In chromyl chloride test for confirmation of Cl^-$Cl^-$ ion, a yellow solution is obtained. Acidification of the solution and addition of amyl alcohol and 10%$10\%$H₂O₂$H_2O_2$ turns organic layer blue indicating formation of chromium pentoxide. The oxidation state of chromium in that is
Acidification of the yellow CrO₄²⁻$CrO_4^{2-}$ solution followed by the addition of H₂O₂$H_2O_2$ and amyl alcohol yields a blue-colored organic layer due to the formation of chromium pentoxide (CrO₅$CrO_5$).
Potassium Dichromate and Chromyl Chloride Test diagram for Q63 - JEE Main 2024 Morning
The structure of chromium pentoxide (CrO₅$CrO_5$) features a distinctive "butterfly" arrangement. It contains one double-bonded oxide oxygen (O²⁻$O^{2-}$) and four peroxide oxygens (O₂²⁻$O_2^{2-}$). Therefore, there are 2 peroxo linkages.
Let the oxidation state of Chromium be x$x$.
x + 1(-2) + 4(-1) = 0$$x + 1(-2) + 4(-1) = 0$$
x - 2 - 4 = 0$x - 2 - 4 = 0$x = +6$x = +6$
Thus, the oxidation state of Cr in CrO₅$CrO_5$ is +6$+6$.
Pattern Recognition
A classic oxidation state trap. Calculating simply via formula CrO₅$CrO_5$ yields x - 10 = 0 x = +10$x - 10 = 0 \implies x = +10$, which is impossible for Chromium (max +6). Whenever calculation exceeds the maximum group valency, peroxide bonds are present.
Chapter Mix
Class 12 Chemistry: d and f Block Elements
Class 11 Chemistry: Redox Reactions
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More d and f Block Elements Previous-Year Questions — Page 8
In alkaline medium. MnO₄^-$MnO_4^-$ oxidises I^-$I^-$ to
A.IO₄^-$IO_4^-$
B.IO^-$IO^-$
C.I₂$I_2$
D.IO₃^-$IO_3^-$
Solution
Core Logic
The behavior of the permanganate ion (MnO₄^-$MnO_4^-$) varies with the pH of the medium.
In a faintly alkaline or neutral medium, MnO₄^-$MnO_4^-$ oxidizes iodide (I^-$I^-$) completely to iodate (IO₃^-$IO_3^-$) while getting reduced to manganese dioxide (MnO₂$MnO_2$).
Rule of thumb for I^-$I^-$ oxidation by KMnO₄$KMnO_4$:
In acidic medium: I^- arrow I₂$I^- \rightarrow I_2$
In alkaline/neutral medium: I^- arrow IO₃^-$I^- \rightarrow IO_3^-$
Chapter Mix
Class 12 Chemistry: d and f Block Elements
Qjee_main_2024_30_january_eveningCompounds of Transition Elements
A and B formed in the following reactions are:
Compounds of Transition Elements
A.A = Na₂CrO₄, B = CrO₅$\text{A = Na}_2\text{CrO}_4\text{, B = CrO}_5$
B.A = Na₂Cr₂O₄, B = CrO₄$\text{A = Na}_2\text{Cr}_2\text{O}_4\text{, B = CrO}_4$
C.A = Na₂Cr₂O₇, B = CrO₃$\text{A = Na}_2\text{Cr}_2\text{O}_7\text{, B = CrO}_3$
D.A = Na₂Cr₂O₇, B = CrO₅$\text{A = Na}_2\text{Cr}_2\text{O}_7\text{, B = CrO}_5$
Solution
Core Logic
Step 1: Chromyl chloride (CrO₂Cl₂$CrO_2Cl_2$) reacts with an alkali like NaOH$NaOH$ to give a yellow solution of sodium chromate (Na₂CrO₄$Na_2CrO_4$).
Step 2: Sodium chromate (Na₂CrO₄$Na_2CrO_4$) reacts with hydrogen peroxide (H₂O₂$H_2O_2$) in an acidic medium (HCl$HCl$) to yield the deep blue colored chromium pentoxide (CrO₅$CrO_5$, also known as chromium(VI) oxide peroxide).
Note: NaCl$NaCl$ formation implies the overall balanced reaction uses the acid for neutralization/salt formation.
Pattern Recognition
Chromyl chloride test intermediate: Yellow solution = Na₂CrO₄$Na_2CrO_4$.
Reaction of chromate with H₂O₂$H_2O_2$ in acid = Blue peroxide CrO₅$CrO_5$ (butterfly structure).
Chapter Mix
Class 12 Chemistry: The d and f Block Elements
Class 11 Chemistry: Redox Reactions
Q70jee_main_2024_30_january_eveningProperties of Transition Metal Compounds
The orange colour of K₂Cr₂O₇$K_2Cr_2O_7$ and purple colour of KMnO₄$KMnO_4$ is due to
B.d arrow d transition in KMnO₄ and charge transfer transitions in K₂Cr₂O₇$\text{d} \rightarrow \text{d transition in KMnO}_4 \text{ and charge transfer transitions in K}_2\text{Cr}_2\text{O}_7$
C.d arrow d transition in K₂Cr₂O₇ and charge transfer transitions in KMnO₄.$\text{d} \rightarrow \text{d transition in K}_2\text{Cr}_2\text{O}_7 \text{ and charge transfer transitions in KMnO}_4.$
D.d arrow d transition in both.$\text{d} \rightarrow \text{d transition in both.}$
Solution
Core Logic
In K₂Cr₂O₇$K_2Cr_2O_7$, Chromium is in the +6$+6$ oxidation state, which means its electronic configuration is d⁰$d^0$. Since there are no d-electrons, d-d$d-d$ transitions cannot occur. The orange color is due to ligand-to-metal charge transfer (LMCT) from oxygen to chromium.
Similarly, in KMnO₄$KMnO_4$, Manganese is in the +7$+7$ oxidation state, which also corresponds to a d⁰$d^0$ configuration. Again, no d-d$d-d$ transitions are possible. The intense purple color is due to ligand-to-metal charge transfer (LMCT) from oxygen to manganese.
Step 1: Final Conclusion
Both compounds owe their colors to charge transfer transitions.
Pattern Recognition
Compounds of transition metals in their highest oxidation states (where they have d⁰$d^0$ configurations, like Cr⁺⁶$Cr^{+6}$, Mn⁺⁷$Mn^{+7}$, V⁺⁵$V^{+5}$) are deeply colored primarily due to Charge Transfer spectra, NOT d-d transitions.
Chapter Mix
Class 12 Chemistry: The d and f Block Elements
Q71jee_main_2024_30_january_eveningPreparation and Properties of KMnO4
Alkaline oxidative fusion of MnO₂$MnO_2$ gives "A" which on electrolytic oxidation in alkaline solution produces B. A and B respectively are:
A.Mn₂O₇ and MnO₄^-$\text{Mn}_2\text{O}_7 \text{ and MnO}_4^-$
B.MnO₄²⁻ and MnO₄^-$\text{MnO}_4^{2-} \text{ and MnO}_4^-$
C.Mn₂O₃ and MnO₄²⁻$\text{Mn}_2\text{O}_3 \text{ and MnO}_4^{2-}$
D.MnO₄²⁻ and Mn₂O₇$\text{MnO}_4^{2-} \text{ and Mn}_2\text{O}_7$
Solution
Core Logic
Step 1: Alkaline oxidative fusion of MnO₂$MnO_2$ (pyrolusite ore) with KOH$KOH$ in the presence of O₂$O_2$ (or an oxidizing agent like KNO₃$KNO_3$) yields the green-colored manganate ion (MnO₄²⁻$MnO_4^{2-}$).
Step 2: Electrolytic oxidation of the manganate ion (MnO₄²⁻$MnO_4^{2-}$) in an alkaline medium converts it to the purple-colored permanganate ion (MnO₄^-$MnO_4^-$).
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