Oxidation and Reduction Oxidation: loss of electrons. (Increase in oxidation number) Reduction: gain of electrons.

(decrease in oxidation number)

Oxidation number: value assigned to each atom in a compound as a measure of electron possession, relative to the atom. It can be used to identify oxidation and reduction in covalent bonding. Changes in oxidation numbers in a reaction indicate redox processes. The number makes it seem as if each atom has complete possession or loss over the electrons. (+) = lost electron control (-) = gain electron control. The higher the positive number, the less control the atom has over its atoms. Oxidation numbers do not have a structural basis. An oxidation number of +7 does not indicate a loss of 7 electrons. Atoms in their elemental state have an oxidation number of zero. In simple ions, the oxidation number is the same as the charge of the ion. The oxidation numbers in a neutral compound add up to zero. In polyatomic ions, the charge adds up to the charge of the ion. The oxidation number of an element is the same as the charge on is most common ion. Some elements have oxidation states that vary in different compounds.

Redox equations Half-equations: separate equations for oxidation and reduction to show electron transfer. Redox equations can be deduced from half-equations. If the half-equations are not balanced, or ions can be added.

The oxidation number of oxygen is -2. If there are three oxygen atoms, their collective charge will be -6. The charges on both sides of the equation must be balanced, so electrons must be added to the side with more positive charge The electrons are the products in the oxidation reaction. Due to this, the number of electrons on both equations must be equalized. Reactivity Oxidizing agent: reactant that accepts electrons. It is being reduced. Reducing agent: reactant that supplies electrons. It is being oxidized. Metals act as reducing agents because they tend to lose electrons. More reactive metals form stronger reducing agents. They displace the ions of weaker reducing agents from molecules. Displacement reactions occur when stronger reducing agents replace weaker metals from a molecule. The displaced reducing agent ions have become reduced. Reactivity series: the relative strength of metals as reducing agents. More reactive non-metals are stronger oxidizing agents than less reactive non-metals. They displace the ions of weaker oxidizing agents from molecules.

Voltaic cells The energy released and electron transfer during redox reactions can be utilized in voltaic cells. Half-cells (voltaic cells) allow the electrons to flow between the two half-equations only through an external circuit. The simplest half-cell is created by placing a metal in a solution of its ions. Electrode potential: the charge separation between the metal and its ions in solution. There will be an equilibrium between ions and atoms, because as the atoms lose electrons, ions in solution gain them. The position of the equilibrium determinates the sizes of the electrode potential. It is dependent on the reactivity of the metal. The less reactive the metal, the further the equilibrium will lie to the right, hence the electrode potential will be high. The more reactive the metal, the more negative the electron potential. Connecting two half-cells creates a voltaic cell. Anode: electrode where oxidation occurs. (Electrode loses electrons) Atoms from the anode release electrons, giving the electrode a negative charge. Cathode: electrode where reduction occurs. (Electrode gains electrons) Ions from the solution accept electrons from the cathode, giving the electrode a positive charge. Electrons flow from anode to cathode.

Salt bridge: a salt bridge is needed to complete the circuit. It allows the negative charge to flow from cathode to anode (the opposite direction to the electrons). Voltage generated will depend on the difference in reducing strength between the electrodes, which can be found from the reactivity series. Standard electrode potentials The electrode potential of a half-cell cannot be measured in isolation. Electrode potentials must be compared against a fixed reference point called the standard hydrogen electrode.

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The surface of the metal is covered with finely divided platinum, because it is inert and acts as a catalyst to the reaction. On the surface, the hydrogen gas reacts with the hydrogen ions, and they remain in equilibrium. The electrode potential of a standard hydrogen electrode is zero volts.

The electric potential depends on the concentration of ions, has pressure, purity of substance and temperature. Standard conditions are used in standard half-cells: Concentration of 1.0 mol dm-3 for solutions Pressure of 100 kPa for gasses. All substances must be pure. Temperature of 298 K/25 C. Platinum is used as the electrode if the cells lack a solid metal. It does not take part in the reaction.

Standard electrode potential (E): the emf generated by connecting a standard hydrogen electrode to a standard half-cell. A positive value indicates a tendency to be reduced than hydrogen ions. Cell diagrams show the composition of a voltaic cell.
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The most oxidized species is usually on the left, and the most reduced is on the right. Single vertical line: phase boundary (e.g.- between a solid electrode and an aqueous solution) Double vertical dashed line: salt bridge.

The standard electrode potential data is always for reduction reactions. The oxidation reaction will have the same electrode potential value, but with the opposite sign. The more positive the value, the more readily it is reduced. More positive electrode potential: cathode More negative electrode potential: anode Electrons flow from the more negative to the more positive. The emf of a voltaic cell can be calculated from electrode potential values of the two half-cells.

if If

is positive, the reaction is spontaneous. is negative, the reverse reaction is spontaneous. .

A metal is able to reduce ions of another metal that has a higher Lower (more negative) = strong reducing agent

A non-metal is able to oxidize ions of another non-metal that has a lower . Higher (more positive) = strong oxidizing agent

Electrolytic cells Electrolytic cells: Non-spontaneous redox reactions can be driven by an external source of electricity. Electricity is used to bring about reactions of chemical breakdown. Electrolyte: the reactant in the process. It is either a molten ionic compound or a solution of an ionic compound. Redox reactions occur at the electrodes. The value of reactive metals are low, so there are no good reducing agents to displace their ions from their compounds. The external power source induces a current from the anode to the cathode. The anode is positive, and the cathode is negative. The electrical current is transferred by ions in the electrolyte. Reduction occurs at the cathode. Positive ions are attracted to the negative electrode. Oxidation occurs at the anode. Negative ions are attracted to positive electrodes. If there are several ions in a solution, the ions with the higher will be preferentially reduced. If the ion with the lower preferentially oxidized. is higher in concentration, it will be value

The nature of the electrodes also influences selective discharge. Factors influencing the amount of product: Charge of the ion. The current. The duration of electrolysis.

Electroplating: the process of using electrolysis to deposit a layer of metal on top of another conductive substance.