Q.Predict the number of unpaired electrons in the square planar [Pt(CN)4]2− ion.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Magnetic Moment Calculation
From a Paperclip to a Magnet: The Intuition
You already know that a magnet can pick up iron nails. But what is actually happening inside that nail when it gets near the magnet? And why does a plastic comb, rubbed on hair, pick up tiny bits of paper — but never iron filings?
The answer lies in magnetization — the process by which a material becomes magnetic.
Think of a piece of iron as a chaotic crowd of tiny compass needles. Each needle is an atomic magnetic moment (a tiny magnet, arising from the spin of electrons). In unmagnetized iron, these needles point in random directions. Their magnetic effects cancel out, so the iron as a whole shows no net magnetism.
Now bring a strong magnet close. Its magnetic field acts like a command: "Line up!" The tiny compass needles inside the iron start rotating, aligning themselves with the external field. The more they align, the stronger the iron's own magnetic field becomes. This alignment is magnetization.
Magnetization is not the same as inducing a current. It is a purely magnetic reorientation of atomic dipoles inside a material.
The Precise Definition
Magnetization (M) is the net magnetic dipole moment per unit volume of a material. It tells you how strongly a material is magnetized — how many tiny atomic magnets are aligned, and in which direction.
If a material has N atoms per unit volume, each with an average magnetic moment μavg, then:
M=Nμavg
The SI unit of M is amperes per metre (A/m). Why? Because a magnetic dipole moment has units of A·m², and dividing by volume (m³) gives A/m.
M=volumetotal magnetic dipole moment
How Magnetization Connects to the Magnetic Field
When a material gets magnetized, it produces its own magnetic field. The total magnetic field B inside the material is the sum of:
- The external applied field H (caused by free currents, like the current in a solenoid)
- The material's response — the magnetization M
The fundamental relation is:
B=μ0(H+M)
where μ0=4π×10−7T⋅m/A is the permeability of free space.
Do not confuse H (magnetic field intensity, or "magnetizing field") with B (magnetic flux density). H is what you apply; M is what the material does; B is the total field you measure.
The Three Kinds of Magnetic Materials
Not all materials respond the same way to an external field. The magnetization M is proportional to H for most materials (at least for small fields):
M=χmH
where χm is the magnetic susceptibility — a dimensionless number that tells you how easily a material magnetizes.
| Material Type | χm | Behaviour | Example |
|---|---|---|---|
| Diamagnetic | Small and negative (≈−10−5) | Weakly repelled by a magnet; M opposes H | Water, copper, bismuth |
| Paramagnetic | Small and positive (≈10−5 to 10−3) | Weakly attracted; M aligns with H | Aluminium, oxygen gas |
| Ferromagnetic | Large and positive (≫1) | Strongly attracted; M can be huge and persists even after H is removed | Iron, nickel, cobalt |
Why this formula?
Magnetic Moment Calculation: Why the Formula Holds
Let's build this from first principles — understanding the why before the formula.
1. What is Magnetic Moment?
A magnetic moment (μ) is a measure of the strength and orientation of a magnet or current loop. It tells us how strongly an object will interact with an external magnetic field.
The core idea: any moving charge creates a magnetic field. A loop of current is like a tiny bar magnet — its magnetic moment quantifies this.
2. The Fundamental Formula: Current Loop
The Setup
Consider a planar loop of wire carrying a steady current I, enclosing an area A.
Why μ=IA?
Step 1: Force on a moving charge
A charge q moving with velocity v in a magnetic field B experiences:
F=q(v×B)
Step 2: Torque on a current loop
For a rectangular loop of sides a and b (A=ab), placed in a uniform B:
- Current I means charge flows. On side of length a, the force magnitude is F=IaB (since I=tq and v=ta).
- These forces on opposite sides form a couple (equal, opposite, not collinear).
- Torque τ=force×perpendicular distance=(IaB)×(bsinθ)
Step 3: Recognize the pattern
τ=I(ab)Bsinθ=IABsinθ
This looks exactly like:
τ=μBsinθ
Comparing, we identify:
μ=IA
Why this works: The torque on a current loop is proportional to the current and the area — this product naturally defines the magnetic moment.
3. For a Single Moving Charge (Orbital Magnetic Moment)
The Setup
An electron of charge −e moves in a circular orbit of radius r with speed v.
Why μ=2evr?
Step 1: Treat orbit as a current loop
- Time for one revolution: T=v2πr
- Current (charge per unit time): I=Te=2πrev
Step 2: Apply μ=IA
- Area of orbit: A=πr2
- So: μ=(2πrev)(πr2)=2evr
Step 3: Express in terms of angular momentum
- Orbital angular momentum: L=mvr
- Therefore: μ=2meL
Why this matters: The magnetic moment is directly proportional to angular momentum. The factor 2me is called the gyromagnetic ratio — it links mechanics to magnetism.
4. For a Solenoid (Many Turns)
The Setup
A solenoid of N turns, length l, carrying current I, cross-sectional area A.
Why μ=NIA? …
The key idea is that the magnetic moment depends on the number of unpaired electrons, which in turn depends on the metal's oxidation state, geometry, and ligand field splitting.
Step 1: Determine the oxidation state and electron configuration of Pt.
Pt is in group 10. In [Pt(CN)4]2−, each CN⁻ is −1, so Pt has oxidation state +2.
Pt(0): [Xe]4f145d96s1
Pt(II): remove two electrons (from 6s first), giving [Xe]4f145d8.
Step 2: Consider the geometry and ligand field. …
The key is to determine the oxidation state of Pt, then its d-electron count, and finally the crystal field splitting in a square planar geometry. For [Pt(CN)4]2−, Pt is in the +2 state with a d8 configuration, and the strong-field CN⁻ ligands cause pairing of all electrons, giving zero unpaired electrons.
Why This Approach Works
Magnetic moment tells us about unpaired electrons. To predict them, we need two things: the number of d-electrons on the central metal ion, and how those electrons arrange themselves under the influence of the ligands.
Square planar geometry is a special case. It arises most commonly for d8 metal ions with strong-field ligands — think Ni²⁺, Pd²⁺, Pt²⁺. The crystal field splitting in a square planar complex is essentially an extreme version of octahedral splitting where two trans ligands are removed, causing one set of d-orbitals to rise dramatically in energy. The result is a large energy gap between the lower and upper d-orbitals, forcing electrons to pair up.
CN⁻ is a strong-field ligand (high up in the spectrochemical series). So we expect maximum pairing.
Let’s walk through it step by step.
- Find the oxidation state of platinum. The complex ion is [Pt(CN)4]2−. Each CN⁻ ligand carries a –1 charge. Let the oxidation state of Pt be x.
x+4(−1)=−2⇒x−4=−2⇒x=+2
So platinum is in the +2 oxidation state.
-
Determine the d-electron count for Pt(II).
Platinum (Pt) has atomic number 78. Its ground-state electron configuration is [Xe]4f145d96s1.
When Pt loses two electrons to become Pt²⁺, it loses the 6s electron first, then one 5d electron.
So Pt²⁺ has the configuration [Xe]4f145d8.
That’s a d8 system.
-
Recall the crystal field splitting pattern for square planar geometry.
In a square planar complex, the d-orbital energies (from lowest to highest) are:
- dxz,dyz (degenerate, lowest)
- dz2 (slightly higher)
- dxy (higher still)
- dx2−y2 (highest, by a large margin)
The energy gap between the dxy and dx2−y2 orbitals is very large — comparable to or larger than the pairing energy for a d8 ion with strong-field ligands.
For square planar d8 with strong-field ligands, the splitting is so large that all eight electrons occupy the four lower orbitals, leaving the dx2−y2 orbital empty.
-
Fill the electrons according to Hund’s rule and the Aufbau principle. …
Method: Crystal Field Theory (CFT) for Square Planar Geometry
Why this method?
Square planar complexes arise from d8 configurations (like Pt2+) when the ligand field is very strong. CFT explains how d-orbital energies split, which directly tells us the electron arrangement and number of unpaired electrons.
Step 1: Determine the oxidation state and d-electron count
- Platinum (Pt) is in Group 10, atomic number 78.
- Each cyanide ligand (CN−) has a charge of −1. Four ligands give −4.
- Complex charge is 2−.
- Let oxidation state of Pt be x:
x+4(−1)=−2⇒x=+2
- Pt2+: neutral Pt has [Xe]4f145d96s1. Removing two electrons (from 6s first) gives 5d8.
- d8 configuration.
Step 2: Recall the square planar d-orbital splitting
For a strong-field square planar complex, the energy order (lowest to highest) is:
dxz,dyz<dz2<dxy<dx2−y2
- The gap between dxy and dx2−y2 is very large (strong field).
- This forces pairing of electrons in the lower orbitals.
Step 3: Fill the d-orbitals (Aufbau + Hund's rule)
For d8 in strong-field square planar: …
Here are the most common mistakes students make when calculating magnetic moments and unpaired electrons for square planar complexes like [Pt(CN)4]2−, along with how to avoid each.
1. Forgetting to Check the Oxidation State of the Metal
The Mistake:
Students jump straight to the geometry without first finding the oxidation number of platinum. This leads to using the wrong dn configuration.
How to Avoid:
Always start with the charge balance.
- Ligand charge: Each CN− is −1, so total from 4 ligands = −4.
- Complex charge: −2.
- Let oxidation state of Pt be x:
x+(−4)=−2⇒x=+2
So Pt is in the +2 oxidation state.
2. Using the Wrong Electronic Configuration for the Metal Ion
The Mistake:
Assuming Pt has the same configuration as Ni or Pd, or forgetting that Pt is a 5d series element.
How to Avoid:
- Pt atomic number = 78.
- Neutral Pt: [Xe]4f145d96s1 (or 5d86s2 — but the 5d96s1 is more stable).
- For Pt2+, remove two electrons — remove the 6s electrons first:
Pt2+:[Xe]4f145d8
So the d-electron count is d8.
3. Assuming Square Planar Always Means Low-Spin
The Mistake:
Students think all square planar complexes are diamagnetic (no unpaired electrons). This is not always true — it depends on the metal and ligand field strength.
How to Avoid:
- For d8 ions, square planar geometry is strongly favoured by strong-field ligands like CN−.
- Strong field → large splitting → electrons pair up in the lower orbitals.
- For Pt2+ (a 5d metal), the splitting is very large due to relativistic effects.
- Result: All 8 electrons are paired → zero unpaired electrons.
4. Confusing Square Planar with Tetrahedral Geometry
The Mistake:
Some students treat [Pt(CN)4]2− as tetrahedral (common for d8 with weak-field ligands like Cl−), leading to a different d-orbital splitting and wrong unpaired electron count.
How to Avoid:
- Pt2+ with strong-field ligands like CN− always forms square planar complexes.
- Tetrahedral d8 would have 2 unpaired electrons; square planar d8 has 0 unpaired electrons.
- Memorise: Ni2+ can be tetrahedral or square planar; Pt2+ and Pd2+ are always square planar.
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Showing the 12 most recent of 34 on this concept.
- AP EAPCET 2026Set eng-2026-05-12-FN1 markMCQQ.Consider the following Ti,V,Cr,Mn,Fe The spin only magnetic moment (in BM) of the metal with lowest melting point in its +3 oxidation state is (A) 15 (B) 24 (C) 35 (D) 3
›Reveal solutionSolution
This tests recognising Mn's anomalous melting point and computing a spin-only magnetic moment; the answer is 24 BM.
Concept and Intuition
Across the 3d series, melting points generally rise then fall with the number of unpaired d-electrons available for metallic bonding, but Mn is a famous outlier: its complex crystal structure (with several inequivalent Mn sites) leads to unusually weak metallic bonding, so Mn has by far the LOWEST melting point among Ti–Fe. Once the correct metal is identified, the spin-only formula μ=n(n+2) BM gives the magnetic moment from the number of unpaired electrons in the specified oxidation state.
Step-by-Step Solution
- Compare melting points of Ti, V, Cr, Mn, Fe: Ti≈1668°C, V≈1910°C, Cr≈1907°C, Mn≈1246°C (anomalously low), Fe≈1538°C. Mn has the lowest.
- Mn (Z=25): ground state [Ar]3d54s2.
- Mn3+: remove 2 electrons from 4s and 1 from 3d ⇒ configuration 3d4.
- By Hund's rule, 3d4 places 4 electrons in 5 d-orbitals all unpaired (free ion, no ligand field specified): n=4. …
- AP EAPCET 2026Set eng-2026-05-13-FN1 markMCQQ.In which of the following, elements are correctly arranged in the increasing order of unpaired electrons? (A) Fe < Co < Ni < Mn (B) Ni < Co < Mn < Fe (C) Mn < Fe < Co < Ni (D) Ni < Co < Fe < Mn
›Reveal solutionSolution
Counting unpaired 3d electrons in Mn, Fe, Co, Ni (Hund's rule) gives Mn=5, Fe=4, Co=3, Ni=2, so the increasing order is Ni < Co < Fe < Mn.
Concept and Intuition
For first-row transition metals, the 4s orbital fills before 3d but electrons in the (n−1)d subshell obey Hund's rule of maximum multiplicity — electrons singly occupy all five d orbitals before any pairing begins. As we move across the row adding one more d-electron at a time past the half-filled d5 configuration, pairing begins and the number of unpaired electrons decreases even though the electron count increases, until d10 (all paired).
Step-by-Step Solution
- Write ground-state configurations (outer shells): Mn = [Ar]3d54s2; Fe = [Ar]3d64s2; Co = [Ar]3d74s2; Ni = [Ar]3d84s2.
- Apply Hund's rule to count unpaired d-electrons:
- Mn, 3d5: all five orbitals singly occupied → 5 unpaired.
- Fe, 3d6: one orbital now doubly occupied, four still singly occupied → 4 unpaired.
- Co, 3d7: two orbitals doubly occupied, three singly occupied → 3 unpaired.
- Ni, 3d8: three orbitals doubly occupied, two singly occupied → 2 unpaired. …
- AP EAPCET 2026Set eng-2026-05-15-AN1 markMCQQ.A transition metal ion X3+ has a magnetic moment of 15 BM. The atomic number of the metal X is (A) 24 (B) 25 (C) 26 (D) 27
›Reveal solutionSolution
15 BM means 3 unpaired electrons; the only ion among the choices that is unambiguously d3 is Cr3+, atomic number 24.
Concept and Intuition
The spin-only magnetic moment formula μ=n(n+2) BM connects the number of unpaired electrons n to the measured moment. Working backwards from a given moment tells you n directly, and then you match n to the d-electron count of the ion.
Step-by-Step Solution
- μ=n(n+2)=15⇒n(n+2)=15⇒n2+2n−15=0⇒(n+5)(n−3)=0⇒n=3.
- So X3+ has 3 unpaired electrons — i.e. it is a d3 ion (three electrons singly occupying the three t2g orbitals with no possibility of pairing, regardless of ligand field).
- Check each candidate atomic number as the neutral atom, then remove 3 electrons for the 3+ ion:
- Z=24, Cr: [Ar]3d54s1⇒Cr3+=[Ar]3d3. Exactly 3 unpaired electrons. ✓
- Z=25, Mn: [Ar]3d54s2⇒Mn3+=[Ar]3d4, which has 4 unpaired electrons (high spin). ✗ …
- AP EAPCET 2026Set eng-2026-05-15-AN1 markMCQQ.How many of the following complex ions contain 4 unpaired electrons? [Cr(H2O)6]2+, [Mn(H2O)6]2+, [Fe(H2O)6]2+, [Co(H2O)6]3+, [Cu(H2O)6]2+, [CoF6]3−, [Cr(CN)6]4−, [MnCl4]2− The correct answer is (A) 3 (B) 4 (C) 2 (D) 5
›Reveal solutionSolution
Working out the d-electron count and spin state for each of the eight complex ions, exactly four of them ([Cr(H2O)6]2+, [Fe(H2O)6]2+, [Co(H2O)6]3+, [CoF6]3−) have 4 unpaired electrons.
Concept and Intuition
The number of unpaired d-electrons in a complex depends on (a) the metal's oxidation state and dn configuration, and (b) whether the ligand field is strong enough to force pairing (low spin) or not (high spin). H2O, F− and Cl− are weak-to-intermediate field ligands, so octahedral complexes with them are high spin; CN− is a strong field ligand, forcing low spin; tetrahedral complexes have such a small crystal field splitting that they are essentially always high spin regardless of the ligand.
Step-by-Step Solution
Go through each ion (metal ion configuration, spin state, unpaired count):
- [Cr(H2O)6]2+: Cr2+=d4, weak field (HS) ⇒t2g3eg1⇒ 4 unpaired.
- [Mn(H2O)6]2+: Mn2+=d5, HS ⇒t2g3eg2⇒ 5 unpaired.
- [Fe(H2O)6]2+: Fe2+=d6, HS ⇒t2g4eg2⇒ 4 unpaired (one paired orbital, four singly occupied).
- [Co(H2O)6]3+: Co3+=d6; H2O is too weak a field to pair Co3+ electrons (only very strong ligands like NH3/CN− do that), so it is HS like Fe above ⇒ 4 unpaired.
- [Cu(H2O)6]2+: Cu2+=d9⇒ 1 unpaired. …
- AP EAPCET 2026Set ap-2026-05-19-FN1 markMCQQ.Which of the following pairs of ions are not paramagnetic in nature? (Atomic Number: La=57, Ce=58, Eu=63, Gd=64, Tb=65, Yb=70, Lu=71) I. La3+,Ce4+ II. Eu2+,Ce3+ III. Lu3+,Yb2+ IV. Tb4+,Gd3+ The correct answer is (A) I & III (B) II & III (C) III & IV (D) I & IV
›Reveal solutionSolution
Determine the 4f-electron count of each lanthanide ion; a pair is diamagnetic (not paramagnetic) only if both ions have a fully empty (4f⁰) or fully filled (4f¹⁴) f-subshell.
Concept and Intuition
Lanthanide ions are paramagnetic whenever they have unpaired 4f electrons. The two 'magic' configurations with zero unpaired electrons are 4f⁰ (empty) and 4f¹⁴ (completely filled) — both diamagnetic. Any partially filled 4f subshell (4f¹ through 4f¹³, excluding the special stable half/fully filled cases which still can have unpaired electrons unless exactly f0/f14) gives unpaired electrons and hence paramagnetism.
Step-by-Step Solution
- La (Z=57): [Xe]5d16s2; La3+ removes all 3 outer electrons → [Xe]4f0 — diamagnetic.
- Ce (Z=58): [Xe]4f15d16s2; Ce4+ removes all 4 → [Xe]4f0 — diamagnetic. So pair I (La3+,Ce4+) is NOT paramagnetic.
- Ce3+ retains one f-electron: 4f1 — paramagnetic. Eu (Z=63): [Xe]4f76s2; Eu2+ → 4f7 — paramagnetic. So pair II IS paramagnetic.
- Yb (Z=70): [Xe]4f146s2; Yb2+ → 4f14 — diamagnetic. Lu (Z=71): [Xe]4f145d16s2; Lu3+ → 4f14 — diamagnetic. So pair III is NOT paramagnetic. …
- AP EAPCET 2026Set eng-2026-05-18-AN1 markMCQQ.In which of the following given sets, complexes are correctly arranged in the increasing order of their spin only magnetic moment values? I. [Fe(CN)6]4−<[Fe(CN)6]3−<[Fe(H2O)6]3+ II. [Co(NH3)6]3+<[Ni(H2O)6]2+<[Cr(H2O)6]3+ III. [V(H2O)6]3+<[Cr(CN)6]3−<[Fe(H2O)6]2+ The correct answer is (A) I, II only (B) I, II, III (C) II, III only (D) I, III only
›Reveal solutionSolution
Working out the d-electron count, spin state (from field strength of the ligand) and hence unpaired-electron count for each complex confirms all three given orderings of spin-only magnetic moment are correct.
Concept and Intuition
Spin-only magnetic moment is μ=n(n+2) BM, where n = number of unpaired electrons. The number of unpaired electrons depends on the metal's oxidation state (which fixes the dn configuration) and whether the ligand is weak-field (high spin, e.g. H2O usually) or strong-field (low spin, e.g. CN−, NH3 for many metals) — strong field ligands pair electrons into t2g before populating eg.
Step-by-Step Solution
Set I:
- [Fe(CN)6]4−: Fe2+, d6, CN− strong field ⇒ low spin, t2g6eg0, 0 unpaired, μ=0.
- [Fe(CN)6]3−: Fe3+, d5, CN− strong field ⇒ low spin, t2g5, 1 unpaired, μ=3=1.73.
- [Fe(H2O)6]3+: Fe3+, d5, H2O weak field ⇒ high spin, t2g3eg2, 5 unpaired, μ=35=5.92.
- Order 0<1.73<5.92 matches I. True.
Set II:
- [Co(NH3)6]3+: Co3+, d6, NH3 strong field for Co3+ ⇒ low spin, 0 unpaired, μ=0.
- [Ni(H2O)6]2+: Ni2+, d8, always t2g6eg2 regardless of field, 2 unpaired, μ=8=2.83.
- [Cr(H2O)6]3+: Cr3+, d3, t2g3, 3 unpaired, μ=15=3.87.
- Order 0<2.83<3.87 matches II. True.
Set III:
- [V(H2O)6]3+: V3+, d2, t2g2, 2 unpaired, μ=8=2.83. …
- AP EAPCET 2025Set ap-2025-05-19-AN1 markMCQQ.Which of the following sets are not correctly matched? I) O22+,O22− - diamagnetic II) O2+,O2 - paramagnetic III) O2−,O22− - diamagnetic IV) O2+,O22− - paramagnetic (A) II & III (B) I & II (C) III & IV (D) I & III
›Reveal solutionSolution
Working out the MO electron configuration and unpaired-electron count for each oxygen species shows sets III and IV are mismatched (superoxide O2− is actually paramagnetic, and peroxide O22− is actually diamagnetic).
Concept and Intuition
For O2 and its ions, molecular orbital theory places 12 valence electrons (for neutral O2) into the sequence σ2s, σ∗2s, σ2pz, π2px=π2py, π∗2px=π∗2py. Removing or adding electrons changes how many go into the degenerate π∗ pair, which determines whether unpaired electrons (paramagnetism) exist.
Step-by-Step Solution
- O2 (12 valence e−): fills up to π∗2px1π∗2py1 — 2 unpaired electrons ⟹ paramagnetic.
- O22+ (10 e−, remove 2 from π∗): π∗ is empty ⟹ all electrons paired ⟹ diamagnetic.
- O2+ (11 e−, remove 1 from π∗): one π∗ orbital has 1 electron ⟹ 1 unpaired electron ⟹ paramagnetic.
- O2− (13 e−, add 1 to π∗): π∗2px2π∗2py1 ⟹ 1 unpaired electron ⟹ paramagnetic (not diamagnetic).
- O22− (14 e−, add 2 to π∗): π∗2px2π∗2py2 ⟹ all paired ⟹ diamagnetic.
- Now check each set:
- I) O22+ (diamagnetic ✓), O22− (diamagnetic ✓) → correctly matched.
- II) O2+ (paramagnetic ✓), O2 (paramagnetic ✓) → correctly matched. …
- AP EAPCET 2025Set ap-2025-05-19-FN1 markMCQQ.Match the following List-I (Complex) List-II (Number of unpaired electrons) A) [MnCl6]3− I) 5 B) [FeF6]3− II) 2 C) [Mn(CN)6]3− III) 0 D) [Co(C2O4)3]3− IV) 4 The correct answer is (A) A-II, B-IV, C-III, D-I (B) A-IV, B-II, C-I, D-III (C) A-III, B-I, C-IV, D-II (D) A-IV, B-I, C-II, D-III
›Reveal solutionSolution
Working out the oxidation state and d-electron count of the central metal in each complex, then applying crystal field theory (weak-field ligands give high spin, strong-field ligands give low spin) gives the unpaired-electron counts: A=4, B=5, C=2, D=0 — matching option (D).
Concept and Intuition
For octahedral transition-metal complexes, the number of unpaired electrons depends on (i) the metal's oxidation state and resulting dn configuration, and (ii) whether the ligand is weak-field (high spin, electrons spread out over t2g and eg following Hund's rule) or strong-field (low spin, electrons pair up in t2g before occupying eg). Halide ligands (Cl−, F−) are weak field; CN− is strong field; oxalate is a chelating ligand that with Co3+ specifically gives a well-known diamagnetic (low-spin) complex.
Step-by-Step Solution
- A) [MnCl6]3−: Mn is +3 here (d4 since Mn is group 7, d4 for Mn3+). Cl− is weak field ⇒ high spin: t2g3eg1 ⇒ 4 unpaired electrons ⇒ matches IV.
- B) [FeF6]3−: Fe3+ is d5. F− is weak field ⇒ high spin: t2g3eg2, all 5 electrons unpaired ⇒ matches I.
- C) [Mn(CN)6]3−: Mn3+ is d4 again, but CN− is strong field ⇒ low spin: t2g4eg0 ⇒ 2 unpaired electrons ⇒ matches II. …
- AP EAPCET 2025Set ap-2025-05-20-AN1 markMCQQ.Consider the following complex ions (only = only) I) [Fe(CN)6]3− II) [Co(CN)6]3− III) [Mn(CN)6]4− IV) [Fe(CN)6]4− Identify the complex ion/s with the least spin only magnetic moment (in BM). (A) II & IV only (B) I only (C) III only (D) I & III only
›Reveal solutionSolution
With the strong-field ligand CN−, d6 metal ions (Co3+, Fe2+) become perfectly diamagnetic (low-spin t2g6), giving the least possible spin-only moment of 0 BM.
Concept and Intuition
Whether a complex is high spin or low spin depends on the ligand field strength versus the pairing energy. CN− sits at the strong end of the spectrochemical series, so it always forces low spin in octahedral 3d complexes. Once you know the metal's dn configuration, low-spin filling (fill t2g completely before touching eg) tells you the unpaired electron count directly.
Step-by-Step Solution
- [Fe(CN)6]3−: Fe3+ is 3d5. Low spin: t2g5eg0 → 3 orbitals hold 5 electrons (2+2+1) → 1 unpaired → μ=1×3=1.73 BM.
- [Co(CN)6]3−: Co3+ is 3d6. Low spin: t2g6eg0 (all three t2g orbitals doubly filled) → 0 unpaired → μ=0 BM.
- [Mn(CN)6]4−: Mn2+ is 3d5 (same electron count as Fe3+). Low spin t2g5 → 1 unpaired → μ=1.73 BM. …
- AP EAPCET 2025Set ap-2025-05-20-FN1 markMCQQ.In 3d series, a metal 'X' has highest second ionisation enthalpy. The spin only magnetic moment (in BM) of X+ ion is (A) 1.73 (B) 0.0 (C) 2.84 (D) 5.92
›Reveal solutionSolution
The 3d-series metal with the highest second ionisation enthalpy is copper, because Cu⁺ has an extra-stable filled 3d10 configuration; this ion is diamagnetic, so its spin-only moment is 0.0 BM.
Concept and Intuition
Ionisation enthalpies show characteristic anomalies in the 3d transition series tied to especially stable electron configurations — half-filled (d5) and fully-filled (d10) subshells resist further electron removal. While Cr (which forms the stable 3d5 configuration in Cr⁺) is often the first anomaly students recall, it is actually copper whose second ionisation enthalpy is exceptionally and uniquely high across the whole row: Cu already achieves the special 3d104s0 (Cu⁺) configuration on losing just its first electron, so knocking out a second electron means breaking into this very stable, fully-filled d-subshell — requiring markedly more energy than for its neighbours.
Step-by-Step Solution
- Ground state of Cu: [Ar]3d104s1.
- First ionisation removes the 4s electron: Cu+=[Ar]3d10 — a fully-filled, extra-stable d-subshell.
- The second ionisation enthalpy of Cu (removing an electron from this stable 3d10 to give Cu²⁺, 3d9) is measurably higher than that of its 3d-series neighbours, making Cu the metal 'X' with the highest second ionisation enthalpy. …
- AP EAPCET 2025Set eng-2025-05-23-AN1 markMCQQ.Identify the complex ion with spin only magnetic moment of 4.90 BM. (A) [Co(NH3)6]3+ (B) [Cr(NH3)6]3+ (C) [Mn(CN)6]3− (D) [MnCl6]3−
›Reveal solutionSolution
This tests computing the number of unpaired electrons in transition-metal complexes based on ligand field strength (CFT) and matching to a given magnetic moment. The answer is [MnCl6]3−.
Concept and Intuition
Spin-only magnetic moment is given by μ=n(n+2) BM, where n is the number of unpaired electrons. To find n for a complex, determine the metal's oxidation state and d-electron count, then decide whether the ligand is strong-field (causes pairing → low spin) or weak-field (electrons stay unpaired → high spin) using the spectrochemical series.
Step-by-Step Solution
- Given μ=4.90 BM. Solve n(n+2)=4.90⇒n(n+2)=24.01⇒n=4 (since 4×6=24).
- (A) [Co(NH3)6]3+: Co is +3, d6. NH3 is a strong field ligand → low spin: t2g6eg0, 0 unpaired electrons. Not a match.
- (B) [Cr(NH3)6]3+: Cr is +3, d3. t2g3, always 3 unpaired electrons (no pairing possible in only 3 orbitals with 3 electrons). μ=15=3.87 BM. Not a match. …
- AP EAPCET 2025Set eng-2025-05-26-AN1 markMCQQ.Identify the ion (hydrated in solution) which is not correctly matched with its spin only magnetic moment (in BM) given in brackets (A) Cr3+ (4.90) (B) Cu2+ (1.73) (C) Co3+ (4.90) (D) Fe2+ (4.90)
›Reveal solutionSolution
Spin-only magnetic moment μ=n(n+2) BM depends on the number of unpaired d-electrons. Cr3+ (d3) always has 3 unpaired electrons giving μ≈3.87 BM, so pairing it with 4.90 BM (which needs 4 unpaired electrons) is the incorrect match.
Concept and Intuition
The spin-only formula μ=n(n+2) BM depends only on the number of unpaired electrons n in the ion's d-subshell. For a d3 configuration, all three electrons must occupy separate t2g orbitals by Hund's rule — there is no possible arrangement (high-spin or low-spin) that changes this, so d3 always gives exactly 3 unpaired electrons. Ions like d6 or d9 can vary in unpaired count depending on ligand field strength, so those need checking against the specific hydrated (weak-field, high-spin) case.
Step-by-Step Solution
- Cr3+: configuration [Ar]3d3. In any octahedral environment (weak or strong field), d3 always has 3 unpaired electrons (t2g3). μ=3(3+2)=15≈3.87 BM — not 4.90 BM as option (A) states. This is the mismatch.
- Cu2+: [Ar]3d9, always 1 unpaired electron regardless of field. μ=1(1+2)=3≈1.73 BM — matches option (B), correctly matched.
- Co3+ (hydrated): [Ar]3d6. The hydrated (aqua) Co3+ ion is a well-known high-spin exception (t2g4eg2), giving 4 unpaired electrons: μ=4(4+2)=24≈4.90 BM — matches option (C), correctly matched. …
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