Q.(a) Transition metals can act as catalysts because these can change their oxidation state. How does Fe(III) catalyse the reaction between iodide and persulphate ions?
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Magnetism and Color
Magnetism and Colour: An Intuitive First Look
You've probably noticed that some materials are magnetic (like iron) and others aren't (like wood). And you've seen that objects have different colours — a rose is red, the sky is blue. At first glance, these two properties seem completely unrelated. But at the deepest level, both magnetism and colour come from the same source: how electrons behave inside atoms.
Let's start with a simple picture.
The Intuition: Electrons as Tiny Magnets and Painters
Imagine an electron orbiting the nucleus of an atom. That moving charge is like a tiny loop of electric current — and any loop of current creates a magnetic field. So every electron is a microscopic magnet. In most materials, these tiny magnets point in random directions and cancel out. But in iron, they align, and the material becomes magnetic.
Now, colour. When light hits an atom, electrons can absorb some of its energy and jump to a higher orbit. The colour we see is the light that wasn't absorbed — the leftover wavelengths. Different atoms absorb different colours because their electrons have different "jump sizes" (energy levels).
So both magnetism and colour are about how electrons move and interact with their environment. One is about the direction of electron spin and orbit (magnetism), the other about the energy of electron jumps (colour).
The Precise Statement
Magnetism and colour are both consequences of the electronic structure of atoms, but they arise from different aspects of electron behaviour:
- Magnetism originates from the magnetic moments of electrons — their spin and orbital motion. A material is magnetic when these moments align cooperatively.
- Colour originates from the absorption of specific wavelengths of light by electrons, which occurs when the photon energy matches the energy difference between two electron states.
How They Connect (and How They Don't)
The two phenomena are linked because they both depend on the arrangement of electrons in orbitals — the so-called electronic configuration. But they are not the same thing, and one does not cause the other.
Here's a table to make the distinction clear:
| Property | Origin | What determines it? | Example |
|---|---|---|---|
| Magnetism | Electron spin and orbital motion | Unpaired electrons, crystal structure | Iron is magnetic because it has 4 unpaired electrons per atom |
| Colour | Electron transitions between energy levels | Energy gap between orbitals | Copper is reddish because its electrons absorb blue-green light |
A material can be magnetic and colourless (like pure iron — it's silvery, not colourful). A material can be brilliantly coloured and non-magnetic (like a ruby). The two properties are independent in most everyday cases.
The Deeper Link: Transition Metals
The most interesting connection appears in transition metals (elements like iron, cobalt, nickel, copper). These atoms have partially filled d orbitals. That partial filling does two things:
- It leaves unpaired electrons, which can align to produce magnetism. …
Why this formula?
Magnetism and Color: Why the Key Formulas Hold
This is a fascinating intersection of physics and perception. The core idea is that color is not a property of light itself, but of our brain's interpretation of different wavelengths. Magnetism, in turn, can influence how these wavelengths are produced or absorbed.
Let's break down the key formulas and their why.
1. The Fundamental Link: Energy, Frequency, and Color
The most important formula connecting magnetism and color is the Planck-Einstein relation:
E=hν
Where:
- E = energy of a photon (light particle)
- h = Planck's constant (6.626×10−34 J⋅s)
- ν = frequency of the light
Why does this hold?
- Quantum nature of light: Light is not a continuous wave, but comes in discrete packets called photons.
- Energy quantization: The energy of a photon is directly proportional to its frequency. Higher frequency means higher energy.
- Magnetism's role: When an electron in an atom jumps from a higher energy level to a lower one, it emits a photon. The energy difference (ΔE) between these levels determines the photon's frequency:
ΔE=hν
- Color perception: Our eyes detect different frequencies as different colors. For example:
- Red light: ν≈4.3×1014 Hz (lower energy)
- Blue light: ν≈6.7×1014 Hz (higher energy)
Key insight: The color you see is determined by the energy gap between electron orbits. Magnetism can alter these energy gaps (via the Zeeman effect, see below).
2. The Zeeman Effect: How Magnetic Fields Split Colors
When a magnetic field is applied to an atom, a single spectral line (one color) splits into multiple lines. This is described by:
ΔE=μB⋅B⋅ml
Where:
- ΔE = energy shift of the spectral line
- μB = Bohr magneton (9.274×10−24 J/T)
- B = magnetic field strength (in Tesla)
- ml = magnetic quantum number (integer: −l,...,+l)
Why does this hold?
- Electron as a tiny magnet: An electron orbiting a nucleus behaves like a tiny current loop, creating a magnetic dipole moment.
- Energy in a magnetic field: This dipole moment interacts with an external magnetic field. The interaction energy depends on the orientation of the electron's orbit relative to the field.
- Quantized orientations: The magnetic quantum number ml tells us which orientation is allowed. Each orientation has a slightly different energy.
- Result: A single energy level splits into 2l+1 sub-levels. Transitions between these sub-levels produce photons with slightly different energies — hence different colors appear.
Example: A sodium lamp emits yellow light. In a strong magnetic field, that yellow line splits into three closely spaced lines (normal Zeeman effect).
3. Faraday Rotation: Magnetic Field Twists Light's Color
When polarized light passes through a material in a magnetic field, its plane of polarization rotates. The rotation angle is:
θ=V⋅B⋅d
Where:
- θ = rotation angle (in radians)
- V = Verdet constant (material-specific, depends on wavelength)
- B = magnetic field strength
- d = path length through the material
Why does this hold?
- Circular birefringence: In a magnetic field, the material has different refractive indices for left- and right-circularly polarized light.
- Phase difference: These two components travel at different speeds, creating a phase difference.
- Recombination: When they recombine, the resulting linear polarization is rotated. …
The key idea here is that transition metals like Fe(III) can cycle between oxidation states, providing an alternate reaction pathway with lower activation energy.
(a) Fe(III) catalyses the reaction between iodide (I−) and persulphate (S2O82−) by undergoing reduction and re-oxidation in two steps:
- Fe(III) is first reduced to Fe(II) by iodide:
2Fe3++2I−→2Fe2++I2
- Fe(II) is then re-oxidised back to Fe(III) by persulphate:
2Fe2++S2O82−→2Fe3++2SO42−
The net reaction is 2I−+S2O82−→I2+2SO42−, with Fe(III) regenerated — hence it acts as a true catalyst.
(b) Three processes where transition metals act as catalysts:
- Haber's process: Iron (Fe) catalyses the synthesis of ammonia from N2 and H2. …
Fe(III) catalyses the iodide–persulphate reaction by shuttling between Fe³⁺ and Fe²⁺, providing a lower-energy pathway. The key is that Fe(III) is reduced by I⁻ to Fe(II), which is then re‑oxidised by S₂O₈²⁻ back to Fe(III), regenerating the catalyst. The overall reaction is unchanged, but the activation energy drops.
Why this works — the idea of a redox shuttle
A catalyst works by offering an alternative reaction path with a lower activation energy. For transition metals, this often comes from their ability to exist in multiple oxidation states with small energy differences. Fe(III) and Fe(II) are both stable in aqueous solution, and the energy barrier to switch between them is modest. That makes iron an ideal electron ferry.
In the uncatalysed reaction, iodide and persulphate ions must collide directly and transfer two electrons in one go — a slow, high‑energy step. With Fe(III) present, the electron transfer is broken into two easier steps, each involving only one electron. The catalyst is consumed in the first step and regenerated in the second, so it is not used up.
Step‑by‑step mechanism
- Fe(III) oxidises iodide Fe³⁺ accepts one electron from I⁻, forming Fe²⁺ and iodine radical (or, in net terms, half an I₂ molecule).
2Fe3++2I−→2Fe2++I2
This step is fast because Fe³⁺ is a good oxidising agent (standard reduction potential E∘(Fe3+/Fe2+)=+0.77 V) and I⁻ is a moderate reducing agent.
- Fe(II) reduces persulphate The Fe²⁺ produced in step 1 now donates an electron to S₂O₈²⁻, regenerating Fe³⁺ and forming sulphate radicals (which quickly become sulphate ions).
2Fe2++S2O82−→2Fe3++2SO42−
This step is also fast because Fe²⁺ is a good reducing agent and S₂O₈²⁻ is a strong oxidiser (E∘(S2O82−/SO42−)=+2.01 V).
- Net reaction is unchanged Adding the two steps cancels the Fe³⁺ and Fe²⁺:
2I−+S2O82−Fe3+I2+2SO42−
The iron ions appear on both sides of the mechanism and therefore do not appear in the overall equation. They are true catalysts — consumed in one step, regenerated in the next.
A common mistake is to think Fe(III) directly oxidises S₂O₈²⁻ or that Fe(II) directly reduces I⁻. Check the reduction potentials: Fe³⁺ is a stronger oxidiser than I₂, so it can oxidise I⁻; Fe²⁺ is a stronger reductant than SO₄²⁻, so it can reduce S₂O₈²⁻. The direction is fixed by thermodynamics. …
Solution Method: Catalytic Mechanism Analysis via Oxidation State Change
(a) Fe(III) Catalysis of Iodide–Persulphate Reaction
Method: Two-step redox cycle (alternating oxidation states)
Steps:
- Identify the uncatalysed reaction The direct reaction between iodide (I−) and persulphate (S2O82−) is:
2I−+S2O82−→I2+2SO42−
This is slow because both reactants are negatively charged — repulsion makes collision unfavourable.
-
Introduce the catalyst — Fe(III)
Fe(III) can accept an electron (get reduced) and later donate it (get reoxidised). This provides a lower-energy pathway.
-
Step 1: Reduction of Fe(III)
Fe(III) oxidises iodide:
2Fe3++2I−→2Fe2++I2
- Step 2: Reoxidation of Fe(II) The Fe(II) formed is then oxidised back by persulphate:
2Fe2++S2O82−→2Fe3++2SO42−
- Net result Adding the two steps gives the overall reaction. Fe(III) is regenerated — it is not consumed, only cycled between +3 and +2 states.
Key insight: The catalyst works because Fe(III)/Fe(II) has a variable oxidation state with a redox potential intermediate between the two reactants, allowing electron transfer in two easy steps instead of one difficult step.
(b) Three Processes Where Transition Metals Act as Catalysts
| Process | Catalyst | Role |
|---------|----------|------| …
Here is a breakdown of the common mistakes and how to avoid them, structured for exam success.
(a) How does Fe(III) catalyse the reaction between iodide and persulphate ions?
This is a classic example of auto-oxidation (or redox catalysis). The key is that the catalyst shuttles between two oxidation states.
The Correct Mechanism (Step-by-Step):
- The Slow Step (Catalyst is Reduced): The catalyst, Fe3+ (Iron III), oxidises the iodide ion (I−).
2Fe3++2I−→2Fe2++I2
- The Fast Step (Catalyst is Regenerated): The newly formed Fe2+ (Iron II) is then oxidised back to Fe3+ by the persulphate ion (S2O82−).
2Fe2++S2O82−→2Fe3++2SO42−
Overall Reaction (Net):
S2O82−+2I−→2SO42−+I2
The Fe3+ is regenerated at the end, so it is not consumed. It simply provides a lower-energy pathway (lower activation energy) for the reaction.
✗ Common Mistake #1: Writing the wrong products for the first step.
- The Error: Students write Fe3++I−→Fe2++I (a single iodine atom). This is incorrect because iodine atoms are highly unstable and immediately pair up.
- How to Avoid: Remember that iodine exists as a diatomic molecule (I2). You must balance the equation. For every 2 electrons gained by Fe3+, you need 2 I− ions to lose 2 electrons to form one I2 molecule. Always balance the charge and the atoms.
✗ Common Mistake #2: Confusing the roles of the ions.
- The Error: Saying "Fe(III) oxidises persulphate" or "Fe(II) reduces iodide." This reverses the entire mechanism.
- How to Avoid: Use the Oxidation Number trick.
- In step 1: Fe3+→Fe2+ (gain of electron = reduction). Therefore, Fe3+ is the oxidising agent for I−.
- In step 2: Fe2+→Fe3+ (loss of electron = oxidation). Therefore, Fe2+ is the reducing agent for S2O82−.
- Mnemonic: "LEO the lion says GER" (Loss of Electrons = Oxidation; Gain of Electrons = Reduction).
✗ Common Mistake #3: Forgetting to mention the regeneration of the catalyst.
- The Error: Only writing the first step and stopping. The examiner wants to see that you understand the catalytic cycle.
- How to Avoid: Always write both steps. The definition of a catalyst is that it is chemically unchanged at the end. You must show how it gets back to its original state (Fe3+).
(b) Mention any three processes where transition metals act as catalysts.
The key here is to be specific. Don't just say "Haber process." Say which metal is the catalyst.
✗ Common Mistake #4: Giving vague or incorrect examples.
- The Error: Saying "Iron is used in the Contact process" (it's Vanadium Pentoxide) or "Nickel is used in the Haber process" (it's Iron).
- How to Avoid: Memorise the Metal + Process + Role triplet.
Here are three correct, high-scoring examples:
- Haber's Process (Ammonia synthesis):
- Catalyst: Finely divided Iron (Fe) with promoters like Mo or K2O. …
- COMEDK 2026Set 2026-M1 markMCQQ.Which one of the following species will impart colour to an aqueous solution? (A) Cr3+ (B) Zn2+ (C) Ti4+ (D) Cu+
›Reveal solutionSolution
Colour in aqueous solution arises from d–d transitions in transition-metal ions with partially filled d-orbitals. Among the options, only Cr³⁺ has an incomplete d-subshell (d³), so it is the species that imparts colour.
The key concept is crystal field theory and d–d transitions. For a transition-metal ion to appear coloured in solution, it must have at least one unpaired electron in its d-orbitals, allowing it to absorb visible light by promoting an electron from a lower-energy d-orbital to a higher-energy one. Ions with completely filled (d¹⁰) or empty (d⁰) d-subshells cannot undergo such transitions and are typically colourless.
Let’s examine each option:
-
Cr³⁺ – Chromium in the +3 oxidation state has the electron configuration [Ar] 3d³. The d-subshell is partially filled (three d-electrons). This allows d–d transitions, so Cr³⁺ solutions (e.g., CrCl₃) are typically violet or green. This will impart colour.
-
Zn²⁺ – Zinc in the +2 state has the configuration [Ar] 3d¹⁰. The d-subshell is completely filled. No d–d transitions are possible, and Zn²⁺ solutions are colourless. No colour.
-
Ti⁴⁺ – Titanium(IV) has lost all four valence electrons, giving [Ar] (no d-electrons). The d-subshell is empty (d⁰). No d–d transitions possible; Ti⁴⁺ solutions are colourless. No colour. …
-
- COMEDK 2025Set 2025-M1 markMCQQ.Choose the correct statement. (A) Ionic compounds of Sc3+ and Cu+are coloured because of d−d electronic transitions (B) The order in which the paramagnetic nature of the 4 cations Cr2+,Mn2+,V2+ and Fe2+ vary is V2+<Cr2+=Mn2+<Fe2+ (C) As the oxidation number of the transition element increases, the ionic nature decreases and the oxides show acidic nature predominantly (D) The metal Cobalt has the electronic configuration [Ar]3 d5 in the +3 oxidation state
›Reveal solutionSolution
The key is to evaluate each statement using principles of transition-metal chemistry: d–d transitions require partially filled d-orbitals, paramagnetism depends on unpaired electrons, ionic character and acidity relate to oxidation state, and Co³⁺ has a 3d⁶ configuration. Only statement (C) is correct.
Concept and Intuition
Transition-metal compounds exhibit colour, paramagnetism, and variable oxidation states due to their partially filled d-orbitals. Each statement here tests a specific concept:
- Colour from d–d transitions requires at least one d-electron and an empty d-orbital to allow excitation.
- Paramagnetic strength is proportional to the number of unpaired electrons.
- Higher oxidation states increase covalent character (Fajan’s rules) and make oxides more acidic.
- The electron configuration of an ion is found by removing electrons from the neutral atom’s configuration, starting with the 4s orbital.
Step-by-step analysis
-
Statement (A):
- Sc³⁺ has the configuration [Ar] (no d-electrons). Without any d-electrons, d–d transitions are impossible.
- Cu⁺ has configuration [Ar] 3d¹⁰ (full d-subshell). A full d-subshell means no empty d-orbital to accept an excited electron, so d–d transitions cannot occur.
- Therefore, neither ion can be coloured via d–d transitions. Statement (A) is false.
-
Statement (B):
- Determine the number of unpaired electrons for each ion (all are 2+ ions of first-row transition metals):
- V²⁺: [Ar] 3d³ → 3 unpaired electrons.
- Cr²⁺: [Ar] 3d⁴ → 4 unpaired electrons (high-spin, as in aqueous complexes).
- Mn²⁺: [Ar] 3d⁵ → 5 unpaired electrons.
- Fe²⁺: [Ar] 3d⁶ → 4 unpaired electrons (high-spin).
- Paramagnetic nature increases with number of unpaired electrons. So the order should be: V²⁺ (3) < Cr²⁺ (4) = Fe²⁺ (4) < Mn²⁺ (5).
- The given order is V²⁺ < Cr²⁺ = Mn²⁺ < Fe²⁺, which incorrectly places Mn²⁺ equal to Cr²⁺ and Fe²⁺ as the most paramagnetic.
- Statement (B) is false.
- Determine the number of unpaired electrons for each ion (all are 2+ ions of first-row transition metals):
-
Statement (C): …
- COMEDK 2024Set 2024-E1 markMCQQ.The Lanthanoid ion which would form coloured compounds is -------------. Atomic numbers: Yb=70,Lu=71,Pr=59,La=57 (A) Yb2+ (B) La3+ (C) Lu3+ (D) Pr3+
›Reveal solutionSolution
Colour in lanthanoid ions arises from f–f transitions, which require at least one unpaired electron in the 4f subshell. Among the given ions, only Pr³⁺ (4f²) has unpaired electrons, so it forms coloured compounds.
Concept & Intuition
Lanthanoid ions often display beautiful colours in solution or in solids. The colour comes from electronic transitions within the partially filled 4f orbitals. These f–f transitions are Laporte-forbidden but become weakly allowed due to vibronic coupling, giving pale but distinct colours. The key requirement is that the ion must have at least one unpaired electron in its 4f subshell. If the 4f subshell is empty (4f⁰) or completely full (4f¹⁴), no such transitions are possible, and the ion is colourless.
Let’s check each option.
-
Yb²⁺ (Ytterbium, atomic number 70)
- Neutral Yb: [Xe] 4f¹⁴ 6s²
- Yb²⁺ loses the two 6s electrons: [Xe] 4f¹⁴
- 4f subshell is completely full → no unpaired electrons → colourless.
-
La³⁺ (Lanthanum, atomic number 57)
- Neutral La: [Xe] 5d¹ 6s²
- La³⁺ loses the 5d and both 6s electrons: [Xe] 4f⁰
- 4f subshell is empty → no unpaired electrons → colourless.
-
Lu³⁺ (Lutetium, atomic number 71)
- Neutral Lu: [Xe] 4f¹⁴ 5d¹ 6s²
- Lu³⁺ loses the 5d and both 6s electrons: [Xe] 4f¹⁴
- Again, 4f subshell is full → no unpaired electrons → colourless.
-
Pr³⁺ (Praseodymium, atomic number 59)
- Neutral Pr: [Xe] 4f³ 6s²
- Pr³⁺ loses the two 6s electrons and one 4f electron: [Xe] 4f² …
-
- KCET 2023Set D-21 markMCQQ.Which of the following is CORRECT with respect to melting point of a transition element? (A) V > Cr (B) Cr > Mn (C) Mn > Fe (D) Ti > V
›Reveal solutionSolution
Recall the NCERT melting-point trend across the 3d series and test each inequality; Mn's anomalously low melting point makes Cr > Mn the robust correct statement.
Step 1 — The concept behind the trend
In a transition metal, the strength of metallic bonding depends on how many unpaired d-electrons are available to take part in interatomic (covalent-like) bonding on top of the metallic sea. Bonding strength — and hence melting point — therefore rises to a maximum near the middle of the series and falls off towards the end as d-electrons begin to pair up.
Step 2 — The data (NCERT, 3d series, ∘C)
Ti 1677V 1917Cr 1903Mn 1244Fe 1535
Step 3 — The Mn anomaly (the point of the question)
Manganese has the configuration 3d54s2. Its half-filled d-subshell is exceptionally stable, so those five electrons are reluctant to delocalise into the metallic bond. With fewer electrons effectively contributing to bonding, Mn's metallic bonding is weak and its melting point (1244∘C) is far below both its neighbours Cr (1903∘C) and Fe (1535∘C). This dip is the famous irregularity in the melting-point curve.
Step 4 — Test each option
- (B) Cr > Mn: 1903>1244 — TRUE, and by a very large margin (this is the Mn anomaly). …
- COMEDK 2023Set 2023-M1 markMCQQ.Ti2+ is purple while Ti4+ is colourless because (A) Ti2+ has 3d2 configuration (B) Ti4+ has 3d2 configuration (C) Ti2+ is very small cation when compared to Ti2+ and hence, doesn't absorb any radiation (D) There is no crystal field effect in Ti4+
›Reveal solutionSolution
Colour in transition-metal ions comes from d–d electronic transitions, which require partially filled d orbitals. Ti2+ (3d2) has d electrons and is coloured (purple); Ti4+ (3d0) has none and is colourless.
Titanium: Ti (Z=22) =[Ar]3d24s2.
- Ti2+: remove the two 4s electrons ⇒[Ar]3d2. With two d electrons, d–d transitions are possible, absorbing visible light and imparting the purple colour. …
- KCET 2021Set B-21 markMCQQ.Which one of the following is correct for all elements from Sc to Cu? (A) The lowest oxidation state shown by them is +2 (B) 4s orbital is completely filled in the ground state (C) 3d orbital is not completely filled in the ground state (D) The ions in +2 oxidation states are paramagnetic.
›Reveal solutionSolution
Every +2 ion from Sc2+ (3d1) to Cu2+ (3d9) carries unpaired 3d electrons, so all are paramagnetic — option (D).
Test each statement across Sc–Cu (the 3d series).
(A) False — Sc's lowest common state is +3 and Cu shows +1, so +2 is not the lowest for every element.
(B) False — in Cr [Ar]3d54s1 and Cu [Ar]3d104s1 the 4s orbital holds only one electron.
(C) False — Cu is [Ar]3d104s1, so its 3d subshell is completely filled.
(D) True — the two 4s electrons are lost first, so each +2 ion is 3dn: …
- KCET 2021Set B-21 markMCQQ.The property of the alkaline earth metals that increases with their atomic number is (A) Ionisation enthalpy (B) Electronegativity (C) Solubility of their hydroxide in water (D) Solubility of their sulphate in water
›Reveal solutionSolution
Only hydroxide solubility rises down group 2; ionisation enthalpy, electronegativity and sulphate solubility all fall.
Step 1 — The governing principle for solubility trends
Whether an ionic solid dissolves depends on the competition between two quantities:
ΔHsoln=ΔHhydration−ΔHlattice
Both lattice and hydration enthalpies decrease as the cation gets bigger down the group. Which one falls faster decides the trend — and that depends on the size of the anion:
- With a small anion (OH−, F−), the lattice enthalpy is very sensitive to the cation size, so it falls faster than the hydration enthalpy ⇒ solubility increases down the group.
- With a large anion (SO42−, CO32−), the lattice enthalpy is dominated by the big anion and barely changes; the hydration enthalpy of the cation falls faster ⇒ solubility decreases down the group.
Step 2 — Apply it to each option
(C) Hydroxides. OH− is a small anion, so the first case applies:
Be(OH)2<Mg(OH)2<Ca(OH)2<Sr(OH)2<Ba(OH)2
Solubility (and hence basic strength) increases with atomic number. Mg(OH)2 is only sparingly soluble (milk of magnesia), while Ba(OH)2 is appreciably soluble and a strong base. ✓ This is the property that increases. …
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