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Paramagnetic vs Diamagnetic

What is the difference between paramagnetic vs diamagnetic substances, and how does electron configuration (or molecular orbital filling) decide which one applies?

Subject: General Chemistry Chapter: Electrons in Atoms Topic: Electron Configuration Answer included
paramagnetic vs diamagnetic paramagnetism diamagnetism unpaired electrons electron configuration magnetic susceptibility molecular orbital theory O2 paramagnetic
Accepted answer Answer included

Paramagnetic vs diamagnetic behavior

Paramagnetic vs diamagnetic classification rests on electron spin pairing. Unpaired electrons create a net magnetic moment that couples to an external magnetic field, producing attraction into the field region. Fully paired electrons produce no permanent net magnetic moment, and the induced response is weakly opposed to the applied field, producing weak repulsion.

Paramagnetic vs diamagnetic: paramagnetic substances contain one or more unpaired electrons and are attracted into a magnetic field; diamagnetic substances have all electrons paired and are weakly repelled.

Electron pairing as the deciding criterion

Electron configuration provides the decisive test for atoms and ions: at least one singly occupied orbital implies paramagnetism, while complete pairing in all occupied orbitals implies diamagnetism. For molecules, the same logic applies to molecular orbitals: singly occupied molecular orbitals imply paramagnetism, while fully paired occupancy implies diamagnetism.

  • Unpaired electrons present → paramagnetic response (attraction).
  • All electrons paired → diamagnetic response (weak repulsion).

Quantitative link to unpaired electrons

In many introductory general chemistry contexts (especially for transition-metal ions and radicals), the magnitude of the magnetic moment correlates with the number of unpaired electrons \(n\) through the spin-only estimate \( \mu \approx \sqrt{n(n+2)}\,\mu_B \), where \(\mu_B\) is the Bohr magneton. The qualitative classification in paramagnetic vs diamagnetic comparisons depends only on whether \(n = 0\) or \(n \ge 1\).

Comparison table

Property Paramagnetic Diamagnetic
Electron occupancy At least one unpaired electron (singly occupied orbital) All electrons paired (no singly occupied orbitals)
Net magnetic moment (no external field) Nonzero at the microscopic level (from unpaired spins) Zero (paired spins cancel)
Response in an external field Attracted into higher-field regions Weakly repelled from higher-field regions
Typical chemistry examples O2, many transition-metal ions with unpaired d electrons, radicals N2, noble gases, closed-shell ions (e.g., Na+, Cl)
Magnetic susceptibility (qualitative) Positive and relatively larger Negative and small in magnitude

Visualization: molecular orbital filling and magnetic behavior

N₂ (diamagnetic) O₂ (paramagnetic) all-paired electrons two unpaired electrons energy energy σ2s σ*2s π2p σ2p π*2p diamagnetic (no unpaired electrons) σ2s σ*2s π2p σ2p π*2p σ*2p paramagnetic (2 unpaired electrons) N S N₂ weakly repelled O₂ attracted
Molecular orbital occupancy illustrates paramagnetic vs diamagnetic behavior: N2 has all occupied orbitals paired (no unpaired electrons, diamagnetic), while O2 places one electron in each degenerate π*2p orbital (two unpaired electrons, paramagnetic). The arrows indicate the qualitative direction of weak repulsion (diamagnetic) versus attraction (paramagnetic) in a magnetic field region.

Worked classifications that commonly appear in general chemistry

Closed-shell atoms and ions (filled subshells) fall on the diamagnetic side of paramagnetic vs diamagnetic comparisons. Species with partially filled subshells or singly occupied molecular orbitals fall on the paramagnetic side.

Species Electron pairing highlight Classification
He \(1s^2\), all paired Diamagnetic
N (atom) \(1s^2 2s^2 2p^3\), three unpaired in \(2p\) Paramagnetic
N2 Valence MOs fully paired Diamagnetic
O2 Two unpaired electrons in π*2p Paramagnetic
Na+ \(1s^2 2s^2 2p^6\), closed shell Diamagnetic
Fe3+ (high-spin, common ionic picture) Unpaired \(d\) electrons present Paramagnetic

Common confusions

The words “magnetic” and “attracted” often evoke ferromagnetism, which is a different phenomenon (domain alignment) and typically involves solids such as iron metal. Paramagnetic vs diamagnetic comparisons in general chemistry refer to weak, electron-based responses that depend on unpaired versus paired electrons, not on permanent magnetic domains.

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