a) Electrolytic Cell b) Voltaic Cell /Galvanic Cell
Electrolysis cell : Electricity energy chemical energy Voltaic cell : Chemical energy electricity energy
The Electrolytic Cell
Electrode connected to the positive terminal of the cell is positive electrode and is given a name, anode. The electrode connected to the negative terminal of the cell is negative electrode and is called the cathode. When electricity is passed through an electrolyte, chemical reaction happens. In this reaction, chemical is splitting up into 2 new substances. All electrolytes are ionic, which means they are composed of positively and negatively charged ions. On passing an electric current through the electrolyte, these ions move towards the oppositely charged electrode. Most negatively charged ions are non-metal ions, such as oxide (O 2- , chloride (Cl - ), Iodide (I - ), etc. During electrolysis, negatively charged ions move towards the positive electrode(anode). The negative ions lose their electron(s) to the anode, which is positively charged. The electron(s) is then move to the cathode through the external circuit (the wire). The positively charged ions move towards the negative electrode(cathode'). These positive ions are metal ions, such as copper (Cu 2+ ), silver (Ag + ), lead (Pb 2+ ), etc, or hydrogen (H + ). At cathode, positive ions gain electron(s) from the cathode, which has an excess of electrons and therefore an overall negative charge. This process results in the chemical decomposition of the electrolyte. It also allows electrons to travel from the cathode to the anode and hence allows conduction of electricity. During the electrolysis, electrical energy is supplied to the system to produce a chemical reaction. Therefore, during electrolysis, electrical energy convert into chemical energy. Example 1:Electrolysis of MOLTEN Lead (II) Bromide
This is composed of lead(II) ions, Pb 2 + , and bromide ions, Br - . Its chemical formula is therefore PbBr 2 . A suitable apparatus which could be used to carry out this electrolysis is shown in Figure above. The bulb helps to show when electricity is flowing in the circuit, and until the lead(II) bromide is completely molten, the bulb does not light up . This confirms that electrolytes have to be molten for the ions to start to move to the electrodes and thereby conduct electricity. At the Cathode At the Anode Observation When electricity is flowing, a silvery deposit of lead metal forms on the cathode. In fact, as it is molten, it is more likely to drip off in a molten blob. Observation When electricity is flowing, brown fumes of bromine gas are seen at the anode. Half equation Pb 2+ + 2e ---> Pb Half equation 2Br - ---> Br 2 + e Explanation The lead(II) ions, as they are positive, move to the negative cathode, where each ion gains two electrons to form a lead atom. Any reaction at a Explanation The bromide ions, as they are negative, move to the positive anode, where each loses an electron to form a bromine atom. Then two of cathode involved is again in electrons. This is called reduction or more exactly, cathodic reduction . these newly formed atoms combine to form bromine gas. Any reaction at an anode involves a loss of electrons. In summary, the lead(II) bromide is split into its component elements : PbBr 2 ---> Pb + Br 2
Electrolysis Of Molten Lead(II) Oxide (electrolysis of aqueous solutions) Introduction We have learnt that electrolyte can be molten ionic compound or aqueous solution of ionic compound, acid or alkali. An aqueous solution is solution of water of a substance. For example, if you heat sodium chloride until it melts, it is called molten sodium chloride, but if you dissolve sodium chloride in water, it is called aqueous sodium chloride. Electrolysis of aqueous solution is different from electrolysis of molten electrolyte. This is mainly because an aqueous solution contain more types of ions. Let us take the example of molten sodium chloride and sodium chloride aqueous. In molten sodium chloride, the ion present are sodium ion (Na + ) and chloride ion (Cl - ), due to the decomposition of the solid sodium chloride. NaCl ---> Na + + Cl -
In sodium chloride aqueous, other than the decomposition of sodium chloride solid to form sodium and chloride ions, some of the water molecule will also disassociates to form hydrogen (H + ) and hydroxide (OH - ) ions. NaCl ---> Na + + Cl -
H 2 O ---> H + + OH -
Which means in an aqueous solution, it can be more than 1 positive and negative ions. When the ions move to the anode and cathode, only 1 negative ion and 1 positive ion will be selected to be discharged, and this is called selective discharge. There are a few factors that determine which ion will be selected to be discharge, and this will be discussed in next section.
Factors Affecting Electrolysis There are three main factors that can affect the electrolysis products, there are: 1. position in the electrochemical series 2. the concentration and 3. the type of electrode Electrochemical series
The chart above lists the ions in order of difficulty of discharge. The ions at the top of the list is more difficult to be discharged, but as we go down the table, they become easier to be discharged. For example, Cu 2+
easier to be discharged compare with H + and OH - is easier to be discharged compare with I - . This series of ions is called the Electrochemical Series. The lower the ion in the electrochemical series, the easier the ion to be discharged during electrolysis.
Electrolysis of Aqueous Sulphuric Acid As sulphuric acid is aqueous, it is composed not only of hydrogen ions (H + ) and sulphate ions (SO 4 2- ), but also of hydroxide ions (OH - ) from the water. H 2 SO 4 + H 2 O --> 2H + + SO 4 2- + H + + OH -
The apparatus used to carry out this electrolysis and collect the gases given off is shown in Figure 9 .8 . When we have more than one type of ion moving to an electrode, selective discharge (or preferential discharge) takes place. This means that the ion which can lose or gain electrons with the greatest ease is discharged, and the other ions, which are harder to discharge, remain in solution . With the electrolyte aqueous sulphuric acid, migration of ions to the electrodes also occurs. At the Cathode At the Anode Here we have only one ion, the hydrogen, H+ (aq), and each ion gains an electron to become a hydrogen atom. Two of these newly formed atoms then combine to form a hydrogen gas molecule . Here we have a choice of either sulphate, SO 4 2-
(aq), or hydroxide OH - (aq) ions. Hydroxide is easier to discharge, so oxygen gas is given off at the anode. Equation: 2H + + 2e ---> H 2
Equation: OH - + 4e ---> O 2 + H 2 O Notes With electrolysis of aqueous solutions of dilute acids or alkalis, the volume of hydrogen given off at the cathode is roughly twice that of the oxygen gas at the anode. Accordingly, the elements of water are lost and as the electrolysis continues, the concentration of the acid or alkali increases . Essentially, the electrolysis of aqueous sulphuric acid is the electrolysis of water, with hydrogen and oxygen gas being given off in a ratio of 2 : 1 . [edit] Concentration If the concentration of a particular ion is high, it will be selected to be discharged even though it is higher in the electrochemical series compares with another ion present in the solution. For example, if dilute hydrochloric acid is electrolysed, hydrogen gas is given off at the cathode and oxygen gas at the anode. However, when concentrated hydrochloric acid is electrolysed, hydrogen gas is still given off at the cathode, but chlorine rather than oxygen gas will be released at the anode, even though chloride is in a higher position in electrochemical series. Electrolysis Of Diluted Or Concentrated Hydrochloric Acid
Electrolysis of Concentrated Sodium Chloride Solution (Brine) The electrolytic cell used for electrolysis of concentrated sodium chloride solution is designed to collect gaseous products at both electrodes as shown in Figure above. At Cathode At Anode The sodium and hydrogen ions move to the cathode . As the hydrogen ion (H + ), is lower in the reactivity series than the sodium ions (Na+ ), it Both the chloride ions (Cl - ) and the hydroxide ions (OH - ) migrate to the anode . The chloride ions (Cl - ) are preferentially discharged because accepts electrons more easily. The hydrogen ions (H + ) are discharged. of their higher concentration Equation: H + + e ---> H Hydrogen atoms join in pairs to give molecules : H + H ---> H 2
Equation: Cl - ---> Cl + e Chlorine atoms join in pairs to give molecules: Cl + Cl ---> Cl 2
Changes in Solution As the hydrogen ions and chloride ions are discharged, sodium ions and hydroxide ions remain in the solution . The solution becomes sodium hydroxide .
Type of Electrode This is best shown if we consider the electrolysis of aqueous copper(II) sulphate solution.
Electrolysis of Copper(II) Sulphate by Using Carbon Electrode Anode 1. If we use carbon electrodes, they are inert electrodes and do not affect the electrolysis . 2. Therefore, at the anode, we have a choice of sulphate or hydroxide ions . 3. The hydroxide ions are easier to discharge, so oxygen gas is given at the anode : Partial equation 40H- (aq) p O2(g) + 2H2O (l) + 4e- (oxygen gas given off) Cathode At the cathode, we have a choice of copper or hydrogen ions . The copper ions are easier to discharge, so we see a pink deposit of copper metal on the carbon electrode. Partial equation Cu2+ (aq) + 2e- p Cu (s) (copper metal deposited) Electrolysis of Copper(II) Sulphate by Using Copper Electrode However, if we use copper electrodes, these are active electrodes and do affect the electrolysis. Anode At the anode, the copper electrode dissolves into solution : Partial equation Cu(s) p Cu 2+ (aq) + 2e (copper electrode dissolves ) Cathode At the cathode, the copper ions are deposited as pink copper metal: Partial equation Cu2+ (aq) + 2e- p Cu (s) (copper metal deposited) Evaluating electrolysis in industry
[edit] Industrial Applications of Electrolysis Electrolysis has many varied industrial applications. The major applications of electrolysis in industry are 1. Extraction of Metals 2. Purification of Metal 3. Electroplating
[edit] Extraction of Metal The extraction of metals from their ores, in particular aluminium and sodium, is important industrial uses of electrolysis. The diagram below shows the methods of extraction for different metals.
We can see that those metals which are less reactive than carbon in reactivity series are extracted from their ore by displacement reaction using carbon. This will be discussed in detail in chapter 3, form 5, Oxidation and Reduction. Copper and mercury can be extracted from their ore by burning directly in air. Silver (Ag) and gold (Au) need no extraction because they exist as element in nature. Those metals which are more reactive than carbon are extracted by electrolysis.
[edit] Extraction of Aluminium Aluminium is the most abundant metal found in the earth's crust. It makes up about 8% by weight of the Earths solid surface. It is also a very useful metal due to its low density and ability to resist corrosion. The main source of aluminium is bauxite ore (Aluminium Oxide). In industry, aluminium is extracted by electrolysis from bauxite ore.
Adding Cryolite In electrolysis, molten aluminium oxide must be used to extract aluminium. Aluminium oxide decompose to form aluminium and oxide ions when melted. Al 2 O 3 ---> 2Al 3+ + 3O 2-
However, the melting point of aluminium oxide is very high (over 2 000C), so another aluminium compound called cryolite (Na3AIF6) is added to lower down the melting point (about 980 o C). The diagram above shows how aluminium is extracted from molten aluminium oxide by electrolysis. Graphite is used as the anode and cathode. During electrolysis, the aluminium ions are attracted towards the graphite cathode. The ions is discharged and become molten aluminium metal. The partial equation of this reaction is as follow: Al 3+ + 3e ---> Al At the anode, oxygen gas which also has commercial value is collected. The partial equation of this reaction is as follow: 2O 2- ---> O 2 + 4e
At the temperature of 980 C, the oxygen burns the carbon anode. Therefore the anode has to be replaced periodically. Also, this cell uses large quantities of electricity, and therefore needs cheap sources of power. [edit] Extraction of sodium chloride
In industry, sodium is extracted from molten sodium chloride. Molten sodium chloride is put into the apparatus as showing in the diagram above. When sodium chloride is melted, the sodium and chloride ions disassociate to become freely move ions, as shown in the chemical equation below. NaCl ---> Na + + Cl -
In thhis electrolytic cell, graphite was used as anode while iron is used as cathode. The negative chloride ions are attracted to the anode and then discharged to form chlorine gas. 2Cl - ---> Cl 2 + 2e Since chlorine gas is also significant in industry, it is collected and stored. In cathode, the sodium ions are discharged to form sodium atom. Na + + e ---> Na Due to high temperature, the sodium metal formed is in molten form. Metal sodium have lower density. Therefore it moves upward and been collected. [edit] Purification Of Copper
In the refining or purification of copper, the impure copper is made the anode and a thin, pure copper plate is used as a cathode. The electrolyte is usually acidified copper(II) sulphate solution. When electricity flows, the copper dissolves from the impure anode and goes into solution as copper ions. Impurities in the copper do not dissolve, and instead fall off the anode as anode sludge. At the cathode, the copper ions are deposited as pure copper metal. Reaction in anode (impure copper) In anode, the copper atoms from the electrode are ionised to form copper(II) ions. Cu ---> Cu 2+ + 2e Reaction in cathode (pure copper) Cu 2+ Cu ---> Cu + 2e [edit] Electroplating
Electroplating: Coating with a Thin Protective Layer of Metal A very common use of electrolysis is to form a thin protective coating of a metal on the surface of another which is likely to corrode. The diagram above illustrate the electroplating of a key with copper. In this process, we need to make the cathode the object for plating (the key. The anode is then made of the metal we wish to plate with (copper), and the electrolyte needs to be a solution of a salt of this metal (copper(II) sulphate). Anode In anode, the copper atoms from the electrode are ionised to form copper(II) ions. Cu ---> Cu 2+ + 2e Cathode In cathode, the copper ions are discharged to form copper atom and then deposit on the surface of the key Cu 2+ ---> Cu + 2e