Chemistry 341 Section X - Mid-term Exam - 1½ hour
October 16th, 2001 Answer all questions. Please be sure to provide adequate explanations of you answers where it is appropriate, including diagrams. All questions carry equal weight. 1. a. The hydrated chromium chloride that is available commercially has the overall composition CrCl3.6H2O. In solution it is violet, and has a molar conductivity similar to that of [Co(NH3)6)]Cl3. In contrast, CrCl3.5H2O is green and has a lower molar conductivity in solution. If a diluted solution of this green complex is allowed to stand for several hours it turns violet. Interpret these observations with structural diagrams. The sort of formulae given in the question might be found on the label on the bottle, or in the chemical supplier catalogs. They do not contain any reliable structural information! You are told that in solution, violet CrCl3.6H2O has a conductivity similar to that of [Co(NH3)6)]Cl3 i.e. it is probably also a 1:3 cation:anion electrolyte. So, the real formula is probably [Cr(H2O)6)]Cl3. The green compound starts out with less water in the solid state. If it too is octahedral there must be at least one Cl- in the Cr3+ coordination sphere. The "lower conductivity" (it does not say how much lower) could correspond to either a 1:2 or 1:1 electrolyte, i.e. either [Cr(H2O)5)Cl]Cl2 or [Cr(H2O)4)Cl2]Cl In aqueous solution, the coordinated Cl- is gradually replaced by H2O, and the violet hexaquo complex is formed. b. The reaction of [ZrCl4(dppe)] with Mg(CH3)2 gives a compound [Zr(CH3)4(dppe)] where the NMR spectrum shows that the CH3 groups are all equivalent. Which geometry, octahedral, or trigonal prismatic, is consistent with this observation. (The ligand dppe is Φ 2PCH2CH2PΦ 2.) The two structures would be:
To work this out you would have to remember the not very memorable levels: my mistake!
. [Fe(CN)6]4This is surely a strong field d6 case because of the combination of Fe2+ and CN-. LFSE = (4 x 0.4 .4∆
c.2 x 0. [NiCl4]2Chloride is quite low in the spectrochemical series. 2.514 + 2 x 0.)
b. LFSE = 6 x 0. The octahedral structure has a two fold axis only and there are two CH3's cis to both the P's.2 x 0.4∆ o (The negative sign is "understood" since it is a stabilization energy. and two trans to one P and cis to the other. the number of unpaired electrons. Determine the d-electron configuration.4 x 0.8∆
d.228)∆ o = 2. so this Ni2+ d8 complex will probably be tetrahedral.6 . LFSE = (4 x 0.The prismatic structure (on the left) has two planes of symmetry which render the 4 CH3 groups equivalent. Please make it clear how you make any necessary decisions: a.4)∆ t = 0. and the ligand field stabilization energy (LFSE) in terms of ∆ o or ∆ t as appropriate for each of the following complexes.428 . [Ni(CN)4]2Cyanide is high in the spectrochemical series so this is Ni2+ d8 complex will probably be square-planar.6)∆ o = 0. so they are inequivalent.4∆ o = 2. [Fe(H2O)6]2+ This is probably a weak field d6 case (Fe2+ and H2O) LFSE = (4 x 0.
Log K2 Log K3 4. a.26 -1. What mechanism of substitution does this observation support? If the rate is only weakly related to the nature of the entering ligand. molecules with fewer coordinated water molecules are less likely in aqueous solution: a molecule where all the water has been removed and replaced by ethylene diamine is the least likely species.0
Cu2+ i. [Ni(CO)4] This is a Ni0 d10 complex and the ligand field stabilization energy is zero in any geometry. Ni2+. The rate constants for the formation of of [CoX(NH3)5]2+ from [Co(NH3)6)3+ for X = Cl-. and Cu2+ are as follows: [M(H2O)6]2+ + en [M(H2O)4en]2+ + en [M(H2O)2(en)2]2+ + en Ion Co2+ Ni
[M(H20)4en]2+ + 2H2O
[M(H20)2(en)2]2+ + 2H2O [M(en)3]2+ + 2H2O K3
log K1 5.05 3.differ by no more than a factor of two.
Why is there a general trend: K1 > K2 > K3 Statistically. and SCN.
3.52 10.e. The equilibrium constants for the successive reactions of ethylene diamine with Co2+. A later section of the course examines the mechanisms of substitution reactions in much greater detail.83 6. Expect questions of a more complex nature on the final exam! b. so there is no reason for it not to be tetrahedral. Br-. N3-.10 4.89 7. then the mechanism is dissociative.
We have to consider the competing equilibrium: [Cu(H2O)2(en)2]2+ [M(en)2]2+ + 2H2O K4
iii. the most probable explanation is a change in the nature of the species involved in the equilibrium.ii. In this case. will be greater for the smaller Ni2+ ion. Deduce the Russell-Saunders terms for the configuration p2. The absolute values of the LFSE i. so the differences should also be greater. ∆ o. and the concentration of [Cu(en)3]2+ would be correspondingly low.e. a.
Why is the value of K3 for Cu2+ so different? When an equilibrium constant seems particularly "out of line" like this. there is a tendency for Cu(II) (d9) to exhibit a large Jahn-Teller distortion to the point of being virtually square-planar. the stability of the ethylene diamine complexes relative to the aquo complexes will be determined by the relative change in ligand field stabilization energies (LFSE). The table below shows the 15 microstates possible for p2 in no particular order. Therefore the concentration of [Cu(H2O)2(en)2]2+ is actually much lower than one would calculate using only the above sequence of equilibria. hence the greater stability. ml 1 0 -1 2 0 -2 1 0 -1 1 0 -1 1 MS = 0 MS = -1 MS = 1 MS = 0
Why are the corresponding values for Ni2+ greater than those for Co2+? All other factors being equal.
0 -1 1 0 -1 The next table contains a count of the number of microstates with the same ML and MS values that can be found in the table above.e.0. (i.e. S = 1.e. MS 0 0 1 2 1 0
2 1 0 -1 -2
1 0 1 1 1 0
-1 0 1 1 1 0
The maximum value of ML for which a microstate exists is 1 (in red) which must be part of a P term (i.-1 and -2). and the only MS value for which this term is found is 0 so it is part of a 1D term. and the largest MS value for which this term is found is 1.) Now remove the 5 microstates corresponding to this from the above table to get the next. so it is part of a 3 P term. MS 0 1 2 3 2 1 MS = 0
2 1 0 -1 -2
1 0 1 1 1 0
-1 0 1 0 1 0
The maximum value of ML for which a microstate exists is 2 (in red). with L = 2 so ML can also be 1. with L = 1 so ML can also be 0 and -1). (S = 0. which must be part of a D term (i.) Now remove the 9 microstates corresponding to this from the above table to get the next. MS 0
. so MS can also be 0 and -1.
B. I found that at ∆ o/B » 7. which has d-d absorptions at 8 500. a d8 ion in octahedral coordination.e. 3T1g (from the 3F term) and 3T1g (from the 3P term). and more precisely by calculation: c. 15 400 and 26 000 cm-1. there are two methods for solving this problem.1 = 1197 cm-1. (i. (The free ion value for Ni2+ is 1041 cm-1.ML
2 1 0 -1 -2
0 0 0 0 0
0 0 1 0 0
0 0 0 0 0 All that is left is one microstate with ML = 0 and MS = 0 which is a 1S term. By trial and error. To find B from the Tanabe-Sugano diagram.
The complex contains Ni(II). for [Ni(H2O)6]2+.1. graphically. As the question implies. B = 8500/7. note that the experimental ratio ν 2/ν 1 = 1. Using the information supplied.
.26 (distributed with the exam) indicates that the first of these transitions at 8 500 cm-1 corresponds to ∆ o. estimate or calculate ∆ o and the Racah parameter. Estimated from Tanabe-Sugano diagram The diagram for d8 shows that the ground state is 3A1g with spin-allowed transitions (in order of increasing frequency or wavenumber) to 3T2g. the required ratio is obtained. Reference to Huheey Table 9. L = 0 and S = 0) b. Therefore.72. and find the point along the ∆ o/B axis that yields the same ratio.
x = 15400
15B + x + 1.26 (distributed with the exam). which is the case here.2∆
Adding (2) and (3) gives: 15B + 3.d transitions are identifable. This diagram is constructed using the information from Huheey Table 9. Calculation Method This method is applicable if all three d .0∆
and substituting from (1) gives: B = 1060 cm-1
. and the knowledge that the 3P term is 15B above the 3F (which is also evident from the TanabeSugano diagram). The diagram for d8 shows that the ground state is 3A1g with spin-allowed transitions (in order of increasing frequency or wavenumber) to 3T2g.d. The following equations can be obtained from the spacings marked on the diagram: ∆
= 8500 cm-1
(1) (2) = 26000 (3)
1. 3T1g (from the 3F term) and 3T1g (from the 3P term).