Question

Ultrapure germanium, like silicon, is used in semiconductors. Germanium of "ordinary" purity is prepared by the high-temperature reduction of \(\mathrm{GeO}_{2}\) with carbon. The Ge is converted to GeCl_ by treatment with \(\mathrm{Cl}_{2}\) and then purified by distillation; GeCl_ is then hydrolyzed in water to GeO \(_{2}\) and reduced to the elemental form with \(\mathrm{H}_{2}\) . The element is then zone refined. Write a balanced chemical equation for each of the chemical transformations in the course of forming ultrapure Ge from GeO \(_{2} .\)

Short answer

The balanced chemical equations for each step in the formation of ultrapure germanium are as follows: 1. Reduction of GeO2 with carbon: \[GeO_{2}(s) + C(s) \rightarrow Ge(s) + CO_{2}(g)\] 2. Conversion of Ge to GeCl4: \[Ge(s) + 2\,Cl_{2}(g) \rightarrow GeCl_{4}(g)\] 3. Reduction of GeCl4 to elemental germanium with H2: \[GeCl_{4}(g) + 2\,H_{2}(g) \rightarrow Ge(s) + 4\,HCl(g)\]

Step-by-step solution

Reduction of GeO2 with Carbon

In this step, GeO2 reacts with carbon (C) to form germanium (Ge) and carbon dioxide (CO2). The balanced chemical equation for this reaction can be written as follows: \[GeO_{2}(s) + C(s) \rightarrow Ge(s) + CO_{2}(g)\]

Conversion of Ge to GeCl4

Germanium reacts with chlorine gas (Cl2) to form germanium tetrachloride (GeCl4). The balanced chemical equation for this reaction is: \[Ge(s) + 2\,Cl_{2}(g) \rightarrow GeCl_{4}(g)\]

Purification of GeCl4 by Distillation

In this step, germanium tetrachloride (GeCl4) undergoes purification through distillation. This step does not involve a chemical reaction, so there is no balanced chemical equation for distillation.

Reduction of GeCl4 to Elemental Germanium with H2, and Zone Refining

In this final step, germanium tetrachloride reacts with hydrogen gas (H2) to form elemental germanium and hydrochloric acid (HCl). The balanced chemical equation for this reaction is: \[GeCl_{4}(g) + 2\,H_{2}(g) \rightarrow Ge(s) + 4\,HCl(g)\] After this reaction, the germanium undergoes zone refining, which is a purification process that does not involve a chemical reaction, so there is no balanced equation for this final step.

Key concepts

Chemical Reactions

During the synthesis of ultrapure germanium, several important chemical reactions occur. These reactions are crucial for transforming raw materials into high-quality germanium used in semiconductors.

The process begins with the reduction of germanium dioxide (GeO extsubscript{2}) using carbon. In this reaction, carbon acts as a reducing agent and helps in gaining elemental germanium ( ext{Ge}). The balanced equation for this step is:

• GeO extsubscript{2}(s) + C(s) → Ge(s) + CO extsubscript{2}(g)

Following the initial reduction, elemental germanium reacts with chlorine gas to form germanium tetrachloride (GeCl extsubscript{4}). This transformation is vital for the purification stages, as the compound GeCl extsubscript{4} is easier to purify. This reaction is represented by:

• Ge(s) + 2Cl extsubscript{2}(g) → GeCl extsubscript{4}(g)

Finally, the GeCl extsubscript{4} is converted back to elemental germanium through a reaction with hydrogen gas. The resulting products are germanium and hydrochloric acid (HCl):

• GeCl extsubscript{4}(g) + 2H extsubscript{2}(g) → Ge(s) + 4HCl(g)

Semiconductors

Semiconductors like germanium play a pivotal role in modern electronics. They are materials with conductivity between conductors (like metals) and insulators.

Germanium is a classic semiconductor material due to its electrical properties and ability to control electron flow. In its ultrapure form, germanium has minimal defects that could disrupt its electronic behavior, which is crucial for devices like diodes, transistors, and photovoltaic cells.

• It can effectively switch between insulating and conducting states.
• Semiconductor properties can be tuned by adding impurities in a process known as doping, which helps in forming p-n junctions essential for semiconductor devices.

Moreover, germanium's compatibility with silicon further enhances its use in electronics, making it an integral part of semiconductors alongside silicon.

Zone Refining

Zone refining is a key process used to achieve the ultrapure germanium necessary for semiconductor applications. It leverages the principle of controlled solidification to purify materials.

In zone refining, a small region or 'zone' of a germanium rod is melted using a heated coil and slowly moved along the rod. As the molten zone travels, impurities concentrate in the liquid phase and are pushed towards one end, resulting in a purer solid form.

• Multiple passes may be needed to achieve the desired purity level.
• This method selectively removes specific impurities, increasing germanium's suitability for electronic uses.

Zone refining doesn't involve any chemical reactions but significantly enhances the material's purity, vital for high-performance semiconductor devices.

Purification Process

The purification process for germanium involves multiple stages, ensuring that the final product is suitable for precise applications in electronics.

Initially, germanium is extracted from ores and subjected to a sequence of chemical reactions, beginning with reduction and conversion. The intermediate compound, GeCl extsubscript{4}, is purified through distillation—a method that involves heating a liquid to create vapor and subsequently cooling it back into a liquid to separate components based on different boiling points.

• Distillation helps in removing volatile impurities from GeCl extsubscript{4}.
• This phase does not involve chemical transformations but is crucial for refining the germanium compound.

Finally, zone refining enhances the purification, achieving ultrapure germanium ready for use in advanced semiconductor technologies. These meticulous steps outline the importance of thorough purification in manufacturing materials that meet the stringent requirements of the semiconductor industry.