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Chapter 21: Electrochemistry

Lesson 21.1: Electrochemical Cells

- Chemical processes can either release energy or absorb energy.

- An electrochemical process is any conversion between chemical energy and electrical energy.
- All electrochemical processes involve redox reactions.

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- Any device that converts chemical energy into electrical energy or electrical energy into
chemical energy is an electrochemical cell.
- A voltaic cell is an electrochemical cell used to convert chemical energy into electrical energy.
- Electrical energy is produced in a voltaic cell by a spontaneous redox reaction within the cell.
- A voltaic cell consists of two half-cells.
- A half-cell is one part of a voltaic cell in which either oxidation or reduction occurs.
- A typical half-cell consists of a piece of metal immersed in a solution of its ions.
- The half-cells are connected by a salt bridge, which is a tube containing a strong electrolyte,
often potassium sulfate
- Salt bridges also contain agar, a gelatinous substance.
- A porous plate may be used instead of a salt bridge.
- The salt bridge or porous plate allows ions to pass from one half-cell to the other but prevents
the solutions from mixing completely.
- A wire carries the electrons in the external circuit from the zinc strip to the copper strip.
- A voltmeter or light bulb can be connected in the circuit.
- The driving force of such a voltaic cell is the spontaneous redox reaction between zinc metal and
copper ions in solution.
- The zinc and copper strips in this voltaic cell serve as the electrodes.
- An electrode is a conductor in a circuit that carries electrons to or from a substance other than a
metal.
- The electrode at which oxidation occurs is called the anode.
Electrons are produced at the anode. Therefore, the anode is labeled the negative electrode in a
voltaic cell.
- The electrode at which reduction occurs is called the cathode.
Electrons are consumed at the cathode in a voltaic cell. As a result, the cathode is labeled the
positive electrode.

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How a Voltaic Cell Works

Step 1 Electrons are produced at the zinc strip according to the oxidation.

Step 2 The electrons leave the zinc anode and pass through the external circuit to the copper
strip. (If a bulb is in the circuit, the electron flow will cause it to light. If a voltmeter is
present, it will indicate a voltage.)
Step 3 Electrons enter the copper strip and interact with copper ions in solution. There, the
following reduction half-reaction occurs:

Step 4 To complete the circuit, both positive and negative ions move through the aqueous
solutions via the salt bridge. The two half-reactions can be summed to show the overall
cell reaction. Note that the electrons must cancel.

- Current applications that use electrochemical processes to produce electrical energy include:
1. Dry cells.
2. Lead storage batteries.
3. Fuel cells.
- A dry cell is a voltaic cell in which the electrolyte is a paste.

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Lead storage batteries.

- A battery is a group of voltaic cells connected together.
- The electrolyte for both half-cells in a lead storage battery is sulfuric acid.
- Using the same electrolyte for both half-cells allows the cell to operate without a salt bridge or
porous separator. The half-reactions are as follows:

- When a lead storage battery discharges, it produces the electrical energy needed to start a car.
The overall spontaneous redox reaction that occurs is the sum of the oxidation and reduction
half-reactions.

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- The reverse reaction occurs when a lead storage battery is recharged. This reaction occurs
whenever the car's generator is working properly.

- The processes that occur during the discharge and recharge of a lead-acid battery are summarized
in Figure 21.6.
- In theory, a lead storage battery can be discharged and recharged indefinitely, but in practice its
lifespan is limited.
- Small amounts of lead(II) sulfate fall from the electrodes and collect on the bottom of the cell.
Eventually, the electrodes lose so much lead(II) sulfate that the recharging process is ineffective
or the cell is shorted out. The battery must then be replaced.
Fuel Cells

- To overcome the disadvantages associated with lead storage batteries, cells with renewable
electrodes have been developed. Such cells, called fuel cells.
- Fuel cells are voltaic cells in which a fuel substance undergoes oxidation and from which
electrical energy is continuously obtained.
- Fuel cells do not have to be recharged.
- They can be designed to emit no air pollutants and to operate more quietly and more cost-
effectively than a conventional electrical generator.
- Perhaps the simplest fuel cell involves the reaction of hydrogen gas and oxygen gas. The only
product of the reaction is liquid water.
- In the hydrogen-oxygen fuel cell shown in Figure 21.7a,
* There are three compartments separated from one another by two electrodes.
* The electrodes are usually made of carbon.
* Oxygen (the oxidizing agent) from the air flows into the cathode compartment.
* Hydrogen (the fuel) flows into the anode compartment.
* The anode and cathode are separated by a thin membrane that allows hydrogen ions to pass
through but not electrons.
* The membrane therefore acts as a salt bridge.
* Electrons from the oxidation half-reaction at the anode pass through an external circuit to
enter the reduction half-reaction at the cathode.
* The half-reactions in this type of hydrogen-oxygen fuel cell are as follows:

* The overall reaction is the oxidation of hydrogen to form water.

* Other fuels, such as methane and ammonia can be used in place of hydrogen.
* Other oxidizing agents, such as chlorine and ozone can be used in place of oxygen.

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