By J Burgess
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Additional info for Ions in Solution: Basic Principles of Chemical Interactions
Ni2 +aq, in an octahedral ligand field. 48 [Ch. 4 Ion-solvent interactions cP systems. Nonetheless, values for the crystal field parameter 6 or lODq can readily be obtained for d2 to d8 ions in ranges of solvents from the bands observed in their ultraviolet-visible spectra. 2. 3. 3 - Values of the Crystal Field splitting parameter, Dq (cm - 1 ), for transition metal cations in aqueous solution Ti3+ y3+ y2+ Cr2 + Mn 2 + Fe 2 + Co2 + Ni2 + Cu 2 + 1230 1410 850 1000 930 890 1200 Cr3 + Mn3+ Fe 3 + Co3 + 2030 1860 1700 2000 1400 1820 Mo 3 + 2630 -2700 in the context of crystal field effects for ligands in general in Fig.
This point is emphasised by comparing the NMR peak area values of six for Mg2+, Zn 2+, Fe 2+, Al 3+, and Cr3+ with the much higher values obtained from kinetic methods. The main reason for this difference is that the ion-movement methods give an 34 Solvation numbers [Ch. 4 - Cation hydration numbers u+ Transport numbers Mobilities Conductivities Diffusion Entropies Compressibilities Activity coefficients Cf. NMR peak areas Na+ K+ 13-22 7-13 4-6 3-21 2-10 5-7 2-3 2-4 1 5 3 5 4 3 4 3 3 cs+ Mg2 + Ca2 + Ba2 + Zn2 + Fe 2 + AIH CrH 4 12-14 8-12 3-5 10-13 10-13 7-11 5-9 10-13 10-13 6 8 8 1 3 9 13 9 10 8 8 8 5 4 3 6 11 12 6 12 12 17 12 13 21 31 12 6 6 6 estimate of the average number of solvent molecules which move with each ion, which clearly includes secondary as well as primary solvation shells.
With the sodium chloride structure, the regular geometrical arrangement gives a radial distribution function with fixed numbers of neighbours at clearly defined distances, as in the two-dimensional case of the regular hexagonal array. This sequence is the same as that used to generate the Madelung constant series for this structure. In the case of solvated ions in solution, each ion has six nearest neighbours at a clearly defined distance. The next shortest regular distance is that between cis-solvent molecules in the octahedral primary solvation shells.