Electrochemistr y

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Electrical devices and circuit symbols

Cell: a source of electricity Battery: a collection of cells Switch: used to stop the flow of current Voltmeter: used to measure voltage Ammeter: used to measure current Resistor: ensures that a suitable amount of current is flowing Variable resistor: a resistor whose rating can be changed Electrodes: plates which carry electricity into the liquid Cathode: electrode connected to the negative terminal of the battery Anode: electrode connected to the positive terminal of the battery Cation: positively charged ion that travels to the cathode Anion: negatively charged ion that travels to the anode

Electrical devices and circuit symbols

Electrodes
Usually made of materials such as graphite, platinum, copper and sometimes mercury

Conductors and nonconductors

A conductor is a substance which conducts electricity but is not chemically changed during the conduction
o Conduction of electricity through the metal is possible because of the freely moving valence electrons within the metals structure

A non-conductor is a substance which does not allow the passage of electricity

o Sometimes they are used to protect something from electricity insulators o Solid substances which act as non-conductors have their valence electrons in fixed positions so they are not free to move o All non-metals except graphite are non-conductors

Electrolytes, weak-electrolyte and non-electrolyte

Electrolytes: compounds which when molten or dissolved in water conduct electricity
o All acids, alkalis and salts are electrolytes o They conduct electricity by the movement of ions between electrodes o Solid ionic substances do not conduct electricity as their ions are held together in fixed positions by strong forces

Weak electrolytes
o Weak acids (vinegar) and weak alkalis (ammonia solution) o Conduct only few ions

Non-electrolytes: a liquid which does not allow the passage of electricity

o Distilled water, alcohol, turpentine, oil, paraffin and other organic solvents o These are covalent substances which do not contain ions

Electrolytes, weak-electrolyte and non-electrolyte

Non-electrolytes Organic liquids or solutions Ethanol, C2H5OH (l) Tetrachloromethane, CCl4 (l) Weak electrolytes Weak acids and alkalis Strong electrolytes Strong acids, alkalis and salt solutions Limewater, Ca(OH)2 (aq) Aqueous sulphuric acid, H2SO4 (aq) Ammonia solution, NH3 (aq) Aqueous nitric acid, HNO3 (aq)

Trichloromethane, CHCl3 (l)

Pure water, H20 (l) Sugar solution, C12H22O11 (aq) Molten sulphur, S (l)

Aqueous ethanoic acid CH3COOH (aq)

Aqueous sulphurous acid, H2SO3 (aq) Aqueous carbonic acid, H2CO3 (aq)

Aqueous hydrochloric acid, HCl (aq)

Aqueous potassium hydroxide, KOH (aq) Aqueous sodium hydroxide, NaOH (aq) Copper(II) sulphate solution, CuSO4 (aq)

Distinguishing electrolytes
The brightness of the circuit bulb indicates the degree of ionisation Accordingly, with a strong electrolyte, the bulb shines brightly With weak electrolytes it is dim With non-electrolytes it does not light up at all

Electrolysis: decomposing using passage of electricity

When electricity is passed through an electrolyte, chemical decomposition occurs This involves splitting up of the electrolyte 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 migrate towards the oppositely charged electrode Negatively charged ions move towards the positive anode and are therefore called anions Positively charged ions move towards the negative cathode and are called cations

Electrolysis
Most anions are non-metal ions, such as oxide (O2-), chloride (Cl-), bromide (Br-) Cations are metal ions, such as copper (Cu2+), silver (Ag+), lead (Pb2+), hydrogen (H+)

Electrolysis
At the anode
o negative ions lose their electron(s) to the anode, which is very ready to accept electrons because it is positively charge - This means it has a lack of electrons

At the cathode
o positive ions gain electron(s) from the cathode, which has an excess of electrons and therefore an overall negative charge this release of ions at the electrode results in the chemical decomposition of the electrolyte o It also allows electrons to travel from the cathode to the anode

Therefore movement of ions during electrolysis allows conduction of electricity

Electrolysis of Lead (II) Bromide (molten only)

This is made up of lead(II) ions, Pb2+ and bromide ions Br Chemical formula: PbBr2
At the anode When electricity is flowing, brown fumes of bromine gas are seen as the anode Br- -> Br + e Br + Br -> Br2 (g) At the cathode When electricity is flowing, a silvery deposit of lead metal forms on the cathode Pb2+ + 2e- -> Pb (l) (molten lead deposited) The lead(II) ions are positive so they move to the negative cathode, where each ion gains 2 electrons to from a lead atom Any reaction at a cathode involved is a gain in electrons (reduction) PbBr2 (l) -> Pb (l) + Br2 (g)

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 The cathode can be platinum or carbon but the anode must be carbon to resist attack by chlorine Ions present
o From sodium chloride: Na+, Clo From water: H+, OH-

Electrolysis of concentrated sodium chloride solution (brine)

At the cathode
o The sodium and hydrogen ions move to the cathode o As the hydrogen ion is lower in the reactivity series than the sodium ions, it accepts electrons more easily o The hydrogen ions are discharged H+ (aq) + e- -> H o Hydrogen atoms join in pairs to give molecules H + H -> H2 (g) o Both the chloride ions and hydrogen ions migrate to the anode o The chloride ions are preferentially discharged because of their higher concentration Cl- (aq) e- -> Cl o Chlorine atoms join in pairs to give molecules Cl + Cl -> Cl2 (g)

At the anode

As the hydrogen ions and chloride ions are discharged, sodium ions and hydroxide ions remain in the solution -> becomes sodium hydroxide

Electrolysis of aqueous sulphuric acid

As sulphuric acid is aqueous, it is composed not only of hydrogen ions and sulphate ions, but also hydroxide ions from the water When we have more than one type of ion moving to an electrode, selective 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
At anode o Hydroxide is easier to discharge (compared to sulphate ions) so oxygen gas is given off at the anode o 4OH- (aq) -> O2 (g) + 2H2O (l) + 4eAt cathode o Each hydrogen ion gains an electron to become a hydrogen atom o Two of these newly formed atoms then combine to form a hydrogen gas molecule o H+ (aq) + e- -> H o H + H -> H2 (g)

Electrolysis of aqueous sulphuric acid

With electrolysis of aqueous solutions of dilute acids of 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 ration 2:1

Preferential discharge
Cations K+ (aq) Na+ (aq) Anions SO4
2- (aq)

NO3- (aq)

Difficulty of discharge decreases

Ca2+ (aq)
Mg2+ (aq) Zn2+ (aq) Fe2 (aq) Pb2+ (aq) H+ (aq) Cu2+ (aq) Ag+ (aq)

Cl- (aq)
Br- (aq) I- (aq) OH- (aq)

The ions at the top require large amounts of energy to be discharged Down the table, they become easier to discharge

Factors affecting electrolysis

2 main factors
o Concentration o Type of electrode

Concentration
Anode
Dilute hydrochloric acid Concentrated hydrochloric acid Oxygen gas Chlorine gas

Cathode
Hydrogen gas Hydrogen gas

Concentration

If the concentration of a particular ion is high, then this can alter the preferential discharge Eg if dilute hydrochloric acid is electrolysed, hydrogen gas is given off at the cathode and oxygen gas at the anode However, when hydrochloric acid is electrolysed, hydrogen gas is still given off at the cathode, but chlorine gas comes off at the anode This is because although the chloride ion is harder to discharge than the hydroxide ion, its high concentration makes it more likely to be given off Cl- (aq) -> Cl + e Cl + Cl -> Cl2 (g)

Type of electrode
Eg: electrolysis of aqueous copper(II) sulphate solution If we use carbon electrodes, they are inert electrodes and do not affect the electrolysis Therefore, at the anode, we have a choice of sulphate or hydroxide ions The hydroxide ions are easier to discharge, so oxygen gas is given at the anode 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
o Cu2+ (aq) + 2e- -> Cu (s)
o 4OH- (aq) -> O2 (q) + 2H2O (l) + 4e-

Anode Copper(II) sulphate with Oxygen gas carbon electrode Copper(II) sulphate with Copper anode dissolves copper electrode

Cathode Copper deposited Copper deposited

Industrial applications: purification of copper

Industrial purifications
o Extraction of metals from ores, esp. aluminium o Purification of metals, esp copper

Refining or purification of copper

o The impure copper is made the anode and a thin, pure copper plate is used as a cathode o The electrolyte is usually acidified copper(II) sulphate solution o When electricity flows, the copper dissolves from the impure anode and goes into solution as copper ions o Impurities in the copper do not dissolve, and instead fall off the anode as an anode sludge o At the cathode, the copper ions are deposited as pure copper metal o A major use of copper is in electrical wiring

Industrial applications: manufacture of sodium hydroxide

Produced by electrolysis of concentrated seawater The chlorine and hydrogen gases which are also produced during this electrolysis are both commercially useful

Industrial applications: electroplating

To form a thin protective coating of a metal on the surface of another which is likely to corrode Eg: galvanising of iron - Iron is electroplated with a layer of zinc Also, stainless steel is electroplated first with nickel and then with a very thin layer of the more expensive but more attractive metal chromium In general, to electroplate, we need to make the cathode the object for plating The anode is then made of the metal we wish to plate with The electrolyte needs to be a solution of a salt of this metal Anode: Cu (s) -> Cu2+ (aq) + 2e- (copper dissolves from the anode) Cathode: Cu2+ (aq) +2e- -> Cu (s) (Copper deposits on the object)

Industrial applications: electroplating

Metal Zinc (galvanise) Chromium Silver Copper Nickel (EPNS) Gold Object Dustbins, buckets Car bumpers, bicycle handle bars Watches, bracelets Saucepans Cutlery (electroplated nickel steel_ Jewellery, watches

Cells and batteries

A device which converts chemical energy into electrical energy is called a cell, or battery It consists of a pair of dissimilar metals in an electrolyte The more reactive metal, magnesium, dissolves in the dilute acid and becomes magnesium ions, thereby producing electrons As electrons are produced, the magnesium acts as the negative electrode Mg (s) -> Mg2+ (aq) + 2e These electrons then travel to the copper electrode and produce bubbles of hydrogen gas at this electrode. As electrons are taken in, the copper is the positive electrode 2H+ + 2e- -> H2 (g)

Cells and batteries

This production and movement of electrons is electricity, so electrical energy has been generated and the bulb lights up Overall, the chemical reaction can be represented by the ionic equation Mg (s) + 2H+ (aq) -> Mg2+ (aq) + H2 (g) How bright the bulb is, depends on the difference in the reactivities of the two metals Magnesium and copper are far apart in the reactivity series, so the bulb is bright However, as the magnesium dissolves rapidly in the acid, the bulb does not stay alight for long Also, the copper electrode gets covered with bubbles of hydrogen gas, which prevent the electricity from flowing This is called polarisation

Reactivity series

Dry cells
If the electrolyte in the cells is a paste, it is called a dry cell Eg in battery operated clocks, torches, games, shavers etc It consists of a carbon rod which is inside a porous container of powdered carbon and manganese(IV) oxide The electrolyte is a paste of ammonium chloride The other electrode is the zinc casing of the cell itself This zinc casing acts as the negative terminal as it produces electrons Zinc -> zinc ions + electrons Zn -> Zn2+ + 2e-

Dry cells
Electrolyte: ammonium chloride paste Positive terminal: carbon electrode Negative terminal: zinc electrode

Dry cells
The positive terminal is the carbon rod, whose surface is increased by surrounding it with powdered carbon Also present is manganese(IV) oxide, which acts as a depolarising mixture, helping to oxidise the hydrogen gas produced when the ammonium ions from the electrolyte take up the electrons produced from the zinc electrode Ammonium ions + electrons -> ammonia + hydrogen 2NH4+ (aq) + 2e- -> 2NH3 (g) + H2 (g)