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CIE A-Level Chemistry Study Notes

9.2.2 Oxidation States of Oxides and Chlorides in Period 3 Elements

Understanding the oxidation states of oxides and chlorides in Period 3 elements is crucial for A-level Chemistry students. This detailed analysis will explore how these oxidation states are linked to the electronic configurations and valence electrons of each element, providing a fundamental understanding of their chemical properties and behaviours.

Introduction to Electronic Configuration and Valence Electrons

Period 3 elements, which span from Sodium (Na) to Argon (Ar), have distinct electronic configurations that profoundly impact their chemical properties, especially in the formation of oxides and chlorides.

  • Sodium (Na): (Ne) 3s¹. It has one valence electron, which it readily loses, affecting its oxidation state and reactivity.
  • Magnesium (Mg): (Ne) 3s². With two valence electrons, it typically exhibits a +2 oxidation state in its compounds.
  • Aluminium (Al): (Ne) 3s²3p¹. The three valence electrons of aluminium influence its +3 oxidation state in compounds.
  • Silicon (Si): (Ne) 3s²3p². Silicon's four valence electrons lead to variable oxidation states, commonly +4.
  • Phosphorus (P): (Ne) 3s²3p³. Phosphorus can exhibit +3 and +5 oxidation states due to its five valence electrons.
  • Sulfur (S): (Ne) 3s²3p⁴. Six valence electrons allow sulfur to have multiple oxidation states, often +4 or +6.
  • Chlorine (Cl): (Ne) 3s²3p⁵. Chlorine, with seven valence electrons, shows a range of oxidation states, commonly -1, +1, +3, +5, and +7.
  • Argon (Ar): (Ne) 3s²3p⁶. Being inert, Argon does not readily form compounds and hence does not have a common oxidation state.
Electronic configuration of Period 3 elements

Image courtesy of Pearson Education

Oxidation States in Oxides

The oxidation state in oxides reflects how the elements combine with oxygen, often losing electrons in the process.

Sodium Oxide (Na₂O)

  • Sodium in Na₂O is always in the +1 oxidation state, consistent with its tendency to lose one electron.

Magnesium Oxide (MgO)

  • Magnesium's consistent +2 oxidation state in MgO is due to the loss of its two valence electrons.

Aluminium Oxide (Al₂O₃)

  • Aluminium in Al₂O₃ has a +3 oxidation state, correlating with its three valence electrons.

Silicon Dioxide (SiO₂)

  • Silicon typically shows a +4 oxidation state in SiO₂, aligning with its four valence electrons.

Phosphorus Oxides (P₄O₆ and P₄O₁₀)

  • Phosphorus exhibits +3 oxidation state in P₄O₆ and +5 in P₄O₁₀, demonstrating its ability to exhibit multiple oxidation states.

Sulfur Oxides (SO₂ and SO₃)

  • Sulfur commonly has a +4 oxidation state in SO₂ and +6 in SO₃, indicating its variable oxidation capabilities.

Chlorine Oxides (ClO, ClO₂, Cl₂O₇)

  • Chlorine shows a range of oxidation states in its oxides: +1 in ClO, +4 in ClO₂, and +7 in Cl₂O₇.

Oxidation States in Chlorides

Chlorides of Period 3 elements also exhibit varied oxidation states, influenced by the electron donating or accepting tendencies of the elements.

Sodium Chloride (NaCl)

  • Sodium manifests a +1 oxidation state in NaCl, in line with its single valence electron.

Magnesium Chloride (MgCl₂)

  • In MgCl₂, magnesium exhibits a +2 oxidation state, reflecting its two valence electrons.

Aluminium Chloride (AlCl₃)

  • Aluminium in AlCl₃ has a +3 oxidation state, correlating with its three valence electrons.

Silicon Tetrachloride (SiCl₄)

  • Silicon displays a +4 oxidation state in SiCl₄, consistent with its four valence electrons.

Phosphorus Chlorides (PCl₃ and PCl₅)

  • Phosphorus shows +3 oxidation state in PCl₃ and +5 in PCl₅, illustrating its variable oxidation state potential.

Sulfur Dichloride (SCl₂)

  • Sulfur in SCl₂ often has a +2 oxidation state, though it can vary in other sulfur chlorides.

Chlorine Chlorides (Cl₂)

  • In Cl₂, chlorine exhibits a range of oxidation states, though it is typically -1 in simple chlorides.
Oxidation States in Oxides and Oxidation States in Chlorides

Image courtesy of PBworks

A clear trend emerges as one moves across Period 3 from left to right:

  • Increasing Oxidation State: There is a noticeable increase in the oxidation state, attributable to the increasing number of valence electrons.
  • Stability and Variation in Oxidation States: Elements like Na and Mg have stable oxidation states, whereas elements like S and Cl exhibit varied oxidation states.
  • Direct Link to Electronic Configuration: The oxidation states correlate with the electronic configurations, as elements aim for stable electronic arrangements.

Implications of Oxidation States on Chemical Properties

These oxidation states play a pivotal role in determining the chemical properties and behaviors of elements:

  • Reactivity: Higher oxidation states often correlate with increased reactivity.
  • Compound Formation: The oxidation state influences the nature and complexity of compounds formed.
  • Bonding and Structural Implications: Oxidation states impact the types of chemical bonds formed, affecting the molecular structure and properties of compounds.

Conclusion

In summary, the study of oxidation states in oxides and chlorides of Period 3 elements offers key insights into their chemical properties. This understanding is fundamental for students to grasp the nuances of chemical periodicity and the behavior of elements across the periodic table.

FAQ

The oxidation states of Period 3 elements can provide insights into the solubility of their oxides and chlorides in water, although solubility is also influenced by other factors like lattice energy and hydration energy. Generally, compounds with lower oxidation states, like sodium oxide (Na₂O) and magnesium oxide (MgO), are highly soluble in water. This is because these basic oxides, formed by elements in lower oxidation states (+1 and +2 respectively), readily react with water to form hydroxides. As we move across the period to elements with higher oxidation states, the solubility patterns change. Aluminium oxide (Al₂O₃) is amphoteric and less soluble, while silicon dioxide (SiO₂) is virtually insoluble due to its macromolecular structure. The acidic oxides of phosphorus, sulfur, and chlorine (e.g., P₄O₁₀, SO₂, Cl₂O) are generally soluble, as they react with water to form acidic solutions. For chlorides, those of elements with lower oxidation states (like NaCl and MgCl₂) are highly soluble due to their ionic nature, which allows them to dissociate easily in water. However, the solubility decreases for chlorides with covalent character, such as SiCl₄, which is hydrolysed by water. Therefore, while oxidation states offer a guide, solubility in water is a complex trait that depends on multiple factors.

Oxidation states play a significant role in determining the bonding and structure of Period 3 chlorides. Starting with sodium chloride (NaCl), where sodium has a +1 oxidation state, the compound forms an ionic bond due to the complete transfer of an electron from sodium to chlorine. As we move to magnesium chloride (MgCl₂) with magnesium in a +2 oxidation state, the ionic character strengthens due to the increased charge difference between magnesium and chlorine ions. In aluminium chloride (AlCl₃), with aluminium in a +3 oxidation state, the compound exhibits ionic bonding at lower temperatures but shows covalent character at higher temperatures due to the smaller size and higher charge of the aluminium ion. Silicon tetrachloride (SiCl₄), where silicon has a +4 oxidation state, forms covalent bonds, as silicon shares electrons with chlorine atoms. Phosphorus and sulfur chlorides, like PCl₅ and S₂Cl₂, where these elements have higher oxidation states, also exhibit covalent bonding. The higher the oxidation state, the more electronegative the central atom becomes, influencing the type of bonding and consequently the molecular structure. Thus, the oxidation state directly impacts the nature of bonding (ionic or covalent) and the resultant structural attributes of these chlorides.

The concept of oxidation states in Period 3 elements is crucial in understanding their reactivity with water. Elements with lower oxidation states, like sodium and magnesium, react vigorously with water. Sodium, with a +1 oxidation state, reacts to form sodium hydroxide (NaOH) and hydrogen gas, indicating its high reactivity due to the ease of losing its single valence electron. Magnesium, in a +2 oxidation state, also reacts with water, albeit more slowly, to form magnesium hydroxide (Mg(OH)₂) and hydrogen. However, as we move across the period and the oxidation states increase, the reactivity with water decreases. Aluminium, with a +3 oxidation state, forms a protective oxide layer, making it less reactive with water under normal conditions. Silicon, phosphorus, sulfur, and chlorine, with even higher oxidation states, do not react with water in the same way. Silicon dioxide (SiO₂) is essentially unreactive with water, while phosphorus, sulfur, and chlorine oxides react differently, often forming acidic solutions. Understanding the oxidation states provides insights into the energy required to remove electrons from an element, which is a key factor in determining its reactivity with water.

Elements in Period 3 form different types of oxides due to variations in their electronic configurations and the resulting differences in their abilities to lose or share electrons. Starting with sodium, which forms a basic oxide (Na₂O), the nature of the oxides changes across the period. Magnesium oxide (MgO) is also basic, while aluminium oxide (Al₂O₃) is amphoteric, displaying both acidic and basic properties. Silicon dioxide (SiO₂) is a giant covalent structure and is acidic. Moving further, the oxides of phosphorus, sulfur, and chlorine (such as P₄O₁₀, SO₂, and ClO₂) are increasingly acidic. This transition from basic to acidic oxides is a direct result of the increasing oxidation states of the elements. Basic oxides are formed by elements with lower oxidation states (like +1 in Na₂O and +2 in MgO), where the element donates electrons to oxygen. In contrast, the acidic oxides are formed by elements with higher oxidation states (like +5 in P₄O₁₀), where the element has a stronger pull on the shared electrons in its bonds with oxygen. This trend illustrates how oxidation states influence the acid-base nature of oxides, reflecting the underlying electronic structure of the elements.

The trend in electronegativity across Period 3 significantly affects the oxidation states of its elements in their compounds. Electronegativity increases from left to right across the period, meaning that elements towards the right have a stronger tendency to attract electrons. Sodium and magnesium, being less electronegative, easily lose their valence electrons, resulting in lower oxidation states (+1 for Na and +2 for Mg). As we move towards elements like aluminium and silicon, the increasing electronegativity reflects in their higher oxidation states (+3 and +4 respectively), as these elements still lose electrons but with less ease compared to their predecessors. Phosphorus, sulfur, and chlorine, with even higher electronegativities, exhibit even higher oxidation states in their compounds. These elements are more capable of attracting and sharing electrons, leading to the formation of compounds with oxidation states of +5, +4, +6 (for sulfur), and varying states for chlorine, including +1, +3, +5, and +7. The increasing electronegativity thus correlates with the ability of an element to maintain a higher oxidation state by either sharing more electrons (in covalent bonding) or by having a stronger pull on the electrons in ionic compounds.

Practice Questions

Explain why the oxidation states of the elements increase from sodium to chlorine in the oxides of Period 3. Use the concepts of electronic configuration and valence electrons in your explanation.

The oxidation states of Period 3 elements in their oxides increase from sodium to chlorine due to the progressive increase in the number of valence electrons. Starting with sodium ((Ne) 3s¹), which has one valence electron and exhibits a +1 oxidation state in Na₂O, each subsequent element has an additional valence electron. Magnesium ((Ne) 3s²) has two valence electrons, forming MgO with a +2 oxidation state. This trend continues, with Aluminium ((Ne) 3s²3p¹) in Al₂O₃ having a +3 oxidation state, Silicon ((Ne) 3s²3p²) in SiO₂ a +4, and so on, up to Chlorine ((Ne) 3s²3p⁵) in ClO₂ with a +4 oxidation state. The increase in valence electrons allows for more electrons to be lost (or shared in covalent bonding), resulting in higher oxidation states.

Describe how the oxidation states of sulfur in its oxides and chlorides reflect its ability to expand its valence shell. Give examples of sulfur compounds to support your explanation.

Sulfur's ability to expand its valence shell is evident in the variable oxidation states observed in its oxides and chlorides. In sulfur dioxide (SO₂), sulfur exhibits a +4 oxidation state, whereas in sulfur trioxide (SO₃), it has a +6 oxidation state. This variation is possible due to sulfur's capacity to utilise d-orbitals, thereby expanding its valence shell beyond the octet rule. Similarly, in sulfur dichloride (SCl₂), sulfur exhibits a +2 oxidation state, but in sulfur hexachloride (SCl₆), a hypothetical compound, it would have a +6 oxidation state. These examples show sulfur's flexibility in forming compounds with different oxidation states, underlining its ability to expand its valence shell.

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