The d- and f-Block Elements • Topic 1 of 3

Transition Elements: Trends

The d-block elements occupy Groups 3 to 12 of the periodic table, sitting between the s-block and the p-block. They are called transition elements because they mark a transition between the most electropositive s-block metals and the more electronegative p-block elements. By the strict IUPAC definition, a transition element has an incompletely filled d subshell either in its elemental state or in one of its common oxidation states. There are three complete series: the 3d series (Sc–Zn), the 4d series (Y–Cd) and the 5d series (La, Hf–Hg).

The general outer electronic configuration is $(n-1)d^{1-10}\,ns^{1-2}$. Two configurations break the simple pattern because half-filled and fully-filled d subshells carry extra stability: chromium is $3d^5\,4s^1$ (not $3d^4\,4s^2$) and copper is $3d^{10}\,4s^1$ (not $3d^9\,4s^2$).

General characteristics

Transition metals are hard, lustrous, high-melting solids that conduct heat and electricity well. They are less reactive than s-block metals, form alloys readily, and act as catalysts. These properties stem from the involvement of $(n-1)d$ electrons in bonding alongside the $ns$ electrons.

Atomic and ionic radii

Across a series the radius first decreases (increasing nuclear charge pulls electrons in), then stays nearly constant in the middle (the added d electron screens the nucleus, balancing the rise in charge), and rises slightly at the end (electron–electron repulsion in the filling d subshell). The 4d and 5d elements of a group have almost identical radii because of the lanthanoid contraction.

Ionisation enthalpies

Ionisation enthalpies increase gradually across a series, but far less steeply than in the s- or p-block, because the added electron enters the inner $(n-1)d$ shell and the increase in nuclear charge is partly offset by screening. Irregularities (e.g. the high $\text{IE}_3$ of Mn and Zn) reflect the stability of $d^5$ and $d^{10}$ configurations.

Oxidation states

The hallmark of transition metals is variable oxidation states, because the $(n-1)d$ and $ns$ electrons have similar energies and can both be lost. Manganese shows the widest range (+2 to +7). The highest states appear in oxides and fluorides (e.g. $\text{Mn}_2\text{O}_7$, $\text{KMnO}_4$).

Metallic character and melting points

All transition elements are metals. Melting points rise to a maximum near the middle of each series (greatest number of unpaired d electrons available for metallic bonding) and fall towards the ends. Manganese and technetium dip because of their stable half-filled configurations.

Why Zn, Cd and Hg are not typical

Zinc, cadmium and mercury have a fully filled $d^{10}$ configuration in both the atom and their common +2 ion. With no partially filled d subshell, they are not coloured, are weakly bonded (low melting points; Hg is liquid), are poor catalysts and form few complexes — so they are not regarded as typical transition elements.

Melting point trend across the 3d transition seriesMelting point (relative)3d series (Sc to Zn)ScTiVCrMnFeCoNiCuZnpeak near CrZn very low
1
Worked Example
Write the ground-state electronic configurations of chromium (Z = 24) and copper (Z = 29) and explain the anomaly.
Solution
  1. Expected: Cr $= [\text{Ar}]3d^4\,4s^2$, Cu $= [\text{Ar}]3d^9\,4s^2$.
  2. Half-filled ($d^5$) and fully-filled ($d^{10}$) subshells are extra stable due to symmetry and exchange energy.
  3. One $4s$ electron shifts into $3d$ to reach these stable arrangements.

Answer: Cr $= [\text{Ar}]3d^5\,4s^1$ and Cu $= [\text{Ar}]3d^{10}\,4s^1$.

2
Worked Example
Why does atomic radius stay nearly constant across the middle of the 3d series?
Solution
  1. Across a period nuclear charge increases, which tends to shrink the atom.
  2. Each added electron enters the $(n-1)d$ shell, which screens the nucleus from the outer $ns$ electrons.
  3. In the middle of the series these two effects nearly cancel.

Answer: Increasing nuclear charge is offset by the screening of the added d electrons, so the radius is almost constant in the middle.

3
Worked Example
Identify the element of the 3d series that shows the maximum number of oxidation states and list them.
Solution
  1. Maximum oxidation states occur when the number of $(3d + 4s)$ electrons available is largest while still allowing a half-filled core.
  2. Manganese has configuration $[\text{Ar}]3d^5\,4s^2$ (seven valence electrons).
  3. All seven can take part, giving states +2 through +7.

Answer: Manganese, with oxidation states +2, +3, +4, +5, +6 and +7.

4
Worked Example
Arrange Sc, Cr and Zn in order of increasing number of unpaired d electrons in the neutral atom.
Solution
  1. Sc $= 3d^1$ → 1 unpaired electron.
  2. Zn $= 3d^{10}$ → 0 unpaired electrons.
  3. Cr $= 3d^5\,4s^1$ → 6 unpaired electrons (5 in 3d + 1 in 4s).

Answer: Zn (0) < Sc (1) < Cr (6).

5
Worked Example
Explain why the first ionisation enthalpy of Zn is higher than that of Cu.
Solution
  1. Cu $= [\text{Ar}]3d^{10}\,4s^1$; the single $4s$ electron is removed relatively easily.
  2. Zn $= [\text{Ar}]3d^{10}\,4s^2$; removing an electron disturbs the stable filled $4s^2$ over a fully filled $3d^{10}$ core.
  3. The higher nuclear charge of Zn also binds the $4s$ electrons more tightly.

Answer: Zn has a higher first ionisation enthalpy because its electron is removed from a stable $4s^2$ pair under a greater nuclear charge.

6
Worked Example
Give two reasons why mercury is a liquid at room temperature whereas tungsten has one of the highest melting points of all metals.
Solution
  1. Metallic bond strength depends on the number of unpaired d electrons available for bonding.
  2. Hg $= [\text{Xe}]4f^{14}5d^{10}6s^2$ has no unpaired d electrons; its weak metallic bonding gives an extremely low melting point.
  3. W has many unpaired d electrons (mid-series, $5d^4\,6s^2$), giving very strong metallic bonding and a high melting point.

Answer: Hg has a filled $d^{10}$ shell (no unpaired d electrons → weak bonding), while W lies mid-series with many unpaired d electrons → very strong bonding.

Key Points

  • d-block elements (Groups 3–12) have outer configuration $(n-1)d^{1-10}\,ns^{1-2}$; Cr is $3d^5\,4s^1$ and Cu is $3d^{10}\,4s^1$.
  • A transition element has a partially filled d subshell in the atom or a common ion; Zn, Cd, Hg ($d^{10}$) are not typical.
  • Atomic radii decrease then level off then rise slightly; 4d and 5d radii are nearly equal due to lanthanoid contraction.
  • Ionisation enthalpies rise gradually; variable oxidation states arise from the close energies of $(n-1)d$ and $ns$ electrons (Mn: +2 to +7).
  • Melting points peak mid-series (most unpaired d electrons) and are low at the ends; Mn dips due to its stable $d^5$ configuration.
Tap an option to check your answer0 / 4
Q1.The correct ground-state configuration of Cu (Z = 29) is:
Explanation: A $4s$ electron shifts to $3d$ to give the extra-stable fully filled $3d^{10}$ subshell.
Q2.Across the 3d series the atomic radius in the middle is almost constant because:
Explanation: The screening by added d electrons balances the increase in nuclear charge, so the size barely changes.
Q3.Which element shows the maximum number of oxidation states?
Explanation: Manganese ($3d^5\,4s^2$) shows +2 to +7, the widest range in the 3d series.
Q4.Why is Hg a liquid at room temperature?
Explanation: With a fully filled $d^{10}$ subshell, Hg has no unpaired d electrons, so its metallic bonding is very weak.