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Q5.25:
Explain the violet colour of the complex ([Ti(H_{2}O)_{6}]^{3+}) on the basis of crystal field theory.

Solution :

Step 1: Electronic Configuration of the Central Metal Ion

The central metal atom is Titanium ($Ti$), which has an atomic number $Z = 22$. Its ground state electronic configuration is $[Ar] 3d^2 4s^2$. In the complex $[Ti(H_2O)_6]^{3+}$, the oxidation state of Titanium is calculated as follows:

$x + 6(0) = +3 \implies x = +3$

Removing three electrons ($2$ from $4s$ and $1$ from $3d$), the configuration of the $Ti^{3+}$ ion is $[Ar] 3d^1$. [Per the Aufbau Principle].

Step 2: Crystal Field Splitting in Octahedral Geometry

In the presence of six water ligands (which are weak-field ligands), the $d$-orbitals of the $Ti^{3+}$ ion undergo splitting into two energy levels due to the octahedral field created by the ligands. [Per Crystal Field Theory (CFT)].

  • $t_{2g}$ orbitals: Lower energy set ($d_{xy}, d_{yz}, d_{zx}$).
  • $e_g$ orbitals: Higher energy set ($d_{x^2-y^2}, d_{z^2}$).
Energy 3d (Free Ion) e_g t_{2g} Δ_o

Step 3: Electronic Transition and Photon Absorption

The single electron in $Ti^{3+}$ occupies one of the $t_{2g}$ orbitals. When white light falls on the complex, the electron absorbs a photon of light corresponding to the energy difference $\Delta_o$ between the $t_{2g}$ and $e_g$ levels and undergoes an $d-d$ transition ($t_{2g}^1 \to e_g^1$).

The energy absorbed by this transition is defined by the relation: $E = h\nu = \frac{hc}{\lambda}$ [Per Planck-Einstein relation].

Step 4: Origin of the Violet Color

For the $[Ti(H_2O)_6]^{3+}$ complex, the energy gap $\Delta_o$ corresponds to the frequency of light in the yellow-green region of the visible spectrum. According to the principle of complementary colors, the light transmitted (and thus perceived by the eye) is the color complementary to the light absorbed.

Light Absorbed Wavelength Absorbed (Approx) Perceived Color
Yellow-Green $490 - 560\ nm$ Violet

Since the complex absorbs yellow-green light, the complementary color perceived is violet. [Per the Complementary Color Theory].

Final Solution: The violet color of $[Ti(H_2O)_6]^{3+}$ arises due to the $d-d$ transition of the single $3d$ electron from the $t_{2g}$ to the $e_g$ level, which involves the absorption of yellow-green light, leaving the violet component of the white light spectrum to be transmitted.


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