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inorganic chemistry

Inorganic Chemistry 5th Edition Catherine Housecroft - Solutions

(a) The IR spectrum of naturally occurring CO shows an absorption at 2170 cm−1 assigned to the molecular vibrational mode. If the sample is enriched in 13C, what change do you expect to see in the IR spectrum?(b) The IR spectra of salts of [Fe(CO)6]2+ and [Fe(CO)4]2−, respectively show
Suggest a suitable experimental technique for each of the following problems.(a) Single crystal X-ray diffraction data show that a compound crystallizes as a dihydrate. How could you show that the bulk sample was anhydrous?(b) The single crystal structure of a compound has been determined, and you
(a) By using the data in Appendix 5, account for the isotopic distribution shown in Fig. 1.1b. (b) The mass spectrum of S8 shows other peaks at lower values of m/z. By considering the structure of S8 shown in Fig. 1.1c, suggest the origin of these lowermass peaks.Figure 1.1b and 1.1c.Data from
Using the list of naturally occurring isotopes in Appendix 5, determine the number of electrons, protons and neutrons present in an atom of each isotope of (a) Al, (b) Br (c) Fe, and give appropriate notation to show these data for each isotope.Data from Appendix 5
‘Arsenic is monotopic.’ What does this statement mean? Using Appendix 5, write down three other elements that are monotopic.Data from Appendix 5
Hydrogen possesses three isotopes, but tritium (3H), which is radioactive, occurs as less than 1 in 1017 atoms in a sample of natural hydrogen. If the value of Ar for hydrogen is 1.008, estimate the percentage abundance of protium, 1H, and deuterium, 2H (or D) present in a sample of natural
Calculate the corresponding wavelengths of electromagnetic radiation with frequencies of (a) 3:0 × 1012 Hz, (b) 1:0 × 1018 Hz (c) 5:0 × 1014 Hz. By referring to Appendix 4, assign each wavelength or frequency to a particular type of radiation (e.g. microwave).Data from Appendix 4 The
Chromium has four isotopes, How many electrons, protons and neutrons does each isotope possess? 50 54 Cr, Cr, Cr and Cr. 53 54 24 24
Four of the lines in the Balmer series are at 656.28, 486.13, 434.05 and 410.17 nm. Show that these wavelengths are consistent with eq. 1.4.Data from Equation 1.4. 1 0 = = = R ( 2²/2 - 1/2 ) R = Rydberg constant for hydrogen = 1.097 x 107 m¹ = 1.097 x 105 cm-¹ 10³ (1.4)
Using data from Appendix 8, construct a graph to show the trend in the third ionization energies of the elements from Li to Kr. Compare the graph with that shown in Fig. 1.16, and rationalize what you observe.Figure 1.16Data from Appendix 8Data are given for the first five ionizations.† IE(n) in
State which of the following n' → n transitions in the emission spectrum of atomic hydrogen belong to the Balmer, Lyman or Paschen series: (a) 3 → 1;(b) 3 → 2; (c) 4 → 3; (d) 4 → 2; (e) 5 → 1.
Calculate the energy (in kJ per mole of photons) of a spectroscopic transition, the corresponding wavelength of which is 450 nm.
Using the Bohr model, determine the values of the radii of the second and third orbits of the hydrogen atom.
(a) Will a plot of R(r) for the 1s atomic orbital of He+ be identical to that of the H atom (Fig. 1.5a)?(b) On the same axis set, sketch approximate representations of the function 4πr2R(r)2 for H and He+.Figure 1.5a. R(r) 1s/(atomic units)-3/2 2 1 0 0 12 Distance from nucleus/atomic units (a)
How is the (a) Energy (b) Size of an ns atomic orbital affected by an increase in n?
Write down a set of quantum numbers that uniquely defines each of the following atomic orbitals: (a) 6s,(b) Each of the five 4d orbitals.
Do the three 4p atomic orbitals possess the same or different values of (a) Principal quantum number,(b) The orbital quantum number and (c) The magnetic quantum number? Write down a set of quantum numbers for each 4p atomic orbital to illustrate your answer.
Using eq. 1.16, determine the energies of atomic orbitals of hydrogen with n = 1, 2, 3, 4 and 5. What can you say about the relative spacings of the energy levels?Data from Equation 1.16 E= kZ² nº k= = a constant = 1.312 x 10³ kJ mol-1 (1.16)
How many radial nodes does each of the following orbitals possess: (a) 2s; (b) 4s; (c) 3p; (d) 5d; (e) 1s;(f ) 4p
Comment on differences between plots of R(r) against r, and 4πr2R(r)2 against r for each of the following atomic orbitals of an H atom: (a) 1s; (b) 4s; (c) 3p.
Draw energy level diagrams (see Fig. 1.15) to represent the ground state electronic configurations of the atoms in problem 1.26.Figure 1.15Data from Problem 1.26For each of the following atoms, write down a ground state electronic configuration and indicate which electrons are core and which are
Write down the sets of quantum numbers that define the (a) 1s, (b) 4s, (c) 5s atomic orbitals.
Write down the three sets of quantum numbers that define the three 3p atomic orbitals.
How many atomic orbitals make up the set with n = 4 and l = 3? What label is given to this set of orbitals? Write down a set of quantum numbers that defines each orbital in the set.
Which of the following species are hydrogen-like: (a) H+; (b) He+; (c) He−; (d) Li+; (e) Li2+
In Fig. 1.16, identify the trends in the first ionization energies of the elements in (a) Descending group 1,(b) Descending group 13, (c) Crossing the first row of the d-block, (d) Crossing the row of elements from B to Ne, (e) Going from Xe to Cs, (f ) Going from P to S. Rationalize each of
Calculate the energy of the 3s atomic orbital of an H atom. Is the energy of the hydrogen 3p atomic orbital the same as or different from that of the 3s orbital?
Figure 1.17 shows the values of IE1 for the first 10 elements. (a) Label each point with the symbol of the appropriate element. (b) Give detailed reasons for the observed trend in values.Figure 1.17. First ionization energy/kJ mol-¹ 2500 2000 1500 1000 500 72 دیا 1 6 9 T 10 8 Atomic number
(a) Using the data in Table 1.5, determine a value for ∆H for the process:(b) Comment on the relevance of the sign and magnitude of your answer to part (a) in the light of the fact that many metal oxides with ionic lattices are thermodynamically stable.Table 1.5 O(g) + 2e¯ 0²(g)
Write down the six sets of quantum numbers that describe the electrons in a degenerate set of 5p atomic orbitals. Which pairs of sets of quantum numbers refer to spin-paired electrons?
How do you account for the fact that, although potassium is placed after argon in the periodic table, it has a lower relative atomic mass? List 1 S6 and Sg 1⁹F and ³¹p isotope of hydrogen ¹²℃ and ¹³℃ hydrogen ion group 1 elements same energy negatively charged particle spin-paired
For a neutral atom, X, arrange the following atomic orbitals in an approximate order of their relative energies (not all orbitals are listed): 2s, 3s, 6s, 4p, 3p, 3d, 6p, 1s.
Using the concepts of shielding and penetration, explain why a ground state configuration of 1s22s1 for an Li atom is energetically preferred over 1s22p1.
Ruthenium, osmium, rhodium, iridium, palladium and platinum (Fig. 1.14) are called the platinum group metals. Most of the world’s reserves of these metals are in mineral deposits in Russia, Canada and South Africa. The platinum group metals are important as catalysts for air pollution control
For each of the following atoms, write down a ground state electronic configuration and indicate which electrons are core and which are valence: (a) Na, (b) F,(c) N, (d) Sc.
Write down the ground state electronic configuration of boron, and give a set of quantum numbers that uniquely defines each electron.
Write down (with reasoning) the ground state electronic configurations of (a) Li, (b) O, (c) S,(d) Ca, (e) Ti, (f) Al.
Draw energy level diagrams to show the ground state electronic configurations of only the valence electrons in an atom of (a) F, (b) Al (c) Mg.
The ground state electronic configuration of a group 16 element is of the type [X]ns2np4 where X is a group 18 element. How are the outer four electrons arranged, and what rules are you using to work out this arrangement?
(a) Write down an equation that defines the process to which the value of IE4 of Sn refers. Is this process exothermic or endothermic? (b) To what overall process does a value of (IE1 + IE2 + IE3) for Al refer?
The first four ionization energies of an atom X are 403, 2633, 3900 and 5080 kJ mol−1. Suggest towhat periodic group X belongs and give reasons for your choice.
(a) How would Fig. 1.9 have to be modified to show boundary surfaces for the 2s and the 3p wavefunctions of a one-electron species?(b) ‘The probability of finding the electron of a ground-state hydrogen atom at a distance r from the proton is at a maximum when r = 52.9 pm.’ Why is this
Figure 1.18 shows the emission spectrum of sodium. Low-pressure sodium street lamps depend upon this bright yellow emission from sodium atoms excited by an electrical discharge. Figure 1.18 shows a simple spectrum (see figure caption), but the National Institute of Standards and Technology (NIST)
What is the evidence that the aufbau principle is only approximately true?
The first list in the table on the left contains symbols or phrases, each of which has a ‘partner’ in the second list. Match the ‘partners’; there is only one match for each pair of symbols or phrases.
Suggest explanations for the following.(a) High values of ionization energies are associated with the noble gases.(b) The enthalpy changes associated with the attachment of the first and second electrons to an O atom are exothermic and endothermic, respectively.(c) In an Li atom in its ground
The sign convention for electron affinity can often cause confusion for students. In this textbook, why have we referred to ‘an enthalpy change for the attachment of an electron’ rather than to an ‘electron affinity’?
Draw Lewis structures to describe the bonding in the following molecules: (a) F2; (b) BF3; (c) NH3;(d) H2Se; (e) H2O2; (f) BeCl2; (g) SiH4; (h) PF5.
One member of each of the following sets of compounds is not isoelectronic with the others. Which one in each set is the odd one out? (a) [NO₂], CO₂, [NO₂] and [N3] (b) [CN], N₂, CO, [NO] and [0₂]²- (c) [SiF6], [PF6], [AlF6]³ and [BrF]¯¯
Using the data in Table 2.2, determine which of the following covalent single bonds is polar and (if appropriate) in which direction the dipole moment acts. (a) N—H; (b) F—Br; (c) C—H; (d) P—Cl;(e) N—Br.Table 2.2
Use the Lewis structure model to deduce the type of nitrogen–nitrogen bond present in (a) N2H4, (b) N2F4, (c) N2F2 (d) [N2H5]+.
Draw the resonance structures for the O3 molecule. What can you conclude about the net bonding picture?
Draw Lewis structures for (a) CO2, (b) SO2, (c) OF2(d) H2CO.
Determine the shapes of each of the following molecules and then, using the data in Table 2.2, state whether each is expected to be polar or not:(a) H2S; (b) CO2; (c) SO2; (d) BF3; (e) PF5 ; (f) cis-N2F2; (g) trans-N2F2; (h) HCN.Table 2.2
In the following table, match a species in list 1 with an isoelectronic partner in list 2. Some species may have more than one partner. Qualify how you have interpreted the term isoelectronic. List 1 F₂ NH3 [GaBr4] [SH] [BH4] [AsF] [PBT4]+ HF List
Each of the following is a radical. For which does a Lewis structure correctly confirm this property:(a) NO, (b) O2, (c) NF2?
(a) Use VB theory to describe the bonding in the diatomic molecules Li2, B2 and C2. (b) Experimental data show that Li2 and C2 are diamagnetic whereas B2 is paramagnetic. Is the VB model consistent with these facts?
Using VB theory and the Lewis structure model, determine the bond order in (a) H2, (b) Na2, (c) S2,(d) N2 (e) Cl2. Is there any ambiguity with finding the bond orders by this method?
(a) Draw resonance structures for CO, choosing only those that you think contribute significantly to the bonding.(b) Figure 2.15a shows an MO diagram for CO. Two MOs are illustrated by schematic representations. Draw similar diagrams for the remaining six MOs.Figure 2.15a Energy S 25+ с 30 40 n*
Does VB theory indicate that the diatomic molecule He2 is a viable species? Rationalize your answer.
Use the VSEPR model to rationalize the structure of SOF4 shown in Fig. 2.19. What are the bond orders of (a) Each S—F bond (b) The S—O bond?Figure 2.19
(a) Use MO theory to determine the bond order in each of [He2]+ and [He2]2+. (b) Does the MO picture of the bonding in these ions suggest that they are viable species?
(a) Construct an MO diagram for the formation of O2; use only the valence orbitals of the oxygen atoms. (b) Use the diagram to rationalize the following trend in O__O bond distances: O2, 121 pm; [O2]+, 112 pm; [O2]−, 134 pm; [O2]2−, 149 pm. (c) Which of these species are paramagnetic?
Confirm that the octet rule is obeyed by each of the atoms in the following molecules: (a) CF4, (b) O2,(c) AsBr3, (d) SF2.
Draw charge-separated resonance structures to give a representation of the bonding in PF5 such that the octet rule is strictly obeyed.
Pick out pairs of isoelectronic species from the following list; not all species have a ‘partner’: HF; CO2; SO2; NH3; PF3 ; SF4; SiF4; SiCl4; [H3O]+; [NO2]+; [OH]−; [AlCl4]−.
State whether you expect the following species to possess stereoisomers and, if so, draw their structures and give them distinguishing labels:(a) BF2Cl;(b) POCl3; (c) MePF4; (d) [PF2Cl4]−.
The table below gives the average composition of the Earth’s atmosphere (ppm = parts per million). Water vapour is also present in small and variable amounts.(a) Draw a Lewis structure for N2O, ensuring that each atom obeys the octet rule. (b) Use the VSEPR model to predict the molecular shapes
(a) On steric grounds, should cis- or trans-[PtCl2(PPh3)2] be favoured?(b) Use the VSEPR model to rationalize why SNF3 is tetrahedral but SF4 has a see-saw geometry.(c) Suggest why KrF2 is a linear rather than bent molecule.
Account for each of the following observations.(a) IF5 is a polar molecule.(b) The first ionization energy of K is lower than that of Li.(c) BI3 is trigonal planar while PI3 is trigonal pyramidal in shape.
Suggest reasons for the following observations.(a) The second ionization energy of He is higher than the first despite the fact that both electrons are removed from the 1s atomic orbital.(b) Heating N2F2 at 373K results in a change from a non-polar to polar molecule.(c) S2 is paramagnetic.
(a) Draw possible stereoisomers for the trigonal bipyramidal [SiF3Me2]− anion (Me = CH3). An X-ray diffraction study of a salt of [SiF3Me2]− shows that two F atoms occupy axial sites. Suggest why this stereoisomer is preferred over the other possible structures that you have drawn.(b) Account
(a) Write down the ions that are present in the compound [PCl4][PCl3F3]. What shape do you expect each ion to adopt? In theory, does either ion possess stereoisomers?(b) Use the VSEPR model to rationalize why BCl3 and NCl3 do not adopt similar structures. Is either molecule expected to be polar?
Assuming that the VSEPR model can be applied successfully to each of the following species, determine how many different fluorine environments are present in each molecule or ion: (a) [SiF6]2−,(b) XeF4, (c) [NF4]+, (d) [PHF5]−, (e) [SbF5]2−.
Critically compare the VB and MO treatments of the bonding in O2, paying particular attention to the properties of O2 that the resulting bonding models imply.
Carbon monoxide is a toxic pollutant which arises from the partial combustion of carbon-based fuels. Complete combustion produces CO2. The toxicity of CO is a result of its competition for the O2-binding sites in blood, i.e. the iron present in haemoglobin (see Chapter 29). When CO binds to the
For each of the following 2-dimensional shapes, determine the highest order rotation axis of symmetry. (a) ΔΔυ (b) (c) (P)
Volcanoes and deep sea hydrothermal vents are both associated with sulfur-rich environments. Mount Etna is classed as a continuously degassing volcano and emissions of SO2 and H2S are around 1.5 Tg y−1 and 100 Gg y−1, respectively (Tg = 1012 g; Gg = 109 g). (a) Draw Lewis structures for
The structure of H2O2 was shown in Fig. 2.1. Apart from the operator E, H2O2 possesses only one other symmetry operator. What is it?Figure 2.1
Which of the following species contain inversion centres? (a) BF3; (b) SiF4; (c) XeF4; (d) PF5;(e) [XeF5]−; (f ) SF6; (g) C2F4; (h) H₂C=C=CH₂.
Give the structures of the following molecules: (a) BCl3; (b) SO2; (c) PBr3; (d) CS2; (e) CHF3. Which molecules are polar?
In group theory, what is meant by the symbols (a) E,(b) σ, (c) Cn(d) Sn What is the distinction between planes labelled σh, σv, σv' and σd?
Draw the structure of SO2 and identify its symmetry properties.
By drawing appropriate diagrams, illustrate the fact that BF3 possesses a 3-fold axis, three 2-fold axes, and four planes of symmetry. Give appropriate labels to these symmetry elements.
Using the answer to problem 3.6 to help you, deduce which symmetry elements are lost on going from(a) BF3 to BClF2(b) BClF2 to BBrClF. (c) Which symmetry element (apart from E) is common to all three molecules?Data from Problem 6By drawing appropriate diagrams, illustrate the fact that BF3
Which of the following species or ions contain (a) A C3 axis but no σh plane, (b) A C3 axis and a σh plane: NH3; SO3; PBr3; AlCl3; [SO4]2−; [NO3]−?
Which of the following species contain a C4 axis and a σh plane: CCl4; [ICl4]−; [SO4]2−; SiF4; XeF4?
How many mirror planes do each of the following molecules contain: (a) SF4; (b) H2S; (c) SF6; (d) SOF4; (e) SO2; (f) SO3
(a) What structure would you expect Si2H6 to possess? (b) Draw the structure of the conformer most favoured in terms of steric energy. (c) Does this conformer possess an inversion centre? (d) Draw the structure of the conformer least favoured in terms of steric energy. (e) Does
Explain what is meant by an ∞-fold axis of rotation.
To which point group does NF3 belong?
The point group of [AuCl2]− is D∞h. What shape is this ion?
In worked example 2.7, the structure of the [XeF5]− ion was predicted. Confirm that this structure is consistent with D5h symmetry.Data from Example 2.7.Predict the structures of (a) XeF2 and (b) [XeF5]− Xe is in group 18 and possesses eight electrons in its valence shell. F is in group 17,
Determine the point group of SF5Cl.
The point group of BrF3 is C2v. Draw the structure of BrF3 and compare your answer with the predictions of the VSEPR model.
Assign a point group to each member in the series(a) CCl4, (b) CCl3F, (c) CCl2F2, (d) CClF3 (e) CF4.
By considering the effect of each symmetry operation of the D3h point group on the symmetric deformation mode shown in Fig. 3.14, confirm that this mode has A2'' symmetry.Figure 3.14 Symmetric stretch (4₁) IR inactive Symmetric deformation (4₂") IR active (498 cmr-¹) Asymmetric stretch
(a) Deduce the point group of SF4. (b) Is SOF4 in the same point group?
Which of the following point groups possesses the highest number of symmetry elements: (a) Oh;(b) Td; (c) Ih?
Determine the number of degrees of vibrational freedom for each of the following: (a) SO2; (b) SiH4; (c) HCN; (d) H2O; (e) BF3.

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