Electrolysis of Molten Ionic Compounds | Study.com (2024)

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This lesson looks into how molten ionic compounds can be electrolyzed. It also provides an understanding on how metals such as aluminum and sodium can be extracted from molten compounds using electrolysis.

Table of Contents

  • Electrolysis and Ionic Compounds
  • Electrolysis of molten Lead (II) bromide
  • Extraction of Aluminum from Molten Aluminum Oxide
  • Extraction of Sodium from Molten Sodium Chloride.
  • Lesson Summary
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Aluminum is the most abundant metal on earth. But did you ever wonder how we obtain this versatile metal? Aluminum actually doesn't occur in the natural state, and we have to resort to the process of electrolysis, or, more precisely, electrolysis of a molten ionic compound.

Usually an ionic compound, with general formula MN, is formed by strong electrostatic bonds that exist between positive and negative ions. These oppositely charged ions are locked into a rigid structure where they are not free to move. This structure does not allow the ionic solid to conduct electricity, and hence, electrolysis cannot take place.

One way in which this rigid structure can be made to conduct electricity is to heat it up to its melting point. At the melting temperature both the cations (Mx+) and anions (Ny-) acquire enough energies that allow them to move freely. This resulting liquid is now known as an electrolyte. If the electrolyte is connected to a power supply through inert electrodes, electrolysis occurs.

Electrolytic arrangement for ionic compounds
Electrolysis of Molten Ionic Compounds | Study.com (1)

The cations (Mx+) will be attracted to the negative electrode or the cathode where they will gain electron(s) to become atoms. Reduction takes place at the cathode according to the following equation:

Electrolysis of Molten Ionic Compounds | Study.com (2)

The anions (Ny-) will be attracted to the positive electrode or the anode where they will lose electron(s) to become atoms. Oxidation takes place at the anode according to this equation:

Electrolysis of Molten Ionic Compounds | Study.com (3)

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Let us now consider the electrolysis of molten lead (II) bromide using inert electrodes.

At room temperature, if we connect the white powdered lead (II) bromide through electrodes to an electrical supply, nothing appears to be happening as solid lead (II) bromide is unable to conduct electricity. However, at a temperature around 370 degrees Celsius, lead ions and bromide ions are released from the solid lead (II) bromide structure. The molten lead (II) bromide allows conduction of electricity and thereafter chemical reactions to occur. So what happens at both the anode and cathode?

At the cathode, a silvery deposit of lead is seen.

Lead ions migrate towards the cathode where each cation gains two electrons to form lead atom.

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At the anode, a brown gas is seen. This gas produced is bromine.

Bromide ions move to the anode where each ion loses an electron to form a bromine atom. Then two of the bromine atoms combine to form bromine gas.

Electrolysis of Molten Ionic Compounds | Study.com (5)

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Now let us turn to the applications of electrolysis that involve molten ionic compounds. We will next discuss the extractions of aluminum and sodium from molten alumina and molten sodium chloride respectively.

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Aluminium oxide or alumina, Al 2 O3, is obtained from bauxite, an ore, which also contains impurities such as iron (III) oxide, Fe2 O3, and silicon dioxide, SiO2. The purification is carried out by a process known as the Bayer process.

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The purified alumina is then electrolyzed in molten cryolite, Na3 AlF6 , by a process commonly known as the Hall-Heroult process. Cryolite not only lowers the melting point of alumina from around 2000 degrees Celsius to about 980 degrees Celsius but also increases its conductivity. The electrolysis is carried out in an electric furnace, using carbon electrodes.

Extraction of Aluminium
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Molten alumina contains Al3+ and O2- ions.

At the cathode, which includes the bottom and sides of the electrolysis cell, aluminum ions are reduced to aluminum metal.

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At the anode, the oxide ions are oxidized to oxygen gas.

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At that operating temperature, oxygen produced reacts with the carbon anodes to produce both carbon dioxide. You will also find that the anodes burn away and there is need to continuously replace them.

The overall equation for the extraction of Aluminum is summarized by the chemical equation:

Electrolysis of Molten Ionic Compounds | Study.com (11)

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Both sodium and chlorine are very reactive and are not found in nature. They are obtainable if you pass an electric current through molten sodium chloride. The challenge was to produce chlorine and sodium apart so that they do not react with each other. This was first accomplished in the 1920s by a chemical engineer named J.Cloyd Downs through a cell which he developed and named as the Downs cell.

Downs Cell
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In a Downs cell, the carbon anode is surrounded by a circular iron cathode. The products are separately formed so that sodium and chlorine do not come together.

The ions present in molten or fused sodium chloride are Na+ (liquid) and Cl- (liquid).

At the graphite anode, chloride ions are oxidized to chlorine gas. Since the gas is less dense than the molten sodium chloride, it rises and is collected at the surface.

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At the iron cathode, sodium ions are reduced to sodium atom. Since sodium metal is less dense than the molten sodium chloride, it also rises and is collected at the surface.

Electrolysis of Molten Ionic Compounds | Study.com (14)

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Electrolysis is a process that will cause any molten ion to decompose into its element. In the electrolysis of molten lead (II) bromide, lead ions are reduced to lead atoms while bromide ions are oxidized to bromine gas.

The process is useful in many industrial processes. Two such examples are:

1. The industrial extraction of aluminum from alumina by the Hall-Heroult process, in which molten aluminum oxide is electrolyzed with graphite electrodes. The cathode produces aluminum while the anode produces oxygen.

2. The industrial extraction of sodium from molten (fused) sodium chloride by the Downs cell, in which the cathode produces sodium while chlorine is formed at the anode. Both the chlorine and the sodium are separately collected.

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FAQs

What does electrolysis do to molten ionic compounds? ›

Electrolysis is a process that will cause any molten ion to decompose into its element. In the electrolysis of molten lead (II) bromide, lead ions are reduced to lead atoms while bromide ions are oxidized to bromine gas. The process is useful in many industrial processes.

Does electrolysis only work ionic compounds? ›

For electrolysis to work, the compound. must contain ions. Covalent. compounds cannot act as electrolytes because they contain neutral atoms.

What happens to ionic compounds when molten? ›

Ionic bonding is the sum of interionic attractions in an ionic compound. These attractions remain in a molten salt, but the solid lattice is no longer able to maintain itself because the individual ions are moving too fast. The ions are still attracted to each other, but they have enough energy to move freely.

When molten ionic compound is electrolyzed a metal is formed? ›

Answer. During the electrolysis of a molten ionic compound, a metal forms at the cathode and a non-metal forms at the anode.

What happens to the ions during electrolysis? ›

Any negative ions will move towards the anode (since it is the positive electrode). Ions are reduced or oxidised. The positive ions will be reduced at the cathode, as they gain electrons. The negative ions will be oxidised at the anode, as they lose electrons.

When a molten ionic compound is electrolysed what happens at the positive electrode? ›

This is summarised below: Anode: the positive electrode attracts negatively charged ions (anions), which will lose electrons to become oxidised. Cathode: the negative electrode attracts positively charged ions (cations) which will gain electrons and become reduced.

What are the products of molten electrolysis? ›

Electrolysis of molten salts
ObservationExplanation
Anode (positive)Bubbles of brown gasBromine vapour (Br2) is produced
Cathode (negative)Silvery liquid metal present at this electrode underneath the remaining molten electrolyteLead (Pb) is produced

What happens when an ionic compound is melted? ›

Cations move to one electrode, while anions move to the other, allowing electricity to flow (see figure below). Melting an ionic compound also frees the ions to conduct a current. Ionic compounds conduct an electric current when melted or dissolved in water.

What are the properties of a molten ionic compound? ›

Ionic compounds have several unique properties, including high melting and boiling points, electrical conductivity in a molten or dissolved state, and poor electrical conductivity in the solid state. They are also typically brittle and have a crystal-like structure.

What happens when a simple ionic compound is electrolysed? ›

Electrolysing ionic solutions

Molten ionic compounds contain only the metal ions and non-metal ions. The products of electrolysis therefore are easy to predict. The metal ions will produce a liquid metal and the non-metal ions will produce a gas.

What happens when a molten ionic hydride is electrolysed? ›

In liquid state or molten states, ionic hydrides are electrolyzed and conduct electricity by liberating hydrogen gas at the anode. Hence, when ionic hydrides of s-block elements in molten states are electrolyzed, hydrogen is liberated at the anode.

What is a metal manufactured by the electrolysis of a molten ionic compound? ›

h) Aluminium is manufactured by the electrolysis of a molten mixture of aluminium oxide and cryolite. Aluminium forms at the negative electrode and oxygen at the positive electrode. The positive electrode is made of carbon, which reacts with the oxygen to produce carbon dioxide.

What happens when a molten ionic hydride is electrolyzed? ›

In liquid state or molten states, ionic hydrides are electrolyzed and conduct electricity by liberating hydrogen gas at the anode. Hence, when ionic hydrides of s-block elements in molten states are electrolyzed, hydrogen is liberated at the anode.

What happens when a molten salt is electrolysed? ›

Here, they lose electrons to form chlorine atoms. The atoms join up in pairs to form Cl2 molecules, so chlorine gas is formed at the positive electrode. During the electrolysis of molten salts, a metal forms at the cathode and a non-metal forms at the anode.

What happens in electrolysis of molten NaCl? ›

Molten (liquid) sodium chloride can be electrolyzed to produce sodium metal and chlorine gas. The electrolytic cell used in the process is called a Down's cell (see figure below).

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