and g-Ge3N4 are the first examples of nitride spinels. What is a spinel, and how do the structures of these nitrides relate to that of the oxide Fe3O4? Comment on any features that distinguish the nitride spinels from typical oxide analogues.(b) The reaction between O3 and AsCl3
(a) Why does fuming nitric acid appear orange in colour?(b) By using nitric acid as an example, explain what is meant by the term azeotrope.
Electron diffraction and spectroscopic studies of mixed fluoro/chloro phosphorus pentahalides are consistent with trigonal bipyramidal structures in which the most electronegative halogens occupy the axial positions. Confirm that this statement is in agreement with PCl3F2, PCl2F3 and PClF4 having
Suggest products for the following reactions:(a) H2O2 and Ce4+ in acidic solution; (b) H2O2 and I− in acidic solution.[Data needed: see Appendix 11.]Data from Appendix 11The concentration of each aqueous solution is 1 mol dm−3 and the pressure of a gaseous component is 1 bar (105 Pa).
Polyphosphazenes are an important class of inorganic macromolecule and have many commercial applications, e.g. fire retardants, elastomers, fuel cell membranes, biomedical applications. The scheme opposite shows synthetic routes to three polymers.(a) Outline how (NPCl2)n is produced on a large
By considering the reactions 8E(g) → 4E2(g) and 8E(g) → E8(g) for E = O and E = S, show that the formation of diatomic molecules is favoured for oxygen, whereas ring formation is favoured for sulfur. [Data: see Table 16.2.]Table 16.2.
(a) Use the values of Eº for reactions 16.32 and 16.33 to show that H2O2 is thermodynamically unstable with respect to decomposition into H2O and O2.(b) ‘20 Volume’ H2O2 is so called because 1 volume of the solution liberates 20 volumes of O2 when it decomposes. If the volumes are measured at
(a) The head of a safety match contains KClO3 and this reacts with red phosphorus which is combined with glass powder on the side of the match box. Write an equation for the reaction that occurs when the match is struck. Show that changes in oxidation states balance. Comment on the role of the
Over 95% of the phosphate rock mined in the US is used to manufacture phosphoric acid and phosphate-based fertilizers. The remaining phosphate rock is used for the production of white phosphorus. (a) Give equations to show how phosphate rock is converted to phosphoric acid and to white
The diagrams below show two views of S6. Confirm that this molecule has D3d symmetry.
(a) Write down, in order, the names and symbols of the elements in group 16; check your answer by reference to the first page of this chapter. (b) Give a general notation showing the ground state electronic configuration of each element.
Write an equation to represent the formation of 210Po from 209Bi.
Write half-equations to show the reactions involved during the electrolysis of aqueous alkali.
The 125Te NMR spectrum of [Me4N][TeF7] (298K in MeCN) consists of a binomial octet (J = 2876 Hz), while the 19F NMR spectrum exhibits a singlet with two (superimposed over the singlet), very low intensity doublets (J = 2876 and 2385 Hz respectively). Rationalize these observations. [Data: see Table
(a) Draw diagrams to show the occupancies of the πg* level in the ground state and first two excited states of O2. Does the formal bond order change upon excitation from the ground to the first excited state (1Δg) of O2? (b) The 1Δg state of O2 lies 94.7 kJ mol–1 above the ground state.
Hydrogen peroxide oxidizes Mn(OH)2 to MnO2.(a) Write an equation for this reaction.(b) What secondary reaction will occur?
Explain why catena-Se∞ is chiral.
Predict the structures of (a) H2Se; (b) [H3S]+;(c) SO2; (d) SF4; (e) SF6; (f) S2F2.
(a) Explain why the reaction of SF4 with BF3 yields [SF3]+, whereas the reaction with CsF gives Cs[SF5]. (b) Suggest how SF4 might react with a carboxylic acid, RCO2H.
The Raman spectrum of solid [SeI3][AsF6] contains absorptions at 227, 216, 99 and 80 cm–1 assigned to the vibrational modes of the [SeI3]+ ion. Explain the origins of the four absorptions. Draw diagrams to represent the modes of vibration, and assign a symmetry label to each mode.
Discuss the trends in (a) The O—O bond lengths in O2 (121 pm), [O2]+ (112 pm), H2O2 (147.5 pm), [O2]2− (149 pm) and O2F2 (122 pm), and (b) The S—S bond distances in S6 (206 pm), S2 (189 pm), [S4]2+ (198 pm), H2S2 (206 pm), S2F2 (189 pm), S2F10 (221 pm) and S2Cl2 (193 pm). [Data:
Comment on the following values of gasphase dipole moments: SeF6, 0 D; SeF4, 1.78 D; SF4, 0.64 D; SCl2, 0.36 D; SOCl2, 1.45 D; SO2Cl2, 1.81 D.
In each of the following series of compounds or ions, identify those that are isoelectronic (with respect to the valence electrons) and those that are also isostructural: (a) [SiO4]4− , [PO4]3− , [SO4]2−;(b) CO2, SiO2, SO2, TeO2, [NO2]+; (c) SO3, [PO3]−, SeO3; (d)
(a) Give the structures of SO3 and [SO3]2− and rationalize the difference between them. (b) Outline the properties of aqueous solutions of SO2 and discuss the species that can be derived from them.
When gallium is dissolved in a solution of KOH in liquid NH3, a salt K[I] is formed which is an amido complex of Ga(III). Heating one equivalent of K[I] at 570K under vacuum liberates two equivalents of NH3, and produces a Ga(III) imido complex K[II]. Partial neutralization of K[I] with NH4Cl
Additional data needed for this question can be found in Appendix 11.(a) Determine EZn2+/Zn (at 298 K) for a half-cell in which [Zn2+] = 0.25 mol dm−3.(b) Calculate the reduction potential for the half reaction:if the ratio of the concentrations of [VO]2+: V3+ is 1 :2 and the pH of the solution
(a) Using standard reduction potentials from Appendix 11, determine values of ΔfGº(K+, aq) and ΔfGº(F‾, aq). (b) Hence, find ΔsolGº(KF, s) at 298 K, if ΔfGº(KF, s) = –537.8 kJ mol–1. (c) What does the value for ΔsolGº(KF, s) imply about the solubility of KF in water?Data from
(a) Use appropriate data from Appendix 11 to determine the ratio of the overall stability constants of the complexes [Fe(phen)3]2+ and [Fe(phen)3]3+ at 298 K.(b) Use the data in Fig. 8.2 to construct a Frost–Ebsworth diagram for manganese in aqueous solution at pH 14. Use your diagram to comment
Use the data in Appendix 11 to rationalize quantitatively why:(a) Mg liberates H2 from dilute HCl, but Cu does not;(b) Br2 liberates I2 from aqueous KI solution, but does not liberate Cl2 from aqueous KCl solution;(c) the role of Fe3+ ions as an oxidizing agent is influenced by the presence of
Suggest likely products for the following reactions (which are balanced on the left-hand sides) in liquid NH3.How does reaction (d) differ from the behaviour of MeCO2H in aqueous solution? (a) ZnI₂ + 2KNH₂ - (b) Zinc-containing product of (a) with an excess of KNH₂ (c) Mg2 Ge + 4NH4Br (d) (e)
(a) In aqueous solution at pH 0, Mn3+ disproportionates to MnO2 and Mn2+. Write equations for the two half-reactions involved in this process. (b) Use Fig. 8.2 to obtain values of Eº for the half-equations in part (a). (c) Determine Eºcell and a value of ΔGº(298 K) for the disproportionation
(a) With the aid of a phase diagram, explain what is meant by a supercritical fluid. Give examples of commercial processes that involve the use of supercritical fluids.(b) Even though CO2 is classified as a ‘greenhouse gas’ (see Box 14.7), why is the use of supercritical CO2 regarded as being
Confirm that the structures of [BrF2]+ and [BrF4]− (9.19 and 9.20) are consistent with the VSEPR model. F Br (9.19) + F J KI Br. F F F (9.20)
Using your answers to problem 7.11, write down expressions for the solubility (in mol dm−3) of (a) AgCl, (b) CaCO3 (c) CaF2 in terms of Ksp.Data from Problem 11Write down expressions for Ksp for the following ionic salts: AgCl; CaCO3; CaF2.
(a) Describe the bonding in the [Al2Cl7]− anion (9.22).(b) Equilibria 9.82 and 9.83 describe part of the NaCl– Al2Cl6 system; additionally [Al3Cl10]− is present. Write an equation to show how [Al3Cl10]− may be formed, and suggest a structure for this anion. Cl CAI CI CI Cl AlCl A CI (9.22)
(a) Give three examples of commonly used ionic liquids. What general properties make ionic liquids attractive in ‘green chemistry’? Are the properties of the liquid itself all that determines whether the ionic liquid is environmentally friendly?(b) The compound shown below was treated with one
Discuss the following observations:(a) The alkene Ph2C = CH2 forms a conducting solution in liquid HCl; when such a solution is titrated conductometrically with a solution of BCl3 in liquid HCl, a sharp end-point is reached when the molar ratio of Ph2C = CH2 : BCl3 is 1 : 1.(b) The following
How would you attempt to demonstrate that AsCl3 ionizes slightly according to the equation:and that there exist acids and bases in the AsCl3 system? 2AsCl3 = [AsCl₂] + [ASC14]
(a) Give four examples of non-aqueous solvents commonly used in organic chemistry, and give one example of a reaction that is carried out in each solvent. (b) Assess the relative importance of the use of aqueous and non-aqueous media in organic and inorganic general synthesis.
Which of the following solvents are polar:(a) Acetonitrile; (b) Water; (c) Acetic acid; (d) Fluorosulfonic acid; (e) Dichloromethane; (f) Bromine trifluoride; (g) Hexane; (h) THF; (i) DMF;(j) Liquid sulfur dioxide; (k) Benzene?
Suggest explanations for the following observations.(a) In aqueous solution, AgNO3 and KCl react to give a precipitate of AgCl, whereas in liquid NH3, KNO3 and AgCl react to produce a precipitate of KCl.(b) Mg dissolves in a concentrated solution of NH4I in liquid NH3.(c) Most common ‘acids’
Early in the study of chemical reactions in liquid NH3, it was noted that nitrogen compounds behave in liquid NH3 in a manner similar to analogous oxygen containing species in water. For example, K[NH2] has an analogue in K[OH], and [NH4]Cl is analogous to [H3O]Cl. What would be the corresponding
(a) Which of the following compounds behave as acids in liquid HF: ClF3, BF3, SbF5, SiF4? Write equations to explain this behaviour.(b) The salt [S8][AsF6]2 can be isolated from the following reaction:What roles does AsF5 play in this reaction?(c) By first considering its reaction in H2O, suggest

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