Question

What is meant by the term lanthanide contraction? What properties of the transition elements are affected by the lanthanide contraction?

Short answer

Lanthanide contraction refers to the progressive decrease in atomic radii of lanthanide series elements (atomic numbers 57-71) due to poor shielding of the 4f electrons, resulting in an increased effective nuclear charge on outer shell electrons. Properties of transition elements affected by lanthanide contraction include atomic and ionic radii, electronegativity, ionization enthalpy, and stability of oxidation states. This phenomenon leads to similar properties between elements before and after the lanthanides, such as Zirconium and Hafnium, Niobium and Tantalum, and Molybdenum and Tungsten.

Step-by-step solution

Definition of Lanthanide Contraction

Lanthanide contraction refers to the phenomenon in which the atomic radii of the elements in the lanthanide series (elements with atomic numbers 57-71) progressively decrease as the atomic number increases. This occurs due to the poor shielding of the 4f electrons, which results in an increased effective nuclear charge experienced by the electrons in the outermost shell.

Properties of Transition Elements Affected by Lanthanide Contraction

1. Atomic and ionic radii: Due to the lanthanide contraction, the atomic and ionic radii of elements in the lanthanide series decrease as you move across the series. As a result, the atomic and ionic radii of the elements after the lanthanides (such as Hafnium, Tantalum, and Tungsten) can be very similar to the radii of the elements before the lanthanides (such as Zirconium, Niobium, and Molybdenum). This similarity in size often causes the elements to have similar properties. 2. Electronegativity: The decrease in atomic radii due to the lanthanide contraction leads to an increase in electronegativity values for the lanthanide elements as you move across the series. This occurs because the electrons in the outermost shell feel a greater pull from the nucleus as the effective nuclear charge experienced by outer shell electrons increases due to poor shielding of the 4f electrons. 3. Ionization enthalpy: As the atomic size decreases with the lanthanide contraction, the ionization enthalpy increases due to the increased effective nuclear charge. This means that more energy is required to remove the outermost electron from an atom in the later lanthanides compared to the earlier ones. The same effect also causes a similar trend in ionization enthalpy for the elements after the lanthanides, such as Hafnium, Tantalum, and Tungsten. 4. Stability of oxidation states: The oxidation states of the transition elements are also influenced by the lanthanide contraction. As the effective nuclear charge experienced by the electrons increases with the lanthanide contraction, the tendency of these elements to form higher oxidation states also increases. However, towards the end of the lanthanide series, the increased effective nuclear charge and the resulting stability of the electronic configuration make it difficult to achieve higher oxidation states, leading to a general decrease in the stability of higher oxidation states.