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inorganic chemistry

Questions and Answers of Inorganic Chemistry

Consider the p orbitals on the four Cl atoms of tetrahedral [CoCl4]2−, with one p orbital on each Cl pointing directly at the central metal atom. (a) Confirm that the four p orbitals which
From the relative atomic orbital and molecular orbital energies depicted in Fig. 3.32, describe the character as mainly F or mainly S for the frontier orbitals e (the HOMO) and 2t (the LUMO) in SF6.
(a) Determine the point group of the PF5 molecule. (Use VSEPR, if necessary, to assign geometry.) (b) What is the maximum degeneracy of its molecular orbitals? (c) Which P3p orbitals
Consider all 12 of the p orbitals on the four Cl atoms of a square planar complex like [PtCl4]2−. (a) Determine how these p orbitals transform under D4h and reduce the representation.(b) Which
Consider the displacements of the atoms in the trigonal bipyramidal molecule PF5. Calculate the number and symmetry of its vibrational modes.
Consider an octahedral complex and construct all the σ- and π-bonding SALCs.
How many vibrational modes does an SO3 molecule have (a) In the plane of the nuclei,(b) Perpendicular to the molecular plane?
What are the symmetry species of the vibrations of (a) SF6,(b) BF3 that are both IR and Raman active?
Consider CH4. Use the projection operator method to construct the SALCs of A1 + T2 symmetry that derive from the four H1s orbitals. With which atomic orbitals on C would it be possible to form MOs
Use the projection operator method to determine the SALCs required for formation of σ bonds in (a) BF3, (b) PF5.
Based on the MO discussion of NH3 in the text, find the average NH bond order in NH3 by calculating the net number of bonds and dividing by the number of NH groups.
Draw the linear combinations of H1s orbitals for linear and square forms of the hypothetical H4 molecule and construct the respective MO diagrams to demonstrate that one of these forms should be
(a) Construct the form of each molecular orbital in linear [HHeH]2+ using 1s basis atomic orbitals on each atom and considering successive nodal surfaces. (b) Arrange the MOs in increasing
In the paper ‘What can the Bohr–Sommerfeld model show students of chemistry in the 21st century?’ (M. Niaz and L. Cardellini, J. Chem. Educ., 2011, 88, 240) the authors use the development of
What is the ratio of the energy of an electronic ground-state He+ ion to that of a Be3+ ion?
Survey the early and modern proposals for the construction of the periodic table. You should consider attempts to arrange the elements on helices and cones as well as the more practical
According to the Born interpretation, the probability of finding an electron in a volume element dt is proportional to ψ2dτ. (a) What is the most probable location of an electron in an H atom
In their 2009 paper ‘Icon of chemistry: The periodic system of chemical elements in the new century’ (Angew. Chem. Int. Ed., 2009, 48, 3404), S. Wang and W. Schwarz claim that the periodic system
The ionization energy of H is 13.6 eV. What is the difference in energy between the n = 1 and n = 6 levels?
The decision about which elements should be identified as belonging to the f block has been a matter of some controversy. A view has been expressed by W.B. Jensen (J. Chem. Educ., 1982, 59, 635).
The ionization energies of rubidium and silver are 4.18 and 7.57 eV, respectively. Calculate the ionization energies of an H atom with its electron in the same outermost orbitals as in these two
Show that the following four lines in the Lyman series can be predicted from eqn 1.1: 91.127, 97.202, 102.52, and 121.57 nm.Equation 1.1. 2 R 1 n² n² (1.1)
During 1999 several papers appeared in the scientific literature claiming that d orbitals of Cu2O had been observed experimentally. In his paper ‘Have orbitals really been observed?’ (J. Chem.
When 58.4 nm radiation from a helium discharge lamp is directed on a sample of krypton, electrons are ejected with a velocity of 1.59 × 106 m s−1. The same radiation ejects electrons from Rb atoms
At various times the following two sequences have been proposed for the elements to be included in Group 3: (a) Sc, Y, La, Ac, (b) Sc, Y, Lu, Lr. Because ionic radii strongly influence
Calculate the wavelength of the line in the atomic spectrum of hydrogen in which n1 = 1 and n2 = 3. What is the energy change for this transition?
In the paper ‘Ionization energies of atoms and atomic ions’ (P.F. Lang and B.C. Smith, J. Chem. Educ., 2003, 80, 938) the authors discuss the apparent irregularities in the first and second
Calculate the wavenumber (ṽ=1/λ) and wavelength of the first transition in the visible region of the atomic spectrum of hydrogen.
The electron configuration of the transition metals is described by W.H.E. Schwarz in his paper ‘The full story of the electron configurations of the transition elements’ (J. Chem. Educ., 2010,
What is the relation of the possible angular momentum quantum numbers to the principal quantum number?
How many orbitals are there in a shell of principal quantum number n?
The second ionization energies of some Period 4 elements areIdentify the orbital from which ionization occurs and account for the trend in values. Ca Sc 1145 1235 Ti 1310 V 1365 Cr 1592 Mn 1509
What are the values of the n, l, and ml quantum numbers that describe the 5f orbitals?
Use sketches of 2s and 2p orbitals to distinguish between (a) The radial wavefunction (b) The radial distribution function.
Predict how many nodes and how many nodal planes a 4p orbital will have.
Use the data in Tables 1.6 and 1.7 to test Mulliken’s proposition that electronegativity values are proportional to I + Ea.Table 1.6.Table 1.7. TABLE 1.6 Electron affinities of the main-group
Draw pictures of the two d orbitals in the xy-plane as flat projections in the plane of the paper. Label each drawing with the appropriate mathematical function, and include a labelled pair of
Consider the process of shielding in atoms, using Be as an example. What is being shielded? What is it shielded from? What is doing the shielding?
Calculate the screening constants for the outermost electron in the elements Li to F. Comment on the values you obtain.
In general, ionization energies increase across a period from left to right. Explain why the second ionization energy of Cr is higher, not lower, than that of Mn.
Compare the first ionization energy of Ca with that of Zn. Explain the difference in terms of the balance between shielding with increasing numbers of d electrons and the effect of increasing nuclear
Compare the first ionization energies of Sr, Ba, and Ra. Relate the irregularity to the lanthanoid contraction.
Give the ground-state electron configurations of (a) C, (b) F,(c) Ca, (d) Ga3+, (e) Bi, (f) Pb2+.
Give the ground-state electron configurations of (a) Sc, (b) V3+, (c) Mn2+ (d) Cr2+, (e) Co3+, (f) Cr6+, (g) Cu, (h) Gd3+.
Give the ground-state electron configurations of (a) W,(b) Rh3+, (c) Eu3+, (d) Eu2+, (e) V5+, (f) Mo4+.
Identify the elements that have the ground-state electron configurations: (a) [Ne]3s23p4, (b) [Kr]5s2, (c) [Ar]4s23d3,(d) [Kr]5s24d5, (e) [Kr]5s24d105p1, (f) [Xe]6s24f6.
Without consulting reference material, draw the form of the periodic table with the numbers of the groups and the periods and identify the s, p, and d blocks. Identify as many elements as you can.
Account for the trends across Period 3 in (a) Ionization energy, (b) Electron affinity, (c) Electronegativity.
Account for the fact that the two Group 5 elements niobium (Period 5) and tantalum (Period 6) have the same atomic radii.
Identify the frontier orbitals of a Be atom in its ground state.
Second order rate constants, k2, for the reaction of trans-[Pt(PEt3)2Ph(MeOH)]+ with pyridine (py) in MeOH to give trans-[Pt(PEt3)2Ph(py)]+ vary with temperature as shown below. Use the data to
What structural features would you expect in the solid state of (a) Cs2[NpO2(acac)3], (b) Np(BH4)4,(c) The guanidinium salt of [ThF3(CO3)3]5−,(d) Li3[LuMe6]·3DME, (e)
Suggest likely products in the following reactions:(a) UF4 with F2 at 570 K; (b) Pa2O5 with SOCl2 followed by heating with H2; (c) UO3 with H2 at 650 K; (d) heating UCl5; (e) UCl3
(a) Compound 27.20 reacts with MeLi with loss of CH4 to give A. When A reacts with TbBr3, a terbium-containing complex B is formed, the mass spectrum of which shows an envelope of peaks at m/z 614 as
(a) At 670 K, CaF2 (mp=1691 K) doped with 1% NaF has an electrical conductivity of 0.1Ω−1 m−1. Suggest how this conductivity arises.(b) The value of Tc for YBa2Cu3O7 is 93 K. Sketch the change
The catalyst [Rh(Ph2PCH2CH2PPh2)]+ can be prepared by the reaction of [Rh(nbd)(Ph2PCH2CH2PPh2)]+ (nbd = 25.37) with two equivalents of H2. In coordinating solvents [Rh(Ph2PCH2CH2PPh2)]+, in the form
Sketch reaction profiles for the reaction pathways described in eqs. 26.5 and 26.6. Comment on any significant features including activation energies.Equations. MLXX → MLX + X intermediate MLx + Y
Under pseudo-first order conditions, the variation of kobs with [py] for reaction of square planar [Rh(cod)(PPh3)2]+ (2 × 10−4 mol dm−3; cod= 24:22) with pyridine is as follows:Show that the
(a) The cis-and trans-isomers of [PtCl2(NH3)(NO2)]− are prepared by reaction sequences 26.19 and 26.20 respectively. Rationalize the observed differences in products in these routes. (b) Suggest
(a) Suggest a mechanism for the reaction:(b) If the intermediate in your mechanism is sufficiently long-lived, what complication might arise? trans-[PtL₂Cl₂] + Y→ trans-[PtL₂CIY]+ + CI CI™
The reaction of trans-[Pt(PEt3)2PhCl] with the strong nucleophile thiourea (tu) in MeOH follows a 2-term rate law withA plot of kobs against [tu] is linear with the line passing close to the origin.
Suggest structures for the [BiCl5]2− and [Bi2Cl8]2− anions, the formation of which was described.
The reaction of InBr with an excess of HCBr3 in 1,4-dioxane (C4H8O2) leads to compound A which is an adduct of 1,4-dioxane and contains 21.4% In. During the reaction, the indium is oxidized. The 1H
Review what is meant by the following terms:(a) Elementary step,(b) Rate-determining step,(c) Activation energy,(d) Intermediate,(e) Transition state,(f) Rate equation,(g) Zero, first and second
Discuss evidence to support the proposal that substitution in square planar complexes is an associative process.
For the reaction:it is found that:and foris positive. Rationalize these data. [Co(NH3)5(OHz)]3+ +X → [Co(NH3)sX]2+ +H_O
Derive rate law 26.45 for the mechanism shown in steps 26.42–26.44.Equations [Co(NH3)sX]+ + [OH] = [Co(NH3)4(NH2)X] +H,O = (26.42) [Co(NH3)4(NH2)X]* k₂ - [Co(NH3)4(NH,)]2+ +X^ (26.43)
The structure of cisplatin is shown below:Despite its success as an anticancer drug, the mechanism by which the drug targets DNA in the body is not fully understood, although it is known that the
The rate constants for racemization (kr) and dissociation (kd) of [FeL3]4− (H2L = 26.12) at several temperatures, T, are given in the table.(a) Determine for each reaction. (b) What can you deduce
Two twist mechanisms for the rearrangement ofare shown in Fig. 26.9. The initial diagrams in (a) and (b) are identical; confirm that the enantiomers formed in (a) and (b) are also identical.Fig.
(a) Rationalize the formation of the products in the following sequence of reactions:(b) Suggest methods of preparing [RhCl5(OH2)]2−, cis-[RhCl4(OH2)2]− and fac-[RhCl3(OH2)3].
Substitution of H2O in [Fe(OH2)6]3+ by thiocyanate is complicated by proton loss. By considering the reaction scheme below, derive an expression forin terms of the equilibrium and rate constants,
Rationalize the observation that when the reaction:is carried out in H2(18O), the water in the complex contains equal proportions of H2(18O) and H2(16O). [Co(NH3)4 (CO3)]* [H₂O]*,
The rate of racemization of [CoL3] where HL = 26.11a is approximately the same as its rate of isomerization into [CoL'3] where HL' =26.11b. What can you deduce about the mechanisms of these
(a) The reaction:occurs by a dissociative mechanism and the first order rate constants, k1, vary with the nature of substituent X as follows: CO 3 ≈ P(OPh)3nBu3: Comment on these data.(b) The
The reaction:in liquid NH3 is catalysed by KNH2. Suggest an explanation for this observation. [Cr(NH3)5 C1]²+ + NH3 → [Cr(NH3)6]³+ + CI
Account for the relative values of the rate constants for the following electron-transfer reactions in aqueous solution:For which reactions is ΔG° = 0? Reaction
(a) The reaction of cis-[PtMe2(Me2SO)(PPh3)] with pyridine leads to cis-[PtMe2(py)(PPh3)] and the rate of reaction shows no dependence on the concentration of pyridine. At 298 K, the value of ΔS‡
Suggest two experimental methods by which the kinetics of the following reaction might be monitored:Comment on factors that contribute towards the suitability of the methods suggested. Ph P Ph₂P Pd
What reason can you suggest for the sequence Co > Rh > Ir in the rates of anation of [M(OH2)6]3+ ions?
Suggest products in the following ligand substitution reactions. Where the reaction has two steps, specify a product for each step. Where more than one product could, in theory, be possible,
Suggest a mechanism for the possible racemization of tertiary amines NR1R2R3. Is it likely that such molecules can be resolved?
Consider the following reaction that takes place in aqueous solution; L, X and Y are general ligands.Discuss the possible competing pathways that exist and the factors that favour one pathway over
Give an example of a reaction that proceeds by an inner-sphere mechanism. Sketch reaction profiles for inner-sphere electron-transfer reactions in which the rate-determining step is (a) Bridge
Discuss, with examples, the differences between inner- and outer-sphere mechanisms, and state what is meant by a self-exchange reaction.
(a) If, in an electron-transfer process, there is both electron and ligand transfer between reagents, what can you conclude about the mechanism?(b) Explain why very fast electron transfer between
(a) By considering Fig. 27.9, suggest a method for the separation of Am from U, Np and Pu.(b) What would you expect to happen when a solution of NpO2(ClO4)2 in 1Μ HClO4 is shaken with Zn amalgam and
Vasovist® is the tradename of a Gd(III) complex which was the first intravascular contrast agent (see Box 4.3) approved in the EU for use in magnetic resonance angiography. Interactions between the
Use Hund’s rules to derive the ground state of the Ce3+ ion, and calculate its magnetic moment. (The spin–orbit coupling constant for Ce3+ is 1000 cm−1 and so the population of states other
(a) What is the lanthanoid contraction? (b) Explain how the lanthanoids can be separated from their ores.
Identify isotopes A–F in the following sequence of nuclear reactions: (a) 238U (b) D (n, y) -B E -B -B- B- C A (n, 7) 242, 242 Am - F
Show that the stability of a lanthanoid dihalide LnX2 with respect to disproportionation into LnX3 and Ln is greatest for X = I.
How would you attempt to show that a given lanthanoid diiodide, LnI2, has saline rather than metallic character?
Comment on each of the following observations:(a) ΔH° for the formation of [Ln(EDTA)(OH2)x]− (x = 2 or 3) in aqueous solution is nearly constant for all Ln and is almost zero.(b) The value of E°
Identify the starting isotopes A–E in each of the following syntheses of transactinoid elements: (a) A + He → 25 Md+n 16. (b) B+¹0152No +5n (c) C+¹B25Lr + 4n (d) D + ¹80104Rf
Comment on the observations that the electronic spectra of lanthanoid complexes contain many absorptions some of which are weak and sharp and similar to those of the gas-phase metal ions, and some of
A typical emission spectrum of a complex of Dy3+ contains sharp maxima between 450 and 800 nm which are assigned to 4F9/2 → 6HJ transitions for values of J = 15/2, 13/2, 11/2 and 9/2.(a) What is
The emission spectrum of an Sm(III) complex contains sharp maxima in the range 525–725 nm. The emitting state is 4G5/2, and transitions are to the 6HJ states for J = 11/2. 9/2, 7/2 and 5/2.(a)
Discuss the variation in coordination numbers among complexes of the 4f metals.
The reactions of Ln(NCS)3 with [NCS]− under varying conditions lead to discrete anions such as [Ln(NCS)6]3−, [Ln(NCS)7](OH2)]4− and [Ln(NCS)7]4−. What can you say about possible structures

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