Q.Assertion: Toxic metal ions are removed by the chelating ligands.
Reason: Chelate complexes tend to be more stable.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Stability of Oxidation States
Stability of Oxidation States – From Intuition to Precision
Imagine you're holding a ball on a hill. If you place it exactly at the top, it's balanced — but the slightest push sends it rolling down. That's an unstable position. If you place it in a small dip on the hillside, it stays put even if nudged — that's stable. Oxidation states work the same way: some are like the hilltop (easily changed), others like the dip (hard to change).
The Core Intuition
An oxidation state is just a number we assign to an atom to track how many electrons it has gained or lost compared to its neutral state. But atoms don't "want" to stay in arbitrary oxidation states — they want to reach a configuration that minimises their energy.
Stability here means: how reluctant is that oxidation state to change under normal conditions? A stable oxidation state resists being oxidised further or reduced further. An unstable one readily changes into something else.
The Precise Statement
Stability of an oxidation state refers to the tendency of an element to maintain that particular oxidation state under given conditions (temperature, pH, presence of other reagents). A stable oxidation state is one that does not easily undergo redox reactions — it is neither easily oxidised nor easily reduced.
This depends on three key factors:
- Electronic configuration – Half-filled and fully-filled d or f subshells confer extra stability (e.g., Fe3+ with d5 is more stable than Fe2+ with d6 in some contexts).
- Inert pair effect – Heavier p-block elements (like Tl, Pb, Bi) show lower oxidation states (e.g., +1 for Tl) as more stable than higher ones (+3 for Tl), because the s-electrons become reluctant to participate.
- Disproportionation tendency – Some oxidation states are unstable because they spontaneously convert into two other states (e.g., Cu+ in aqueous solution gives Cu2+ and Cu).
Stability is relative — it depends on the environment. Mn2+ is stable in acidic solution but easily oxidised in alkaline medium. Always specify conditions when discussing stability.
Examples That Make It Concrete
Transition metals – Cr3+ (d3) and Mn2+ (d5) are exceptionally stable because half-filled/half-filled-like configurations have low energy. Cr2+ (d4) is easily oxidised to Cr3+ — it's unstable.
p-block elements – Pb2+ is stable, Pb4+ is a strong oxidising agent (unstable). Sn2+ is a reducing agent (easily oxidised to Sn4+), so Sn4+ is more stable for tin.
Common pattern – For most elements, the most common oxidation state is the most stable one under standard conditions. But "most common" isn't always "most stable" — e.g., Fe3+ is common but Fe2+ is more stable in acidic solution.
Do not confuse "stability" with "occurrence". Mn7+ (as MnO4−) is common in the lab but is a powerful oxidising agent — it is not stable in the sense of resisting change. It readily accepts electrons.
How to Think About It in Exams …
Why this formula?
Stability of Oxidation States: Why It Works
This concept explains why certain oxidation states of an element are more stable than others — and why some states are never observed at all.
The Core Idea: Energy Minimisation
An oxidation state is stable when the total energy of the system is at a minimum. This depends on three competing factors:
- Ionisation energy (energy needed to remove electrons)
- Lattice energy (for ionic compounds) or bond energy (for covalent compounds)
- Electronic configuration (half-filled / fully-filled subshells)
There is no single formula for stability — instead, we use trends and principles that act as "formulae" for prediction.
Key Principle 1: Inert Pair Effect (for p-block elements)
Why it holds:
For heavier elements (e.g., Tl, Pb, Bi), the 6s² electrons are held very tightly due to poor shielding and relativistic effects. They resist removal.
- Result: Lower oxidation state (e.g., +1 for Tl, +2 for Pb) becomes more stable than the higher state (+3, +4).
- Example: TlX3+ is a strong oxidising agent — it readily gains two electrons to become TlX+.
Derivation logic:
The energy cost to remove the 6s² electrons is greater than the energy gained by forming additional bonds or lattice. So the system stays in the lower state.
Key Principle 2: Half-Filled / Fully-Filled Subshell Stability
Why it holds:
A half-filled (d5, f7) or fully-filled (d10, f14) subshell has extra exchange energy and symmetry — making it unusually stable.
- Example: MnX2+ (d5) is more stable than MnX3+ (d4). FeX3+ (d5) is more stable than FeX2+ (d6).
Derivation logic:
The exchange energy (Hund's rule) is maximum for half-filled configurations. Removing an electron from a half-filled shell costs extra energy — so the half-filled state is favoured.
Key Principle 3: Lattice Energy / Hydration Energy Compensation
For transition metals, stability of a particular oxidation state in aqueous solution depends on:
ΔG∘=ΔHhydration∘−ΔHionisation∘
Why it holds:
- Higher oxidation states have higher ionisation energy (harder to remove electrons).
- But they also have higher hydration energy (smaller, more charged ions attract water more strongly).
- The balance determines which state is stable.
Example:
- CuX+ is unstable in water because its hydration energy is too low to compensate for the loss of the second electron.
- CuX2+ is stable in water.
Key Principle 4: Disproportionation
Some oxidation states are unstable and spontaneously convert to two other states:
2CuX+Cu+CuX2+
Why it holds: …
The key idea is stability of chelate complexes — chelating ligands form multiple bonds with a metal ion, producing a more stable complex than a comparable monodentate ligand.
- Assertion is true: Toxic metal ions (e.g., Hg2+, Pb2+) are removed from the body using chelating ligands like EDTA or dimercaprol, which bind the metal and allow excretion.
- Reason is true: Chelate complexes are thermodynamically more stable due to the chelate effect (entropy gain from displacing many monodentate ligands). …
The assertion is true (toxic metal ions are removed by chelating ligands) and the reason is true (chelate complexes are more stable). The greater stability of the chelate complex is exactly why it can bind the toxic metal ion tightly enough to remove it from biological circulation — so the reason correctly explains the assertion. The correct option is (i).
The Concept: Why Chelation Works for Detoxification
The key idea here is the chelate effect — a thermodynamic principle that makes multidentate ligands form far more stable complexes than their monodentate counterparts. But the reason chelating ligands are used to remove toxic metal ions isn't just "they're stable." It's that they bind selectively and irreversibly enough to prevent the metal from interacting with biological molecules, while still allowing the complex to be excreted.
Let's break this down step by step.
1. Understanding the Assertion
Toxic metal ions like Pb2+, Hg2+, Cd2+, and As3+ cause damage by binding to enzymes and proteins, disrupting their function. Chelating ligands (e.g., EDTA, dimercaprol, penicillamine) are administered as antidotes. They wrap around the metal ion like a claw (from Greek chele = claw), forming a stable, water-soluble complex that can be excreted via urine.
The assertion is true — chelation therapy is a standard medical treatment for heavy metal poisoning.
2. Understanding the Reason
Chelate complexes are indeed more stable than analogous complexes with monodentate ligands. This is the chelate effect, quantified by comparing the equilibrium constants.
For example, consider the reaction of Ni2+ with ammonia (monodentate) vs. ethylenediamine (bidentate):
Ni2++6NH3Ni2++3en⇌[Ni(NH3)6]2+logK≈8.6⇌[Ni(en)3]2+logK≈18.3
The chelate complex is about 1010 times more stable! This stability comes from two factors:
- Entropy gain: One chelating ligand replaces several monodentate ligands, increasing the number of free particles in solution (favourable entropy).
- Enthalpy contribution: The bite angle of the chelate ring often matches the metal's preferred geometry, giving stronger bonds.
The chelate effect: ΔG∘=−RTlnK — more negative ΔG∘ for chelates means greater stability.
So the reason is true — chelate complexes are more stable.
3. Connecting Assertion and Reason — The Critical Point
Does the stability of chelate complexes explain why they remove toxic metal ions? Yes — directly. …
Method: Assertion–Reason Analysis (Fact + Logic Check)
This is the standard approach for CBSE / competitive exam Assertion–Reason questions. The steps are:
Step 1: Check the Assertion for truth
- Assertion: Toxic metal ions are removed by the chelating ligands.
- Fact: Yes — chelating ligands (like EDTA, DMSA) bind strongly to toxic metal ions (e.g., Pb2+, Hg2+, Cd2+) and help excrete them from the body. This is the basis of chelation therapy.
- ✓ Assertion is true.
Step 2: Check the Reason for truth
- Reason: Chelate complexes tend to be more stable.
- Fact: Yes — chelate complexes are more stable than complexes with monodentate ligands due to the chelate effect (entropy-driven stability).
- ✓ Reason is true.
Step 3: Check if Reason correctly explains the Assertion
- The reason (greater stability of chelate complexes) is exactly why chelating ligands can out-compete the toxic ion's biological binding sites and lock it into an inert, excretable complex. …
Common Mistakes & How to Avoid Them
Mistake 1: Thinking a General Property Can't Also Be the Explanation
Why students make this mistake:
Students read the reason ("chelate complexes tend to be more stable") as just a general fact about chelates, disconnected from the specific claim in the assertion about removing toxic ions.
How to avoid:
Ask: why does forming a more stable complex remove a toxic ion from circulation? Because the chelating ligand binds the metal ion more strongly (forms a MORE STABLE complex) than the weaker bonds the metal ion would otherwise form with biological molecules (enzymes, proteins). This higher stability is exactly what lets the chelator out-compete and sequester the toxic ion so it can be safely excreted.
✓ Correct approach:
- Assertion: True
- Reason: True
- The reason (greater stability of the chelate) is the correct explanation → Option (i)
Mistake 2: Thinking the Assertion is False
Why students make this mistake:
Some students confuse "removal" with "neutralization" or think chelating ligands only bind, not remove. They forget that chelation therapy (e.g., EDTA for lead poisoning) is a standard medical procedure.
How to avoid:
Recall a real example:
- EDTA (a hexadentate ligand) binds Pb²⁺, Ca²⁺, etc.
- The complex is water-soluble and excreted via urine.
- This is a fact in coordination chemistry and medicine.
✓ Key takeaway: Chelating ligands do remove toxic metal ions from the body.
Mistake 3: Thinking the Reason is False
Why students make this mistake:
Some students think "stability" is vague or that chelate complexes are not always more stable than monodentate complexes. They forget the chelate effect — entropy gain makes chelates more stable.
How to avoid:
Remember the chelate effect:
- A bidentate ligand replaces two monodentate ligands.
- Number of particles increases → entropy increases → ΔG becomes more negative → complex is more stable. …
- TG EAPCET 2026Set eng-2026-05-11-FN1 markMCQQ.Which one of the following is an outer orbital complex and exhibits paramagnetic behaviour? (A) [Co(C2O4)3]3− (B) [MnCl6]3− (C) [Mn(CN)6]3− (D) [Fe(CN)6]3−
›Reveal solutionSolution
The key is to identify which complex uses outer d-orbitals (sp³d² hybridisation) and has unpaired electrons. Only [MnCl6]3− fits both criteria, so the answer is (B).
Concept & Intuition
In coordination chemistry, "outer orbital" complexes use the metal’s outer d-orbitals (nd) for hybridisation, typically sp³d², and are formed with weak-field ligands. These complexes tend to be high-spin, meaning they retain unpaired electrons and are paramagnetic. In contrast, "inner orbital" complexes use inner d-orbitals ((n−1)d) for d²sp³ hybridisation, usually with strong-field ligands, and are often low-spin (fewer or no unpaired electrons). So we need to check each complex for: (1) the ligand field strength, (2) the resulting electron configuration, and (3) whether the hybridisation uses outer or inner d-orbitals.
Step-by-step reasoning
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Identify the metal oxidation states and d-electron counts
- (A) [Co(C2O4)3]3−: Oxalate is a bidentate ligand with charge −2. Let Co be x: x+3(−2)=−3⇒x=+3. Co³⁺ has electron configuration [Ar]3d6.
- (B) [MnCl6]3−: Cl⁻ has charge −1. Let Mn be x: x+6(−1)=−3⇒x=+3. Mn³⁺ has [Ar]3d4.
- (C) [Mn(CN)6]3−: CN⁻ is −1, same calculation gives Mn³⁺, 3d4.
- (D) [Fe(CN)6]3−: CN⁻ is −1, so Fe is +3. Fe³⁺ has [Ar]3d5.
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Determine ligand field strength and spin state
- Oxalate (C2O42−) is a moderate-field ligand — it can cause pairing but not as strongly as CN⁻. For Co³⁺ (3d6), oxalate typically gives a low-spin configuration (all electrons paired) because Co³⁺ has a high pairing energy and oxalate is strong enough to cause pairing. So [Co(C2O4)3]3− is diamagnetic (no unpaired electrons).
- Cl⁻ is a weak-field ligand — it cannot cause pairing. For Mn³⁺ (3d4), weak field gives high-spin: t2g3eg1 (4 unpaired electrons).
- CN⁻ is a strong-field ligand — it forces pairing. For Mn³⁺ (3d4), strong field gives low-spin: t2g4 (2 unpaired electrons).
- CN⁻ with Fe³⁺ (3d5) gives low-spin: t2g5 (1 unpaired electron).
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Decide inner vs. outer orbital hybridisation
- Inner orbital (d²sp³) uses two inner (n−1)d orbitals, so it requires at least two empty d-orbitals in the inner set. This happens when electrons are paired to vacate d-orbitals.
- Outer orbital (sp³d²) uses outer nd orbitals, so it occurs when the inner d-orbitals are too filled to allow d²sp³ — typically in high-spin configurations.
- For (A): Low-spin Co³⁺ (t2g6) has all three t2g orbitals filled, but the eg orbitals are empty. It uses two eg (inner d) orbitals → inner orbital (d²sp³). …
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- TG EAPCET 2026Set eng-2026-05-11-AN1 markMCQQ.How many of the following molecules / ions are paramagnetic in nature? N2,O2,F2,NO,CO,O2+,O2−,O22−,N2+,NO+,NO−,H2 (A) 7 (B) 6 (C) 5 (D) 4
›Reveal solutionSolution
Paramagnetism arises from unpaired electrons. By constructing molecular orbital (MO) diagrams for each diatomic species and counting unpaired electrons, we find that 6 of the 12 listed species are paramagnetic.
Concept & Intuition
Paramagnetism occurs when a molecule has one or more unpaired electrons. The key tool is the molecular orbital (MO) diagram for homonuclear diatomic molecules (and closely related heteronuclear ones like NO). For second-period elements, the order of MOs is:
σ1s,σ1s∗,σ2s,σ2s∗,π2px=π2py,σ2pz,π2px∗=π2py∗,σ2pz∗
(For O2 and beyond, the σ2pz is lower than the π2p∗ orbitals, but the key is filling electrons in order and applying Hund’s rule.)
We will determine the electron configuration for each species and check for unpaired electrons.
Step-by-step analysis
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N2 (14 electrons)
Configuration: (σ1s)2(σ1s∗)2(σ2s)2(σ2s∗)2(π2p)4(σ2pz)2
All electrons paired → Diamagnetic.
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O2 (16 electrons)
Configuration: … (σ2pz)2(π2p∗)2
The two π∗ electrons occupy separate orbitals (Hund’s rule) → 2 unpaired electrons → Paramagnetic.
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F2 (18 electrons)
Configuration: … (π2p∗)4 → all paired → Diamagnetic.
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NO (15 electrons)
Similar to O2+ (15 e⁻). MO diagram: … (π2p∗)1 → 1 unpaired electron → Paramagnetic.
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CO (14 electrons)
Isoelectronic with N2 → all paired → Diamagnetic.
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O2+ (15 electrons)
Remove one electron from O2’s π∗ orbital → (π2p∗)1 → 1 unpaired electron → Paramagnetic.
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O2− (17 electrons)
Add one electron to O2’s π∗ → (π2p∗)3 → one orbital doubly occupied, one singly → 1 unpaired electron → Paramagnetic.
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O22− (18 electrons)
(π2p∗)4 → all paired → Diamagnetic.
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N2+ (13 electrons) …
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- TG EAPCET 2026Set ap-2026-05-04-AN1 markMCQQ.The hybridization and magnetic nature of [CoF6]3− respectively are (A) sp3d2 and paramagnetic (B) sp3d2 and diamagnetic (C) d2sp3 and paramagnetic (D) d2sp3 and diamagnetic
›Reveal solutionSolution
The complex [CoF6]3− has Co3+ in a weak-field ligand environment (F⁻), leading to high-spin d6 configuration with four unpaired electrons, sp3d2 hybridization, and paramagnetic behavior. The correct option is (A).
The key to this question lies in two decisions: the oxidation state of cobalt, and whether the ligand (fluoride) is strong-field or weak-field. Fluoride is a weak-field ligand — it does not force pairing of electrons. That choice determines the entire electronic arrangement and hence the hybridization and magnetic properties.
Let’s walk through it step by step.
- Find the oxidation state of cobalt. The complex is [CoF6]3−. Fluoride has a charge of −1 each, so six fluorides contribute −6. The overall charge is −3. Let the oxidation state of Co be x:
x+6(−1)=−3⇒x−6=−3⇒x=+3.
So cobalt is in the +3 oxidation state.
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Write the electronic configuration of Co3+.
Cobalt (atomic number 27) has ground-state configuration [Ar]3d74s2. Removing three electrons (the two 4s electrons and one 3d electron) gives Co3+: [Ar]3d6.
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Consider the ligand field.
Fluoride (F−) is a weak-field ligand. In the spectrochemical series, F− lies far to the left (small Δ). This means the crystal field splitting energy Δ is small, so electrons prefer to occupy all five d orbitals singly before pairing — the high-spin configuration.
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Arrange the six d electrons in the octahedral field.
In an octahedral field, the d orbitals split into t2g (lower energy, three orbitals) and eg (higher energy, two orbitals). With weak field, Hund’s rule applies:
- First three electrons go into t2g with parallel spins.
- Next two electrons go into eg with parallel spins.
- The sixth electron goes into t2g, pairing with one electron there. The result: t2g4eg2 — four electrons in t2g (one pair, two unpaired) and two unpaired in eg. Total unpaired electrons = 4. …
- TG EAPCET 2026Set ap-2026-05-04-FN1 markMCQQ.X, Y are the complexes of Mn+ ion. The spin only magnetic moment values of X, Y respectively are 3.87 BM, 1.73 BM. Mn+ is (A) Mn2+ (B) Co2+ (C) Fe2+ (D) Cr3+
›Reveal solutionSolution
The spin-only magnetic moment μ=n(n+2) BM, where n is the number of unpaired electrons. 3.87 BM corresponds to 3 unpaired electrons, and 1.73 BM corresponds to 1 unpaired electron. The metal ion that can give both these configurations in different complexes is Fe2+.
The key idea here is that the same metal ion can have different numbers of unpaired electrons depending on the ligand field — weak field (high spin) vs strong field (low spin). The magnetic moment tells us exactly how many unpaired electrons are present, and we match that to the possible d-electron configurations.
The spin-only formula is μ=n(n+2) BM, where n is the number of unpaired electrons. Let’s decode what the given values mean.
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For μ=3.87 BM:
n(n+2)=3.87
Squaring: n(n+2)=15
Solving n2+2n−15=0 gives n=3 (the positive root). So complex X has 3 unpaired electrons.
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For μ=1.73 BM:
n(n+2)=1.73
Squaring: n(n+2)=3
Solving n2+2n−3=0 gives n=1. So complex Y has 1 unpaired electron.
So the same metal ion Mn+ can exist in one complex with 3 unpaired electrons and in another with just 1 unpaired electron. That means it must have a d-electron count that allows both a high-spin (weak field) and a low-spin (strong field) configuration.
Watch outNot all dn configurations can show both high-spin and low-spin behaviour. Only d4, d5, d6, and d7 can do so in octahedral complexes. For d1, d2, d3, d8, d9, d10, the number of unpaired electrons is fixed regardless of field strength.
Now check each option:
- (A) Mn2+: d5 configuration. High spin: 5 unpaired electrons (μ=35≈5.92 BM). Low spin: 1 unpaired electron (μ=3≈1.73 BM). But 3.87 BM (3 unpaired) is not possible for d5 — it’s either 5 or 1. So not this. …
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- TG EAPCET 2024Set ap-2024-05-08-FN1 markMCQQ.Which of the following is correct? (A) Ruby is Al2O3 containing 5% Cr3+ ions (B) Mn2(CO)10 contains two bridged carbonyl groups (C) [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]3+ is an outer orbital complex (D) [Ni(CN)4]2−, [NiCl4]2− both have tetrahedral geometry
›Reveal solutionSolution
The correct statement is (C). It accurately describes [Co(NH3)6]3+ as an inner orbital complex (due to Co3+ being d6 with a strong field ligand) and [Ni(NH3)6]3+ as an outer orbital complex (due to Ni3+ being d7, which cannot form an inner orbital complex).
The problem requires us to evaluate the correctness of four statements related to inorganic chemistry, covering topics like gemstone composition, metal carbonyl structures, and coordination complex properties (hybridization, geometry, and orbital type). The core concepts involve understanding oxidation states, d-electron configurations, ligand field strength, and how these factors dictate the electronic structure and geometry of coordination compounds.
Here's a detailed evaluation of each option:
1. Evaluating Option (A): Ruby composition
- Statement: Ruby is Al2O3 containing 5% Cr3+ ions.
- Concept: Ruby is a variety of the mineral corundum, which is aluminium oxide (Al2O3). Its characteristic red color is indeed due to the presence of trace amounts of chromium(III) ions (Cr3+) substituting for Al3+ ions in the crystal lattice.
- Analysis: While the chemical formula Al2O3 and the presence of Cr3+ ions are correct, the concentration of Cr3+ is typically very low in natural rubies, usually ranging from 0.5% to 2%. A concentration of 5% Cr3+ would be unusually high for a natural ruby and would likely result in a much darker, almost opaque, or brownish-red color, rather than the vibrant red typically associated with ruby.
- Conclusion: The statement is incorrect due to the specified concentration of Cr3+ ions.
2. Evaluating Option (B): Mn2(CO)10 structure
- Statement: Mn2(CO)10 contains two bridged carbonyl groups.
- Concept: This statement relates to the structure of dimeric metal carbonyls, which can often be predicted using the 18-electron rule. The 18-electron rule states that stable organometallic compounds often have 18 valence electrons around the central metal atom.
- Analysis:
- Manganese (Mn) is a Group 7 element, so it has 7 valence electrons.
- A carbonyl (CO) ligand is a 2-electron donor.
- In Mn2(CO)10, each Mn atom is bonded to five CO ligands.
- Electrons contributed by ligands to one Mn atom: 5×2=10 electrons.
- Total electrons around one Mn atom from its own valence electrons and ligands: 7+10=17 electrons.
- To satisfy the 18-electron rule, each Mn atom needs one more electron. This is achieved by forming a single metal-metal bond between the two Mn atoms.
- The structure of Mn2(CO)10 is (CO)5Mn−Mn(CO)5, which consists of two Mn(CO)5 units linked by a direct Mn-Mn bond. There are no bridging carbonyl groups in this molecule.
- Conclusion: The statement is incorrect.
3. Evaluating Option (C): Inner and outer orbital complexes
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Statement: [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]3+ is an outer orbital complex.
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Concept: This involves determining the oxidation state of the metal, its d-electron configuration, the nature of the ligand (strong or weak field), and then predicting the hybridization and whether it's an inner (d2sp3) or outer (sp3d2) orbital complex.
- Inner orbital complex: Uses inner d orbitals (e.g., 3d for a 3d series metal) for hybridization, typically d2sp3. This requires two empty d orbitals.
- Outer orbital complex: Uses outer d orbitals (e.g., 4d for a 3d series metal) for hybridization, typically sp3d2.
- Ligand field strength: NH3 is generally considered a strong field ligand, causing electron pairing in d orbitals for certain configurations.
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Analysis for [Co(NH3)6]3+:
- Let the oxidation state of Co be x. Since NH3 is a neutral ligand, x+6(0)=+3⟹x=+3.
- Electronic configuration of Co: [Ar]3d74s2.
- Electronic configuration of Co3+: [Ar]3d6.
- In an octahedral field, the d orbitals split into t2g (lower energy) and eg (higher energy) sets.
- NH3 is a strong field ligand, causing maximum pairing of electrons in the t2g orbitals.
- For d6, all six electrons pair up in the t2g orbitals: t2g6eg0.
- This leaves two empty 3d orbitals (the eg orbitals) available for hybridization.
- Hybridization: d2sp3. This is an inner orbital complex.
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Analysis for [Ni(NH3)6]3+:
- Let the oxidation state of Ni be y. Since NH3 is a neutral ligand, y+6(0)=+3⟹y=+3.
- Electronic configuration of Ni: [Ar]3d84s2.
- Electronic configuration of Ni3+: [Ar]3d7.
- NH3 is a strong field ligand.
- For d7 in an octahedral field, even with strong field ligands, the electrons will fill the t2g orbitals first, then the eg orbitals.
- The t2g orbitals can accommodate 6 electrons. The 7th electron must go into an eg orbital.
- Configuration: t2g6eg1. …
- TG EAPCET 2023Set ap-2023-05-10-FN1 markMCQQ.Which of the following is not paramagnetic? (A) O2− (B) O2+ (C) CO (D) NO
›Reveal solutionSolution
Paramagnetism depends on unpaired electrons. Using molecular orbital theory, we find that CO has no unpaired electrons, while O2−, O2+, and NO all have at least one unpaired electron. Therefore, CO is not paramagnetic — the answer is (C).
The key idea is simple: a substance is paramagnetic if it contains unpaired electrons. Diamagnetic substances have all electrons paired. So to decide which of these molecules or ions is not paramagnetic, we need to determine the number of unpaired electrons in each. The most reliable tool for small diatomic molecules and ions is molecular orbital (MO) theory, which gives the electron configuration and tells us exactly how many electrons are unpaired.
For second-period homonuclear diatomics (like O2 and its ions), the MO energy order is:
σ1s<σ1s∗<σ2s<σ2s∗<σ2pz<π2px=π2py<π2px∗=π2py∗<σ2pz∗
For heteronuclear diatomics like CO and NO, the same general filling pattern applies, with the π2p orbitals lying below σ2pz.
Let's work through each species step by step.
- O2− (superoxide ion) Neutral O2 has 16 electrons. Its MO configuration is:
σ1s2σ1s∗2σ2s2σ2s∗2σ2pz2π2px2π2py2π2px∗1π2py∗1
That gives two unpaired electrons in the π∗ orbitals — O2 is paramagnetic.
O2− has one extra electron (total 17). That electron goes into one of the π∗ orbitals, giving:
π2px∗2π2py∗1
So there is one unpaired electron. Hence O2− is paramagnetic.
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O2+
Neutral O2 has the configuration π2px∗1π2py∗1 in its antibonding π∗ orbitals (16 electrons total). Removing one electron to form O2+ (15 electrons) removes one of these π∗ electrons, leaving π2px∗1π2py∗0 (or the reverse). This leaves one unpaired electron, so O2+ is paramagnetic.
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CO (carbon monoxide)
CO has 14 electrons total (6 from C, 8 from O). Its MO configuration is:
σ1s2σ1s∗2σ2s2σ2s∗2π2px2π2py2σ2pz2 …
- TG EAPCET 2023Set eng-2023-05-12-FN1 markMCQQ.Match the following List - I (complex) A. [Co(NH3)6]3+ B. [CoF6]3− C. [Ni(CO)4] D. [Fe(CN)6]3− List - II (electronic configuration of metal/ion) I. t2g5eg0 II. t2g6eg0 III. t2g4eg2 IV. t2g6eg0 (A) A - II, B - III, C - IV, D - I (B) A - III, B - IV, C - II, D - I (C) A - IV, B - III, C - I, D - II (D) A - II, B - I, C - IV, D - III
›Reveal solutionSolution
The key is to determine the oxidation state and geometry of each complex, then apply crystal field theory to find the d-electron count and splitting pattern. The correct matches are A–II, B–III, C–IV, D–I, so option (A) is correct.
We need to match each complex with the correct t2g and eg electron configuration of the central metal ion. This requires knowing:
- The oxidation state of the metal (to get the d-electron count).
- The geometry (octahedral or tetrahedral) and the ligand field strength (strong-field vs. weak-field), which determines whether the complex is low-spin or high-spin.
Let’s work through each complex step by step.
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Complex A: [Co(NH3)6]3+
- Cobalt is in the +3 oxidation state (each NH₃ is neutral). Co atomic number = 27, so Co³⁺ has 3d6 configuration.
- NH₃ is a strong-field ligand (spectrochemical series: NH₃ > H₂O > F⁻). In an octahedral field, strong-field ligands cause a large splitting, so electrons pair up in the lower t2g orbitals.
- For d6 in a strong octahedral field: all six electrons fill the t2g set (three orbitals, each with two electrons) → t2g6eg0.
- This matches II (and also IV, but note II and IV are identical in the list; we’ll see which one fits elsewhere). So A → II.
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Complex B: [CoF6]3−
- Again Co is +3 (F⁻ is –1, total charge –3 gives Co³⁺). So again d6.
- F⁻ is a weak-field ligand. In a weak octahedral field, the splitting is small, so electrons occupy all five d-orbitals singly before pairing (Hund’s rule).
- For d6 weak-field: first five electrons go one per orbital (three t2g, two eg), then the sixth electron pairs in a t2g orbital → t2g4eg2.
- This matches III. So B → III.
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Complex C: [Ni(CO)4]
- CO is a neutral ligand, and the complex is neutral. Nickel is in the 0 oxidation state. Ni atomic number = 28, so Ni⁰ has 3d84s2, but in complexes the 4s electrons are lost first; effectively Ni⁰ is d10 (since 4s² electrons are promoted or involved in bonding, but the common treatment: Ni(0) in carbonyls is d10).
- CO is a strong-field ligand, but more importantly, Ni(CO)₄ is tetrahedral (not octahedral). In tetrahedral geometry, the splitting is reversed and smaller: the e set (lower energy) and t2 set (higher energy).
- For a d10 ion, all orbitals are completely filled regardless of geometry. In tetrahedral notation: e4t26. But the given options use octahedral notation t2g and eg. For a tetrahedral complex, we often still use the same labels but with the understanding that the t2 set is higher. However, the problem lists only octahedral-style configurations.
- Since Ni(CO)₄ is diamagnetic and d10, the only way to represent it in the given notation is t2g6eg0 (all electrons paired in lower set? That doesn’t fit). Wait — careful: For a d10 system, all d-orbitals are full. In octahedral field, that would be t2g6eg4, but that’s not an option. The options only have t2gxegy with x+y=6 or 5 or 4. So something is off.
- Actually, Ni(CO)₄ is tetrahedral, and the metal is Ni(0) with d10. In tetrahedral splitting, the e set (lower) holds 4 electrons, the t2 set (higher) holds 6. But the problem’s options are clearly in octahedral notation. The trick: For d10, the configuration is completely filled, so it is often written as t2g6eg4 in octahedral, but that’s not listed. However, look at the options: IV is t2g6eg0. That would imply only 6 d-electrons, not 10.
- This suggests that the problem expects us to consider the effective d-electron count after considering the strong-field CO ligands causing pairing? No, that’s not right.
- Let’s re-evaluate: Ni(CO)₄ is a classic example of a d10 tetrahedral complex. But the given configurations in List II all sum to 6 electrons (since t2g and eg together hold 6 in octahedral). So they are not meant for d10. Perhaps the problem considers Ni in a different oxidation state? No, Ni(CO)₄ is Ni(0).
- Wait — maybe the complex is actually [Ni(CO)4] but the metal is considered as Ni²⁺? That would be wrong.
- Let’s check the options: C is matched with IV in options (A) and (D). IV is t2g6eg0. That is a d6 low-spin configuration. Could it be that Ni(CO)₄ is actually diamagnetic and the 10 d-electrons are all paired? In tetrahedral, the e set holds 4, t2 holds 6, so the configuration is e4t26. If we relabel e as eg and t2 as t2g (which is not correct but sometimes done loosely), then it would be eg4t2g6, which is not t2g6eg0. …
- TG EAPCET 2022Set ap-2022-07-30-FN1 markMCQQ.Which of the following pair of ions in the presence of a weak ligand will have the same spin only magnetic moments? (A) Sc3+ and Cu2+ (B) Ti2+ and Co2+ (C) V2+ and Co2+ (D) V2+ and Ni2+
›Reveal solutionSolution
Weak ligand means high-spin, so count unpaired d-electrons and use μ=n(n+2) BM. V2+ (d3) and Co2+ (d7, high-spin) both have 3 unpaired electrons, giving identical moments. Answer: (C).
Concept & Intuition
The spin-only magnetic moment is μ=n(n+2) Bohr magnetons, where n is the number of unpaired electrons. It depends only on n, so two ions match when their high-spin d-configurations give the same number of unpaired electrons. A weak ligand is a weak-field ligand, so electrons fill orbitals following Hund's rule (high-spin) before pairing.
Step-by-step
Count unpaired electrons for each ion (high-spin):
- Sc3+: [Ar]3d0⇒n=0
- Ti2+: 3d2⇒n=2
- V2+: 3d3⇒n=3
- Co2+: 3d7 (high-spin t2g5eg2) ⇒n=3
- Ni2+: 3d8⇒n=2
- Cu2+: 3d9⇒n=1
Now test the pairs: …
- TG EAPCET 2022Set eng-2022-07-20-FN1 markMCQQ.The elements with full d10 electronic configuration in their “+2” oxidation state are (A) Cu, Ni, Zn (B) Ni, Au, Cd (C) Au, Hg, Pd (D) Zn, Cd, Hg
›Reveal solutionSolution
The key is that a d10 configuration in the +2 state means the neutral atom must have lost two s-electrons, leaving a filled d-subshell. The elements that satisfy this are Zn, Cd, and Hg — all group 12 metals. The correct option is (D).
The question asks which set of elements, in their +2 oxidation state, have a completely filled d10 electronic configuration. This is a classic test of your understanding of how transition and post-transition metals lose electrons, and which ones have a stable, full d-subshell after losing two electrons.
Let’s break it down.
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What does d10 in the +2 state mean?
For an element to have a d10 configuration when it is in the +2 oxidation state, the neutral atom must have exactly two more electrons than the d10 core. Those two electrons are almost always the outermost s-electrons, because s-electrons are lost before d-electrons in transition metals. So the neutral atom’s electron configuration ends in ...d10s2. When it loses both s-electrons, the ion becomes ...d10.
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Which elements have a d10s2 configuration in their ground state?
This is the hallmark of group 12 elements: zinc (Zn), cadmium (Cd), and mercury (Hg). Their configurations are:
- Zn: [Ar]3d104s2
- Cd: [Kr]4d105s2
- Hg: [Xe]4f145d106s2 In each case, the d-subshell is already full, and the two s-electrons are the valence electrons. Losing both gives a d10 ion: Zn2+, Cd2+, Hg2+.
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Check the other elements mentioned in the options.
- Cu (copper): Neutral Cu is [Ar]3d104s1. In the +2 state, it loses the 4s electron and one 3d electron, giving 3d9 — not d10.
- Ni (nickel): Neutral Ni is [Ar]3d84s2. In the +2 state, it loses both 4s electrons, giving 3d8 — not d10.
- Au (gold): Neutral Au is [Xe]4f145d106s1. In the +2 state, it loses the 6s electron and one 5d electron, giving 5d9 — not d10. …
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- TG EAPCET 2021Set eng-2021-08-05-FN1 markMCQQ.The magnetic moment of the high spin complex is 5.92 BM. What is the electronic configuration? (A) t2g3 eg1 (B) t2g4 eg2 (C) t2g3 eg2 (D) t2g5 eg0
›Reveal solutionSolution
The magnetic moment of 5.92 BM corresponds to 5 unpaired electrons. For a high‑spin complex, this gives the configuration t2g3 eg2, which is option (C).
The magnetic moment of a transition‑metal complex tells us directly how many unpaired electrons the metal ion has. The formula that connects them is the spin‑only formula:
μ=n(n+2) BM
where n is the number of unpaired electrons and μ is the magnetic moment in Bohr magnetons (BM). This formula works well for first‑row transition metals because orbital angular momentum is often quenched by the ligand field.
Given μ=5.92 BM, we solve for n:
5.92=n(n+2)
Squaring both sides:
35.05≈n(n+2)
We look for an integer n that satisfies this. Trying n=5:
5×7=35
That’s a near‑perfect match (the small difference is due to rounding 5.92). So n=5 unpaired electrons.
Now, the complex is described as high‑spin. In an octahedral field, the d orbitals split into t2g (lower energy) and eg (higher energy). For a high‑spin configuration, electrons fill all five d orbitals singly before pairing — Hund’s rule applies fully. That means the five unpaired electrons occupy all three t2g orbitals and both eg orbitals, each with one electron.
That gives the configuration:
t2g3 eg2
Let’s check the options:
- (A) t2g3 eg1 → 4 unpaired electrons → μ≈4×6=24≈4.90 BM — not a match.
- (B) t2g4 eg2 → 4 unpaired electrons (one pair in t2g) → same μ as above — not a match.
- (C) t2g3 eg2 → 5 unpaired electrons → μ≈5.92 BM — matches. …
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