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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
2. Determine the d-electron configuration, the number of unpaired electrons, and the
ligand field stabilization energy (LFSE) in terms of ∆ o or ∆ t as appropriate for
each of the following complexes. Please make it clear how you make any
necessary decisions:
a. [Fe(CN)6]4-
This is surely a strong field d6 case because of the combination of Fe2+ and
CN-.
b. [Fe(H2O)6]2+
c. [NiCl4]2-
Chloride is quite low in the spectrochemical series, so this Ni2+ d8 complex
will probably be tetrahedral.
d. [Ni(CN)4]2-
Cyanide is high in the spectrochemical series so this is Ni2+ d8 complex
will probably be square-planar.
To work this out you would have to remember the not very memorable
levels: my mistake!
e. [Ni(CO)4]
This is a Ni0 d10 complex and the ligand field stabilization energy is zero in
any geometry, so there is no reason for it not to be tetrahedral.
3.
a. The rate constants for the formation of of [CoX(NH3)5]2+ from
[Co(NH3)6)3+ for X = Cl-, Br-, N3-, and SCN- differ by no more than a factor
of two. What mechanism of substitution does this observation support?
If the rate is only weakly related to the nature of the entering ligand, then
the mechanism is dissociative.
iii. Why are the corresponding values for Ni2+ greater than those for
Co2+?
All other factors being equal, 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 absolute values of the LFSE i.e. ∆ o, will be greater for the
smaller Ni2+ ion, so the differences should also be greater, hence
the greater stability.
4.
a. Deduce the Russell-Saunders terms for the configuration p2.
ml
ML 1 0 -1
2
0 MS = 0
-2
1
0 MS = 1
-1
1
0 MS = -1
-1
1 MS = 0
0
-1
1
0 MS = 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.
MS
1 0 -1
2 0 1 0
1 1 2 1
ML 0 1 3 0
-1 1 2 1
-2 0 1 0
MS
1 0 -1
2 0 0 0
1 1 1 1
ML 0 1 2 1
-1 1 1 1
-2 0 0 0
MS
1 0 -1
ML 2 0 0 0
1 0 0 0
0 0 1 0
-1 0 0 0
-2 0 0 0
The diagram for d8 shows that the ground state is 3A1g with spin-allowed
transitions (in order of increasing frequency or wavenumber) to 3T2g, 3T1g
(from the 3F term) and 3T1g (from the 3P term).
Reference to Huheey Table 9.26 (distributed with the exam) indicates that
the first of these transitions at 8 500 cm-1 corresponds to ∆ o.
The diagram for d8 shows that the ground state is 3A1g with spin-allowed
transitions (in order of increasing frequency or wavenumber) to 3T2g, 3T1g
(from the 3F term) and 3T1g (from the 3P term).
The following equations can be obtained from the spacings marked on the
diagram:
B = 1060 cm-1