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5th Year OL · Chemistry
Structure of Matter · Atomic models and periodicity

Quantum numbers and electron configurations

Every electron in an atom has a complete "address": which main energy level it is in, which type of sublevel, which orbital exactly, and which way it spins. That address is the set of four quantum numbers. The rules for filling these addresses explain the shape of the periodic table.

The four quantum numbers

In a magnetic field, the lines of the hydrogen emission spectrum split into very close components (the Zeeman effect). The Bohr model cannot explain this. How can we describe exactly the different states available to an electron within one main energy level?

Diagram of the sublevels and orbitals in the main energy level n = 3: the 3s, 3p and 3d sublevels with their magnetic quantum numbers. n = 3 l = 0 (3s): 1 orbital (m = 0) l = 1 (3p): 3 orbitals (m = -1, 0, +1) l = 2 (3d): 5 orbitals (m = -2, -1, 0, +1, +2)
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Consider the principal quantum level n = 3 for the electrons in the electron shell of an atom. a) State, with reasoning, all possible values of the secondary or…

Consider the principal quantum level n = 3 for the electrons in the electron shell of an atom.

  1. a) State, with reasoning, all possible values of the secondary or azimuthal (l) and magnetic ($m_l$) quantum numbers associated with this principal level, specifying the type of subshell or orbital represented by each value of l.
  2. b) Calculate the total maximum number of electrons that level n = 3 can hold by applying the Pauli exclusion principle to each of its subshells.
Solve
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Determine, giving reasons, whether each of the following combinations of four quantum numbers $(n,l,m_l,m_s)$ is physically allowed or forbidden for describing the state…

Determine, giving reasons, whether each of the following combinations of four quantum numbers $(n,l,m_l,m_s)$ is physically allowed or forbidden for describing the state of a single electron in an atom:

  1. a) (3, 2, -2, -1/2)
  2. b) (2, 2, 0, +1/2)
  3. c) (4, 1, +2, -1/2)
  4. d) (1, 0, 0, +1/2)

If a combination is not allowed, state explicitly which rule or restriction on the quantum numbers is violated.

Solve

The Pauli exclusion principle

The Pauli exclusion principle: an orbital with two electrons of opposite spin is allowed, and one with parallel spins is forbidden. allowed:opposite spins forbidden:same spin

Filling orbitals: the Aufbau principle and Hund's rule

Isolated nitrogen atoms ($Z = 7$) are attracted by a strong magnet, while neon atoms ($Z = 10$) are very slightly repelled. By what rules are orbitals filled, and why do some atoms keep unpaired electrons?

Ions and transition metals

Magnetic measurements show that $\mathrm{Fe}^{3+}$ has five unpaired electrons and $\mathrm{Fe}^{2+}$ has four. The $4s$ sublevel fills before $3d$ when building the neutral atom, so which sublevel loses electrons first when a positive ion forms?

Ionisation of a neutral iron atom to the Fe²⁺ ion, showing the two 4s electrons being lost first. Neutral Fe 4s² 3d⁶ lost first Fe²⁺: 4s² lost → [Ar] 3d⁶
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Iron is a transition element with atomic number Z = 26. a) Write the electron configuration of the neutral iron atom in its ground state and justify why, when it ionises…

Iron is a transition element with atomic number Z = 26.

  1. a) Write the electron configuration of the neutral iron atom in its ground state and justify why, when it ionises to form the cation $\mathrm{Fe}^{2+}$, it loses the 4s electrons before those of the 3d sublevel.
  2. b) Write the electron configuration of the cation $\mathrm{Fe}^{3+}$ and determine, giving reasons, which of the two species, $\mathrm{Fe}^{2+}$ or $\mathrm{Fe}^{3+}$, will have the greater number of unpaired electrons and, consequently, stronger paramagnetic behaviour.
Solve
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Chromium (Z = 24) and copper (Z = 29) show recognised anomalies with respect to the usual mnemonic rule of the Moeller diagram. a) Write the ground-state electron…

Chromium (Z = 24) and copper (Z = 29) show recognised anomalies with respect to the usual mnemonic rule of the Moeller diagram.

  1. a) Write the ground-state electron configuration predicted by the standard Moeller filling order for $\mathrm{Cr}$ and $\mathrm{Cu}$, and compare each with the experimentally verified actual configuration.
  2. b) Justify the quantum and energetic cause of these anomalous configurations, based on the stability associated with half-filled or completely filled sublevels and on the small energy difference between the 4s and 3d orbitals.
Solve
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Consider the chemical species $\mathrm{S}^{2-}$ (Z = 16), $\mathrm{K}^+$ (Z = 19) and $\mathrm{Ti}^{2+}$ (Z = 22). a) Write the complete electron configuration of each…

Consider the chemical species $\mathrm{S}^{2-}$ (Z = 16), $\mathrm{K}^+$ (Z = 19) and $\mathrm{Ti}^{2+}$ (Z = 22).

  1. a) Write the complete electron configuration of each of the three species in its ground state and state, giving reasons, which of them are isoelectronic with each other.
  2. b) Deduce the magnetic character (paramagnetic or diamagnetic) of each ion, justifying the number of unpaired electrons in each case, and propose a valid set of quantum numbers $(n,l,m_l,m_s)$ for one of the valence or outermost electrons of the species $\mathrm{Ti}^{2+}$.
Solve
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Copper (Z = 29) usually forms two stable ions: the cuprous ion $\mathrm{Cu}^+$ and the cupric ion $\mathrm{Cu}^{2+}$. a) Deduce the electron configuration of both ions…

Copper (Z = 29) usually forms two stable ions: the cuprous ion $\mathrm{Cu}^+$ and the cupric ion $\mathrm{Cu}^{2+}$.

  1. a) Deduce the electron configuration of both ions in their ground state, starting from the actual configuration of the neutral copper atom and bearing in mind the order in which electrons are lost when transition metals ionise.
  2. b) Justify in detail which of the two ions is diamagnetic and which is paramagnetic, based on the pairing of their electrons. Then state how many electrons with spin quantum number $m_s=+1/2$ the cation $\mathrm{Cu}^+$ contains in total.
Solve

Back to the start: the periodic table has blocks that are 2, 6, 10 and 14 columns wide because these match the maximum number of electrons in the $s$ ($2 \cdot 1 = 2$), $p$ ($2 \cdot 3 = 6$), $d$ ($2 \cdot 5 = 10$) and $f$ ($2 \cdot 7 = 14$) sublevels.

Summary

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