ELECTROLYSIS ‘A process in which electrical energy is used to bring about a non- ‘spontaneous chemice! reection Reverse of what happens in a galvanic cel! Used to produc reactive matals (strong raductants) and strong oxidants ike Chlorine which cannot otherwise be made ‘The olectrocherricel series is stil used to predict which reactions occur atthe anode and cathode and generally the strongest oxidant and reductant wil react ‘but conditions (i.e. concentrations) can be adjusted to alter the products formed - Metals such as Li, Na, K, Ca, and Mg will never be plated cut atthe cathode from an aqueous solution (because the water will be reduced more easily than the metal [ons ~ see SEF table) therefore these metals willbe produced from rotten salts of the metal MAIN FEATURES OF AN ELECTROLYTIC CELL (the 26'e) ‘¥ ELECTROLYTE ~ soiution which contains free-moving ions which can aocept cr donate electrons allowing elacrone to move through the axiemel circuit > ELECTRODES tho anode (which has a positive charge in an electrolytic coll) and the cathode (which has @ negative charge in an electrolytic cll) EXTERNAL SOURCE OF ELECTRONS ~ a batiery or power pack provides lectrons moving in one direction (DC — direct currant) NE REDUCTION STILL OCCURS AT THE CATHODE OXIDATION STILL OCCURS AT THE ANODE BUT THE POLARITIES OF THE ELECTRODES ARE OPPOSITE TO THAT OF A GALVANIC CELL! Le. The cathode has a negative charge‘COMPARING ELECTROLYTIC AND GALVANIC CELLS Involves @ non-epontaneous reaction to produce electrical ‘odox reaction which will only energy ‘occur if anergy is supplied to foroe the reaction to 2ccur | + process carriec out in two carried out in one Celivsepareted compartments ‘calcompariment oxidant and reductant mustnot| + oxidant and reductant in direct ‘come in direct contact contact Salt bridge allows for flow of + no saitbridge ‘lecirons and completes electrical ciruit ‘anode ie negative © anode is postive ‘osthodie is positive (polarty oi | + cathode is negative (polarity ‘slectrodas is due tothe {due to the power supply) reaction et the electroce) ‘tection flow from anode © alactron flow from anode to (where the strongest reductant cathode 's present) to the cathode (where the strongest oxidant Is present) varie | Fora eloctroonamical calle ( iD slectoivicy + oxidation always occurs atthe anode (NB: vowels} reduction always oours athe cathode (NB: Reduction ROCKs!) according fo convention, tre enode ie shown on the lat of tha cathode ott hat cate and compile intemal and externet parte ofthe ciroult re required to sae eigncant reaction cations flow sowscds the eathode af ine call and ank ne anode enw tomes igh she vata pet ofthe circu (electfodes/niras) by acttos fiow from Anode 1o Cathode ‘emarnbar the ordar). Elactrone are toc movemael of fone cerres the curaPREDICTING REACTIONS DURING ELECTROLYSIS 4. Determine al species present atthe baginning of the reaction. Use the lectrochemical series to locate all half reactions Involving these species, Wits ‘these hall-equations out in the order they appear in the SEP table 2, Identty the strongest oxidant (nighest species on the left) and the strongest reductant (lowest species on the right) present and circle them 3. Rewrite the two half-equations involved showing both species as reactants. ‘The equation where electrons are produced will occur atthe postive electrode {ands} and wil be the oxidation reaction. ‘Tne equation where electrons are accepted will occur at the negative electrode {cathode} and will bs the reduction reaction 4. Determine the overall equation by ading the two hali-aquations together ensuring thatthe elections are balanced 5. Datermins the minimum voltage required to achieve the reactin by using the formula: minimum voltage required = E° oaswn~ Ewan NB: Jsually 2 voltage above this value is used to force the reaction to occur,0 An aqueous solution of Sabre is slectolysed using Inert alsctrodes 9}, Drew « ekstch ofthe colt, showing 1) the drection of electron flow inthe exterl circuit and ‘through the electrolyte +) Write hat-equations for the expectad reactions et each electrode, then write the overal equation ©) Calculate the minimum 6.1. needed to eloctrohse the solution under standart! conditions 0} Explain how the procucts of electrolysis would dtfer if tin electrodes wore used. Predict the products at the anode end cathode, write an overall equation and tarnine the minimum cel voltage required for the electrolyas using carbon slectrodes of ) Melten sodium bromioe An aqueous solution of sodium bromide 9 eo2 "Why is it thet the products produced during electrolysis cm differ from those predicted using the electrochemical series? because ‘The electrochemical series is determnined using standard conditions (1M ‘concentrations at SLC - 101925 Pa and 25°C). ‘we alter the concltions (i.e. don't use standard conditions), we can alter the order in the electrochemical caries. Factors affecting electrolysis of aqueous solutions include: + the concentration of the electroyie / concentration of ions © the neture ofthe electrolyte + the nature ofthe electrodes © temperature © interaction between reactants and products If allowed to mis + amount of applied potential leading to mixture of products + eelavant values forthe elactroda reactions bo how cap we know whet i producad? We can only definitely know the products when substances are slectrolysed by ‘carrying out an experiment under the intended conditions Industral production ot ‘many substances depends on knowing the products formed! under diferent conditions: and selecting the right conditions to favour the production ofthe desired chemicalYPES OF €1 STROLYSIS: 1) Slectrolyste of moiten tonto compounds Fp the elecrolysis of motien sodium chloride Poaction at anccs(axidation) Reaction at csthod(reduction} vera! Reaction: 2) Electrolysis of water Ep Use of ¢ Hofmann voltameter to carry out the electrolysis of water a ‘3) Electrolysis of aqueous olutions of ionke compounds 30u8 eodium chloride recaacal Ther " Possible Reactions at anode( oxidation) Possible Reactions at eothode( reduction): Reaction occurring at anode Reaction occurring ot cathod Overall Reaction.FARADAY'S LAWS: 1, Fataday’s tist iaw of slectroivsie “The amount of substance produced during electrolysis ie directly proportlonas 10 the quantity of electrical charge passed through the cell” (B=B] where is the electrics! charge in covionas (C} Us the current in empores (A) {is the time in seconds (6) Using experimental data where the Curent is Kept constent and the time the power is supplied i altered (end thorefore Qis varied), thal the mass deposted of & metal increases es @ ineresses Le. ma “The charge on one electron is 1.602 x 10°C. One mova of electrons (6.02x 10 parcles) therefore has a charge of 6.0210 x 1 602x10" G or 8.648xi0°C. This ‘number is called the Feraday constant end has the value 86500 Cio. Faradav's second iaw of electrolysis ‘in order to produce one mole of a substance a whole number (one, two or ir09) of moles of electrons (faradays) must be consumed according to the helt cell equation” or fietectrans) =% where Cis the electrical charge in coutombs (C) (electron) isthe number of mole of electrons needed according tothe hatf-cat equation F is Feradsy's constant which has the value of 985000/mo! ‘9 For the haf-cel ration, Zn®* + 20 — Zn, 2 faradays (or 2x98500C) must be passed to liberate one mole of zinc etoms (68.4g of zinc) {arecaQUESTIONS G7 Calculate the mass of zinc deposited atthe cethode when @ ealution of zing nitrate Undergoes electrolysis for one hour and fitean minutse using @ current of 0.75A Ge When @ current of 0.08004 flowed through an electrofytic oa for one hour and six ‘minutes, the mass of the cathode increased by 0.2549 dus tothe deposition of @ metal with a relative atomic mass of 207. Caloulete the charge on the cetione ofthis metal QS a) Consider the electrolysis ofa liute aqueous solution of sodlum chloride, and a sample of melted (iquid) sodium chloride, Complete the table below to show the half reactions occurring in each case ‘Melted NaCt “Reaction at nods (postive electrode) Reaction at cathode (negative electrode) Dilute aqueous NACI )Explain why differant products are Obtained Wn he Bove WO Cases ©} Stver metal is deposited during the electroiysis of an aqueous solution of Silver nitrate, Give two factors that wil affect the raass of elver depoctted ©) When 425 C of elactroty is passed through @ dilute aqueous solution of in (i) chloride (Sn), 0.2629 of tin metal is deposited. How many coulomb of loctrcty would D8 needed to deposit the same mase oftin from a lute Solution of tin (1V) chloride (SnCl) . Show how you arrived at your answer. BOS, 1997 06 16 minutes 24244 -+3= 11 marks)pou DNISIGONY doo andy + | sous pau soddoo ad sonposd oF SNINIAUOMIDATA VIED LANOBAB-TIVEShiorine production by electrolysie 9 are two methods that you will need to know about 1) Diaphragm cell ‘The diaphragm coll has es asbestos membrane that ensure that chlorine gas 09s not mix with products. Asbestos is chemical that can produce esbestoele. Chlorine is produced atthe dtanium anode and hydrogen gee and hydroxide fons are produced atthe cathode, Sodium hydroxide and some sodium chloride sre also ‘leased from the cal. (Note thet the chlorine is further purified by iquetying under FeSSura as Some oxygen is produced due to hydraxide ions accepting electrons to form waler and oxygen. The oxygen stays ae a gas when compressed al ordinarymbrane call ‘The membrane cell uses a plastic membrane which enauree thatonly poeitive ions ‘cen pass through but not the chloride ions which are negatively charged. The process's success rests on the nature of the membrane. Itis @ modified PTFE called Naflon (a du Pont polymer), the structure being given below. fo, i | : ly. ape ‘The sulphony! groups (- SOsH make it a cation-exchange membrane sit wil past cations but not anions between compartments ofthe cell. This as nothing te do with poe sizes it ‘depends only onthe fons being positively charged, Thus sodium fons can pase (othe cathode ‘compartment, but chloside (or ther anions) cannot snd 0 cannot contaminate the NaOH product. Chlorine is ei produced atthe anode and hydrogen and hydroxide ion atthe ‘cathode. However the sodium hydrazide produced i now pure. tans hysogen Wy cen chlorine be produced from aqusous solution but not sodium? 2. What are the advantages of using & membrane call compered lo @ dlaghragmDOWN'S CELL THE PRODUCTION OF SODIUM eoupettich ———] che 3 fo \ | oe ° 000 j 1) me oes or . + r J} Cathal aie ‘The Down's Cell is used io make sodium commer ‘Anodet+ ally. Molten sodium ctlorde is lectrolysed in the process. Sodium chloride i added as needed into the Dowa's cell td er iron mesh soreen separates the products whic h are liquid sodium and chlorine 88. Sodium chloride cormally melts st 801°C but the addition of calcium chloride (fu) allows « lower temperature of SO0°C to be used. Chlorine gas is collected from the to ofthe cell whereas sodium metal due to its lower density than the electrolyte “oats to the surface where i lowe over into # separate container Product at snode: Chlorive gas Product at cathode quid ediasn suet ‘Anode reection (oxidation) CT) + Chayyt 26 node reaction (eesuction) ‘ABIeCley + 2NEqy + ClayQ. Why isthe calcium chioride added? (Q, Why are the electrodes separated by an iron mesh screen’? Q. Why must the products be kept separate? (Q. A curent of 300004 is passed through s Down's cel fora period of two hours. Calvlate '8) the mass of sodium produced in two hours 1) the volume of chlorine gus produced t SLC per hour » »9) thas i waked on rox. every 3 weeks 2 production and ng which migProduct at anode (+); Carbon dioxide ges Product at cathode (): Liquid aluminium Anode reaction (xiation)s 207 in cryolite)-> Ory + 4e Cay 20%Gn eras) S Cougs de (Cathode reaction (reduction): AGn ryote) +3 > Aly Overall Celt Reaction: AO in erylite) + 3Cyy> Aly +300ay Q Why s eryotite used? What ie its formale? (Q. Why do the carbon anodes need 1 be replaced? (Q. Why can’t aluminium be produced from aquecus tolution '. What is one environmental problem associsted with the production of luriniom using » Hall-Herouk es”eaespotspureonpormn ci smpen sn sonnbe eee eterna sore on nnn ng fg ney ea olan an oe apn ap He sessing aoe Sue iva pa mom og c