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Ch.21 - Transition Elements and Coordination Chemistry
Chapter 21, Problem 21.105

The [Cr(H2O)6]3+ ion is violet, and [Cr(CN)6]3- is yellow. Explain this difference using crystal field theory. Use the colors to order H2O and CN- in the spectrochemical series.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Crystal Field Theory

Crystal Field Theory (CFT) explains the electronic structure of transition metal complexes by considering the effect of surrounding ligands on the d-orbitals of the metal ion. When ligands approach the metal ion, they create an electric field that splits the degenerate d-orbitals into different energy levels. The extent of this splitting depends on the nature of the ligands and their arrangement around the metal ion.
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The study of ligand-metal interactions helped to form Ligand Field Theory which combines CFT with MO Theory.

Spectrochemical Series

The spectrochemical series is a list that ranks ligands based on the strength of the field they produce when coordinating to a metal ion. Strong field ligands, like CN<sup>-</sup>, cause a larger splitting of the d-orbitals, leading to higher energy transitions and different colors. Conversely, weak field ligands, such as H<sub>2</sub>O, result in smaller splitting and lower energy transitions, which can be observed in the color of the complexes.
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Activity Series Chart

Color and d-Orbital Splitting

The color observed in transition metal complexes is a result of the specific wavelengths of light absorbed during electronic transitions between split d-orbitals. The energy difference between these orbitals corresponds to specific colors in the visible spectrum. For example, the violet color of [Cr(H<sub>2</sub>O)<sub>6</sub>]<sup>3+</sup> indicates that it absorbs light in the yellow-green region, while the yellow color of [Cr(CN)<sub>6</sub>]<sup>3-</sup> suggests it absorbs light in the violet region, reflecting the differences in ligand field strength.
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d Orbital Orientations