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Activity · Q1

Q.The reaction of chromium metal with H2SO4 in the absence of air gives blue solution of chromium ion.
Cr(s) + 2H+(aq) -> Cr2+(aq) + H2(g)
Cr2+ forms octahedral complex with H2O ligands.

(a) Write formula of the complex
(b) Describe bonding in the complex using CFT and VBT. Draw crystal field splitting and valence bond orbital diagrams.
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Step 1. (a) Formula of the complex. Chromium metal reacts with H2SO4 (air-free) to give Cr2+(aq): Cr(s)+2H⊕(aq)→Cr2⊕(aq)+H2(g)\text{Cr(s)}+2\text{H}^{\oplus}(aq)\rightarrow\text{Cr}^{2\oplus}(aq)+\text{H}_2(g). Cr2+ forms an OCTAHEDRAL complex with six H2O ligands (given): the complex ion is [Cr(H2O)6]2+.

Step 2. (b) Free-ion configuration. Chromium (Z=24) has the anomalous ground-state configuration [Ar]3d5 4s1 (half-filled-shell stability). Cr2+ is formed by removing 2 electrons -- the one 4s electron plus one 3d electron -- giving a free-ion configuration of 3d4.

Step 3. CFT description. H2O sits toward the weaker-field end of the spectrochemical series (Table 9.6), so [Cr(H2O)6]2+ is HIGH SPIN. For a high-spin d4 ion (Table 9.7), the CFT diagram (Fig. 9.2 pattern) shows all four electrons occupying the t2g and eg sets singly, following Hund's rule: t2g3 eg1, i.e. three of the lower t2g orbitals and one of the upper eg orbitals each hold one electron -- 4 unpaired electrons total. (This is a genuine, well-known real-world case: high-spin d4 octahedral complexes like [Cr(H2O)6]2+ characteristically also show Jahn-Teller distortion, though that refinement is beyond this chapter's scope.)

Step 4. VBT description. Since this is a HIGH SPIN complex, no pairing of the 3d4 electrons happens before hybridisation; with no 3d orbital left vacant for hybridisation, the complex must instead use OUTER-orbital hybridisation: one 4s, three 4p and two 4d orbitals, giving sp3d2 hybridisation (matching the [CoF6]3- high-spin worked example of section 9.9.2). The six sp3d2 hybrid orbitals overlap with the six H2O lone pairs to form the Cr-O coordinate bonds, while the 3d4 electrons remain unpaired.

Step 5. Diagrams (described). Crystal field splitting diagram: t2g (lower, 3 orbitals, one electron each) and eg (upper, 2 orbitals, one electron in one, one empty), separated by Delta-o, matching Fig. 9.2's layout. Valence bond orbital diagram: 3d4 (4 singly-occupied orbitals, unaffected by bonding) shown alongside the six newly-formed sp3d2 hybrid orbitals (built from 4s, three 4p, two 4d) each overlapping with one H2O ligand.

✓Final answer

Complex: [Cr(H2O)6]2+. High spin, 4 unpaired electrons, sp3d2 (outer orbital) hybridisation, paramagnetic.

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