Problem 151 - A Complete Resource Book in Chemistry for JEE Main

Question

The lanthanide contraction is responsible for the fact that \([\mathbf{2 0 0 5}]\) (a) \(\mathrm{Zr}\), Hf have about the same radius (b) \(\mathrm{Zr}, \mathrm{Y}\) have about the same radius (c) \(\mathrm{Zr}\), Nb have same oxidation state (d) \(\mathrm{Zr}, \mathrm{Zn}\) have same oxidation state

Step-by-Step Solution

Answer

The correct answer is (a) \(\mathrm{Zr}, \mathrm{Hf}\) have about the same radius.

Step 1: Understanding Lanthanide Contraction

The lanthanide contraction refers to the steady decrease in the size of the lanthanide series elements (from La to Lu) on the periodic table. This is due to poor shielding effect of the 4f orbitals, resulting in a greater effective nuclear charge being felt by electrons in the outer shells.

Step 2: Analyzing Atomic Radius Trends

As a result of lanthanide contraction, elements following the lanthanides, especially in the same groups of the periodic table, have smaller atomic radii than expected. Specifically, elements such as zirconium (Zr) and hafnium (Hf) in group 4 of the periodic table have almost the same size despite Hf having more protons, because Hf is directly preceded by the lanthanides.

Step 3: Reviewing the Options

Options (b), (c), and (d) are unrelated to lanthanide contraction. Option (b) incorrectly suggests a similarity between Zr and Y, which is more influenced by their group position on the periodic table rather than lanthanide contraction. Options (c) and (d) relate to oxidation states, which are not directly affected by the lanthanide contraction. Only option (a) relates directly to the size of the atoms being impacted by lanthanide contraction.

Step 4: Conclusion

The lanthanide contraction is responsible for the fact that (a) \(\mathrm{Zr}, \mathrm{Hf}\) have about the same radius. This option aligns with how the lanthanide contraction affects atomic sizes for elements in group 4.

Key Concepts

Effective Nuclear Charge

The effective nuclear charge is a key concept in understanding atomic structure. It represents the net positive charge experienced by an electron in an atom. This is not the same as the total charge from all protons in the nucleus because electrons between the nucleus and the electron of interest can shield some of this positive charge.

Factors affecting effective nuclear charge include:

• Shielding Effect: Inner electrons repel outer electrons, reducing the effective charge felt by the outer electrons.
• Penetration: How certain orbitals allow electrons to experience the nucleus's charge more effectively than others.

These factors lead to an increase in the effective nuclear charge across a period as electrons are added to the same shell. Understanding this helps explain why electrons in later elements of a period feel a stronger pull from the nucleus. This concept is crucial when discussing the lanthanide contraction, where the poor shielding effect of 4f electrons plays a primary role.

Lanthanide Series

The lanthanide series comprises 15 metallic elements from lanthanum (La) to lutetium (Lu) on the periodic table. These elements are known for filling their 4f orbitals with electrons. The series is particularly interesting due to the unique properties and consistencies across its span. Some important characteristics of the lanthanide series include:

• Similar Chemical Properties: All lanthanides exhibit similar chemical behavior, largely due to the fact that they usually display the +3 oxidation state.
• Contraction: As electrons fill the 4f orbitals, the size of the atoms decreases steadily, which is not the usual trend across a series in the periodic table.
• Magnetic and Optical Properties: Many of these elements are used in electronics and optics due to their magnetic and luminescent characteristics.

The lanthanide contraction refers to the gradual decrease in atomic and ionic sizes from La to Lu. This is due to poor shielding by 4f electrons, which causes a greater effective nuclear charge. This contributes to the unique size similarities seen in elements following this series, such as zirconium (Zr) and hafnium (Hf).

Atomic Radius Trends

Atomic radius trends help us understand how the size of an atom changes as you move across periods and down groups in the periodic table. Typically, the atomic radius decreases across a period and increases down a group. Some key trends to consider:

• Across a Period: Atomic radii generally decrease due to an increased effective nuclear charge, where additional protons pull the electron cloud closer to the nucleus.
• Down a Group: Atomic radii increase since new electron shells are added, making atoms larger and the effect of increased nuclear charge is somewhat offset by increased distance from the nucleus.
• Irregularities: Exceptions can occur, such as the lanthanide contraction, where added 4f electrons do not contribute to increased shielding, resulting in smaller atomic radii in later elements.

In the case of the lanthanide contraction, we see an abnormal trend where elements like Zr and Hf have similar atomic radii despite Hf having more protons. This defies the typical expectations of how atomic size should change with increased atomic number and is key to understanding some peculiarities in the periodic table.