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NCERT Exemplar · Q35

Q.Illustrate by taking examples of transition elements and non-transition elements that oxidation states of elements are largely based on electronic configuration.

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Oxidation states are fundamentally determined by an element's electronic configuration, specifically the number and accessibility of its valence electrons, which dictates how many electrons can be lost, gained, or shared to achieve stability. Non-transition elements typically exhibit fixed or a limited range of oxidation states to achieve noble gas configurations, while transition elements show variable oxidation states due to the involvement of both nsns and (n−1)d(n-1)d electrons in bonding.

The oxidation state of an element is a measure of the degree of oxidation of an atom in a chemical compound. It represents the hypothetical charge an atom would have if all bonds were purely ionic. This value is directly rooted in the atom's electronic configuration because the configuration dictates how many electrons are available for bonding and how readily they can be lost, gained, or shared to achieve a more stable state, typically a noble gas configuration or a stable subshell configuration.

Let's illustrate this with examples of both non-transition and transition elements.

Non-Transition Elements (s-block and p-block)

Non-transition elements generally exhibit oxidation states that allow them to achieve a stable noble gas electronic configuration. This usually involves losing or gaining a fixed number of electrons.

  1. Group 1 Elements (e.g., Sodium, Na):

    • Electronic configuration of Na is [Ne]3s1[Ne] 3s^1.
    • Sodium has one electron in its outermost shell (3s13s^1). To achieve the stable noble gas configuration of Neon ([Ne][Ne]), it readily loses this single 3s3s electron.
    • This results in a stable Na+Na^+ ion with an oxidation state of +1.
    • Na→Na++e−Na \rightarrow Na^+ + e^-
    • This configuration ([Ne][Ne]) is highly stable, making other oxidation states very rare and energetically unfavorable.
  2. Group 2 Elements (e.g., Magnesium, Mg):

    • Electronic configuration of Mg is [Ne]3s2[Ne] 3s^2.
    • Magnesium has two electrons in its outermost shell (3s23s^2). It loses both these electrons to achieve the stable noble gas configuration of Neon ([Ne][Ne]).
    • This forms a stable Mg2+Mg^{2+} ion with an oxidation state of +2.
    • Mg→Mg2++2e−Mg \rightarrow Mg^{2+} + 2e^-
    • Like Group 1, this is the predominant and most stable oxidation state.
  3. Group 17 Elements (Halogens, e.g., Chlorine, Cl):

    • Electronic configuration of Cl is [Ne]3s23p5[Ne] 3s^2 3p^5.
    • Chlorine has seven valence electrons. It can achieve a stable noble gas configuration ([Ar][Ar]) by gaining one electron.
    • This leads to the Cl−Cl^- ion with an oxidation state of -1.
    • Cl+e−→Cl−Cl + e^- \rightarrow Cl^-
    • However, chlorine can also exhibit positive oxidation states (+1, +3, +5, +7) when bonded to more electronegative elements like oxygen or fluorine. This is because it can utilize its empty 3d3d orbitals for electron promotion and bond formation. For example, in HClO4HClO_4 (perchloric acid), chlorine has an oxidation state of +7, where all its seven valence electrons (3s23p53s^2 3p^5) are involved in bonding. The availability of empty dd-orbitals in the valence shell allows for expansion of the octet.
  4. Group 16 Elements (e.g., Oxygen, O):

    • Electronic configuration of O is [He]2s22p4[He] 2s^2 2p^4.
    • Oxygen has six valence electrons. It typically gains two electrons to achieve the stable noble gas configuration of Neon ([Ne][Ne]).
    • This results in the O2−O^{2-} ion with an oxidation state of -2.
    • O+2e−→O2−O + 2e^- \rightarrow O^{2-}
    • Due to its high electronegativity, oxygen almost always exhibits a -2 oxidation state, except in peroxides (e.g., H2O2H_2O_2, -1), superoxides (e.g., KO2KO_2, -1/2), and compounds with fluorine (e.g., OF2OF_2, +2).
Important

For non-transition elements, the oxidation states are largely predictable based on their group number and the desire to achieve a stable noble gas configuration by losing or gaining electrons. Elements in the third period and beyond can also exhibit variable positive oxidation states by involving their empty dd-orbitals.

Transition Elements (d-block)

Transition elements are defined as those elements which have partially filled dd-orbitals in their elemental state or in any of their common oxidation states. A key characteristic of transition elements is their ability to exhibit multiple, variable oxidation states. This variability is directly linked to their electronic configuration, specifically the involvement of both the (n−1)d(n-1)d and nsns electrons in bonding. The energy difference between these orbitals is very small, allowing both sets of electrons to participate.

Let's consider the first transition series (3d series):

  1. Scandium (Sc):

    • Electronic configuration: [Ar]3d14s2[Ar] 3d^1 4s^2.
    • Scandium typically exhibits only one oxidation state: +3.
    • It loses all three of its valence electrons (two 4s4s electrons and one 3d3d electron) to achieve the stable noble gas configuration of Argon ([Ar][Ar]).
    • Sc→Sc3++3e−Sc \rightarrow Sc^{3+} + 3e^-
    • The resulting Sc3+Sc^{3+} ion has a stable, empty 3d3d subshell.
  2. Titanium (Ti):

    • Electronic configuration: [Ar]3d24s2[Ar] 3d^2 4s^2.
    • Titanium commonly shows oxidation states of +2, +3, and +4.
    • It first loses the two 4s4s electrons to form Ti2+Ti^{2+} ([Ar]3d2[Ar] 3d^2).
    • Then, it can lose one 3d3d electron to form Ti3+Ti^{3+} ([Ar]3d1[Ar] 3d^1).
    • Finally, it can lose both 3d3d electrons along with the 4s4s electrons to form Ti4+Ti^{4+} ([Ar][Ar]), achieving a stable noble gas configuration.
    • The +4 state is the most stable for titanium.
  3. Vanadium (V):

    • Electronic configuration: [Ar]3d34s2[Ar] 3d^3 4s^2.
    • Vanadium exhibits oxidation states from +2 to +5.
    • It loses the two 4s4s electrons to form V2+V^{2+} ([Ar]3d3[Ar] 3d^3).
    • It can then progressively lose its 3d3d electrons, leading to V3+V^{3+} ([Ar]3d2[Ar] 3d^2), V4+V^{4+} ([Ar]3d1[Ar] 3d^1), and V5+V^{5+} ([Ar][Ar]).
    • The +5 state corresponds to the loss of all nsns and (n−1)d(n-1)d electrons, resulting in a stable noble gas configuration.
  4. Manganese (Mn):

    • Electronic configuration: [Ar]3d54s2[Ar] 3d^5 4s^2. …

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