By the end of this spread, you should be able to... ing agent and reducing agent ‘% Explain the terms redox, oxidation number, half-reaction, ox for simple redox reactions. + Construct redox equations using relevant half-equations or oxidation numbers. ~ Interpret and make predictions for reactions involving electron transfer. During the study of redox in AS chemistry (see AS Chemistry spreads 1.1.14 and 1.1.16), you leamed: «that oxidation and reduction involve electron transfer Uncombined element | 0 * the rules for assigning oxidation states Combined oygen | -2 «that oxidation and recuction can be expressed in terms of changes in oxidation number, Combined hydra " ‘The most important oxidation number rules are listed in Table 1 as a reminder Simple or Redox contieiors |= Ina redox reaction, both reduction and oxidation take place ae 1) sition is Reduction is Teble(l Chicken tutier (ues ‘© the loss of electrons * the gain of electrons ‘an increase in oxidation number, * a docrease in oxidation number z ‘The substance that is reduced is an oxidising agent - it takes electrons from the Nevergetin amuddle—use ORIG: cup stance that is oxicised ‘The substance that is oxidised is a reducing agent - it gives electrons to the substance that is reduced. * Reduction must always be accompanied by oxidation. species gains (reduction), another species loses the . i : 7 same number of electrons (oxidation, Constructing redox equations using relevant half-equations Redox reactions take place when electrons are transferred. We can construct an overall ‘equation fora redox reaction i we know the oxidation and reduction hatf-reactions. «In the oxidation haif-reaction, electrons ere lost Oxidation i loss of electrons, or an «In the reduction haif-teaction, electrons are gained. Rereess Ost area TTo construct a balanced equation, we must follow a series of steps. These are illustrated Reduction is gain of electrons, ora in the worked example below. decrease in oxidation number | Worked example Rares een | Iron reacts with aqueous copper) ions to form iron(ll ions and copper metal ‘Step 1: identity the oxidation and reduction half-equations, ‘Equations for the separate oxidation and reduction reactions are shown lined up. Fo 4 Fe +36" oxidation (oss of electrons) Cut + 22° Cu reduction (gain of electrons) Step 2: Balance the electrons : The hatf-equations are scaled so that the number of electrons isthe same in each. Here, we need to multiply the oxidation half-equation by 2 and the reduction half-equation by 3: Fe == 3 2Fe +6 oxidation 30uR* + 6 —> Su reduction ‘Step 3: Add the two half equations together and cancel the electrons. 30ur* + Fe +e —> DFe* + 90u +66" So the balanced equation is 30u"* + 2Fe—> 2Fe + 8Cu 182ty ed cd Constructing redox equations using oxidation numbers ee Oxidation and réduction can be described in terms of oxidation numbers. ‘You can easily identity the oxidation and reduction processes using oxidation numbers. ‘An oxidation number is assigned to each atom in the redox reaction. You can then easily ‘see any changes in oxidation number. Oxidation numbers make it easy to account for electrons and are a great way of balancing complex redox reactions. . 2 Worked example 2. ce Hydrogen iodide, HI, is oxidised to iodine, [,, by concentrated sulfuric acid, H,S0,, which is reduced to hydrogen sutfide, H,S. Step 1: Identity the reactants and products from the information given The reactants and products are witten down to give an incomplete cratt equation: HI+H,S0,—>HSS +l, Don't worry that there is no ‘O' on the right-hand side of the equation - wee wail sort that out later. ‘Step 2: Identity the oxidation number changes White oxidation numbers underneath the ators that change oxidation number. Balance any atom that changes oxidation number. Identify the total changes in oxidation numbers. 2HI+H,SO,—> HS +1, 8 poreesio ‘Step 3: Balance the oxidation numbers changes it one species decreases its oxidation The equation must be balanced so that: ‘number eduction), then another Dare ears och ae Hee Weneed tomy 2H, by 4 obec te oa Oedation rune ee ree eee oes ‘equals the total decrease in oxidation BHI 4 H,S0,—> H,S + 4I, umber al poe 8x1 ———_5 4x02 : 48 Questions ‘Step 4: Check to see if anything else needs to be balanced 1 Construct redox equations Here there are 8H and 4O extra on the left-hand side, We can easily complete the following hal-equations the equation by adding 4H,0 to the right-hand side. (@) A—> AP + 80 This gives the tinal equation Cu + 2° —> Cu; (b) 287 — Br, + 26 GHI+ H.SO,—> H.S + 41, + 4H.O MnO, + BH" + Se°—> Mn? + 4H,0. Hints for completing the redox equations 2 Use oxidation states to construct 3ometimes you wil find that you are short of H’ on one side. In general, you may have to redox equations for the folowing add H’, OH or H.0. reactions * Ifthe reaction has been carried out in acid conditions, then simply add the number of (a). Hydrogen bromide, HBr, is H* ions that that you need. oxidised to bromine, Br., by » For alkaline conditions, you can add OH concentrated sulfuric aci, dito "IH and ‘O" need to be added, think H.O' fas in Step 4 in the worked example above). H,SO,, which is rec sulfur dioxide, $0, ‘uture use of redox equations (b) Hydrogen sulfide, H,S, is ‘ou will need to be able to combine hatf-equations in the next section on electrocherhicel ised to sulfur, 8, by nitic , 2.10-2.2.14). You will also nead to combine hal-equations and use id, HNO,, which is xidation numbers when you study redox titrations (spreads 2.3.9-2.3.1 reduced to nitrogen 30 this section is extremely important as it underpins much future work monoxide, NO. 183Cells and half cells By the end of this spread, you shouldbe able to... ya) (10 % Describe simple half cells made from (metals or non-metalsin contact with their ions in aqueous solution; (ii) ions of the same element in different oxidation states. Describe how half cells can be combined to make an electrochemical cell. Electricity from chemical reactions In redox reactions, electrons are transferred, An electrochernical call controls the electron transfer to produce electrical energy. The controlled transfer of electrons is the basis of all cels end batteries. Cells and half cells A half cell comprises an element in two oxidation states. The simplest half call has a metal placed in an aqueous solution of its ions. For example, a copper hat cell comprises a solution containing CuF*(aq) ions (oxidation state +2) into whichis placed a strip or rod of copper metal (oxidation state O) £n equilbrium exists atthe surface ofthe copper between these oxidation states of copper: uF*(aq) + 26° = Cubs} + The forward reaction involves electron gain and is reduction, | ‘© The reverse reaction involves electron loss and is oxidation. Figure + Coppar raf cell- copper metal By Convention, the equilibrium is written with the electrons on the left-hand side. The = is placed in an aqueous solution electrode potential of the haf coll indicates its tendency to lose or gain electrons in this contaring Cue ions. An equlbfurnis equilibrium. fet up atthe surface of the soled Gu wah aqueous Ov" ons: Cells from metal/metal ion half cells AA simple electroctiemical cell can be made by connecting together two haif cells with different electrode potentials: * one half coll releases electrons * the other hatf cell gains electrons. ‘The aitference in electrode potential is measured with a voltmeter CwMag) +26" Acoppeo cals town Fae 2 Thetwo al laid ur aie ares brags vi * The wire connects the two metals, allowing a electrons to be transferred between the two half cas ri ce he wre cman copper p Sosvousin incon hao the she G , electrode in the zinc half cell, The voltmeter has a | Garett ows asl bub wooo Highesitance voimetr Sat bilge the volmetr, the bub would ght up + | © The salt bridge connects the two solutions, | aowing ions tobe transfered betwéen the half | cels. A simple sat bridge can be made out of a Solution of Sulton ot strip of filter paper soaked in an aqueous solution “ Aleph} | oe 5 ‘of an ionic compound that does not react with ) LL eithor of the hatf-cell solutions. Usually aqueous Figure 2 Cooper-tinc electrochemical cell KNO,{aq) oF NH,NO,aq) is used. 184The redox equiliorium in each hait cell is shown below: Zn*(aq) + 2e" = Znis) CuP*(aq) + 26 = Culs) The Zr#*/Zn equibrium releases electrons more readily than the Cu*/Cu equillbrium. The Zn®*/Zn equilrium releases electrons into the wire, making zinc the negative electrode, . * Electrons fiow along the wire to the Cu electrode of the Cu’/Gu half cal, + The Zn**/Zn equiibrium loses electrons and moves to the loft: Zn + 26° = Zn + The Cu/Cu equilibrium gains the electrons and moves to the right Cu*(aq) + 28° = Culs) The reading on the voltmeter measures the potential difference of the cell ~ this measures the difference between the electrode potentials of the half cells, Non-metal/non-metal ion half cells ‘Anal cel can be made from a non-metal and its aqueous ions. For example, a hydrogen half cell comprises hydrogen gas, H,, in contact with H'(aq) ions. The redox equlbrium is: 2H(aq) + 26° = Hla) There isa problem in using ths type of haf cell when constructing a cal - there is no electrode to connect wire to. To overcome this, a platinum electrode is placed in the solution so that itis in contact with both H,(q) and Hfaq) ions. The platinum is inert and does not réact at all - its sole purpose is fo allow the transfer of electrons info and dut of tho halt cell via a connecting wite. The suriace of the platinum electrode is coated with ‘Platinum black, a spongy coating-in which electrons can be transferred between the non- metal and its ions. . ‘A standard hydrogen half cal is used as the reference for the measurement of voltages in electrochemical cals. A standard hydrogen haf cell comprises: * hydrochloric acid, HCi{aq), of concentration 1 mol dr’, as the source of Haq) + hydrogen gas, H,(g), at 100 kPa (1 atmosphere) pressure + an inert platinum electrode to allow electrons to pass into or out ofthe half cell via a The use of a standard hydrogen half ca is discussed in the next spread. ‘Metal ion/metal ion half cells This type of half call contains ions of the same element in different oxidation states. For example, a half cell can contain Fe"(aq) and Fe(aq) ions: Fe*(aq) + e = Fe™(aa) , standard Fe’(aq/Fe™(aq) half cell is made up of: * a solution containing Fe”(aq) anc Fe" (aq) ions with the same concentrations ‘equimolar’ ‘© an inert platinum electrode to allow electrons to pass into or out of the half cell via a connecting wire, Question 1 (a) What does a standard hydrogen half cell consist of? {b) When two cftferent naif cols are connected, how does the electric current fow (between the two electrodes; {i betwoen the two solutions? Ur IT Pd coy Cerri ls tube Hila t 2906) thes and faim inte loa | | bunks ot | Righto | | escape Patou | stetade Aid solution containing Oma. dm Han) Figure 9 Standard hydrogen half call Solution ‘antaining equal bancentratons ot Fe) ana Fe(ag) Peatinum slectrode Figure 4 Fo/Fe® hat cal 185‘The standard electrode potential of a half cll, E®, isthe ems, of aha cell compared with a standard hycrogen half cel, measured at 298K with solution concentrations of mol da? and a gas pressure of 100KPa (1 atmosphere). Remember tha the particles that cary charge in the electric circutt are * clectrons inthe wire * jons in the sat bridge, The sign of the standard electrode potential of hal cel ives the sion (poaiy) ofthe electrode compared ‘ith he nyarogen hat cet ONES By the end of this spread, you should be able to *% Define the term standard electrode redox) potential, E°. Describe how to measure standard electrode potentials using a standard hydrogen elf cel, % Gleulate a standard cell potential by combining two standard electrode potentials. Standard electrode potentials In spread 2.2.10 we discussed how two haif cells can be connected together to make a cel * A standard hydrogen hat cell is used as the reference stander for the measurement of cel ems '* An electromotive force, e.mf,, is the voltage produced by a cell when no current flows, We can compare the tendency of diferent half cells to release or accept electrons by measuring the e.m. when the half cells are combined separately with a hydrogen half ce. ‘To make this comparison meaningful, we use standard haif cells and standarc-conditions, * The resuiting ext. is called the standard electrode potential of a half cel * The standard electrode potential of a hydrogen half cells defined as exactly OV. Measuring standard electrode potentials A standard electrode potential is measured by connecting a standard half cell to a standard hydrogen half cell. Figure 1 shows how a hydrogen half cell can be used to measure the standard electrode potential of a Zn’-/Zn half cell. The reading on the voltmeter gives the standard electrode potential of the zinc half cell igh-esistance voltmeter oT 5 way —()) sin |) are stip Pratinum | | | q | mse t F i igure 1 Measuring eure Ie J get ee ey 1.0 mol dm" | {1.9 moldm-*} potential of a ZniZn* a = ‘The measured standard electrode potential of the Zn**/Zn half cellis -0.76 V. Standard cell potentials and cell reactions in the previous spread, we saw that a cell can be constructed by connecting together two hat calsr The standard cell potential of a cell is the e.m.t. between the two half cells making up the cell under standard conditions. ‘© The standard call potential of any cell is the difference between the standard electrode potentials of each half cell ‘The cell reaction is the overall chemical reaction taking place in the cell * The cel reaction is the sum of the reduction and oxidation half reactions taking place half cel,Ord Energy rae Worked example 1: the standard cell potential of a silver-copper cell A siver-copper callis made by connecting together two half cells: * an Ag/Ag' half col + aCu/Gv* hat cell ‘Step 1: Identify the two relevant redox equilioria and the sign of each electrode The more negative of the two systems is the negative terminal of the cell Agiteg) +e" = Aa(s) +0.80V postive terminal Cur(aq) +26 = Cus) 4034 negative terminal ‘Step 2; Calculate the standard cell potenti! The standard cell potential, Ey, is simply the difference between the standard electrode potentials ofthe half cel. Subtract E® of the negative terminal from E° of the postive terminal E&= E°(postive terminal) - E° (negative terminal) s. E&y= 40.80- (+0.34) 0.46 ‘Worked example : Step 1: Work out the direction of electron flow in the redox equilioia + From Worked example 1, we know the Cu®/Cu equilibrium has the more ‘negative E® value. This shows that the Cu"/Cu redox equilbrium has a = SSgeste- tendency tolose-tectrons thantheAg'/Aghal cal The Ou/Cu equilibrium loses electrons and moves to the let: Cu +26 = Cu Question 1. You are provided with the The Cu'/Gu equiibrium releases electrons into the wire. Electrons flow along f folowing standard electrode the wie to the Ag electrode of thé Ag'/Ag hal cal eae + The Ag'/Ag equliorium gains the electrons and moves tothe nght: ee ie See P= 44.98 V Ag'(aq) +e = Agis) ‘Step 2: Combine the haif-equations to aive the cell reaction The equations taking place at each electrode are: (aq) + 26" = Cul) = + Cu (aq)+2e oxidation Ag'(aq) + & —> Aais) reduction ‘The Ag’/Ag half-equation must be multipfed by 2 to balance the electrons: (@) Caloulate the standard cal Culs) — CuM(aq) + 26° potential for the following 2Ag'(aq) + 2° —> 2AgIs) solo roped under standard conditions: The two half-equations are then added together and electrons are cancelled @ Over endcu*cu (i) Fete and Cre/Cr Culs) + 2Ag'(aq) +22° —s 2Ag\s) + Cu*(aq) + 26> Gil) C#*/Cr and CLy/Ct This gives the equation for the overall cell reaction: Culs} + 2Ag'(aq) > 2Ag(s) + Cu(aq) determine the averall cel reaction. 187By the end of this spread, you should be able to ... 4 using standard cell potentials, the feas » Consider the limitations of predictions made using standard cell potentials, in terms of kinetics and concentration. Using standard electrode potentials to predict redox reactions Standard electrode potentials can be used to predict the feasibilly ofa redox reaction. Two redox equilibria are shown tselow Cu*(aq) + 2% ‘Culs} E°=40.94V NO,(aq) + 2H"(aq) + 6 = NO(6) +H,00) £°= +0.80V We can predict the redox reaction that may take place between the species present in these redox equilibria by treating the redox systems as i they are half cells. Step 1: Work out the direction of electron flow in the redox equllioria * The Cu%/Cu equilibrium has the more negative (ess positive) E* value - this ‘shows that the Cu’*/Cu redox equilibrium suppies elactrons and moves to the let. * The NO;/NO, equiliorium has the more positive (less negative) E° value - this, ‘shows that the NO,-/NO, redox equiliorium accepts elactrons and moves to the right pct Cu{aq) + 26° = Cuts) NO; (aq) + 2H'(aq) +6 =NO,g)+H.0) E°=+0.80V more positive We can therefore predict that Cu wil react with NO," anc. ‘Step 2: Write down the half-equations for the oxidation and reduction The hatf-equations taking place are: Culs)—> OuP(aq) + 20° oxidation a NO, (eq) + 2H"(aq) + © —> NO,Q) +H.0() reduction Figure 1 Redoxreaction of corcentated tap 3: Check the balance of electrons hi erat oer 2 Pm ‘The second haif-equation must be mutioled by 2 to balance the electrons: iitrogen dioxide gas, NO. Cus) —> Cu*(aq) + 26° 2NO;faq) + 4H'(aq) + 26° —> 2NOJa) + 2H.01) 0.34. — fess positive — SCT Nites hata eck kes ace Stop 4: Construct the overal equation ‘between reactants taken from different ‘The two half-equations are added together and the electrons cancelled: See Meteo cee tal ones Cul) + 2NO,(aq) + 4H'{aq) + 2e-—> Cu*(aq) + 2NO,{g) + 2H, 01) + 26° ‘The equilibrium with the more negative * This gives the equation for the overall reaction: E® value goes tothe lt. CU(s) + 2NO, (aq) + 4H"(aq) —> Cu™(aq) + 2NO.{a) + 2H,0() The electrochemical series \When comparing two redox equilibria, it is conventional to show the electrons on the lett-hand side. Shown like this, we can predict that @ reaction may take place between: * the species on the right-hand side ofthe redox equilirium with the more negative E> and «the species on the left-hand side ofthe redox equilibrium with the more positive E* 188The list below shows several redox equiliria arranged with the most negative E® value at the top. This is often called the electrochemical series. ‘The horizontal arrows show the preferrad direction of reaction. Fe*(aq) + 26 = Fels) Fe2-0.44V 2H'aq) + 26° =H.) ov CuP*(eq) + 26° = Cuts) £240.34 : Brfg) +20 = 28r(aq) E°= 1.07 V Cig) +22 =2Craq) E°= 41.96 V Of those in the list, the redox equiliorium Fe + 20° = Fe ‘+ has the most negative E® value = has the greatest tendency to release electrons and shift the equilibrium to the left. We can predict that Fe(s) would react with every species below and on the left in the lst: © Ht, Cu®, Br, and Cl, The redox equilibrium Cu* (aq) + 2e" = Cuts) © has a more negative E* value than the two redox equiliria below it in the list We can predict that Culs) would react with every species below and on the left in the list: * Br andCl, Limitations of predictions using standard electrode poten’ Electrode potentials and concentrs Non-standard conditions alter the value of an electrode potential. The haif-equation for the copper half cel is: QuP(aq) + 26 Cul) From le Chatelier's principle, on increasing the concentration of Cu**{aq): * the equilbrum opposes the change by moving to the right = electrons are removed front the eqaiioriany the electrode potential becomes less negative, or more positive, ‘A change in electrode potential resulting from concentration changes means thet predictions made an the basis ofthe standard value may not be valid. Is Will a reaction actually take place? Remember that these are equillbrium processes in aqueous conditions. * Predictions can be made about the equilibrium position but not about the reaction rate, which may be extremely slow because of a high activation energy. ‘© The actual conditions used for a reaction may be different from the standard conditions used to measure E® values. This will affect the value of the electrode potential (see above) ‘= Standard electrode potentials apply to aqueous equilibria - many reactions take place under very different conditions. ‘As @ general working rule: «the larger the difference between E® values, the more likaly itis that a reaction will take place « if the cifference between E° values is less than 0.4 V, then a rea take place. tion is unlikely to Question 1 Use the standard electrode potentials below to answer the questions that fotow, Fe*(aq) + & Fe*(aq) & 0.77 Brag) + 2¢° = 2Brfaq) E* = 41.07V Ne"aq) +26 = Nis) E® =-0.25V x(q) + 4H"(aq) + 4e- = 2H,0) | EP = 41.23 (2) Procict the reactions that could take place under standard conditions. (b) Write an overall equation for each reaction in (a). rT con AIL In the worked example, we know that 1 mol dav nitric acid was used because the electrode potential Used was the standard value. Predict the effect of using concentrated acid on the electrode potential given in the worked example Explain why the redox reaction between copper and nitric acid is ‘more likely to take place with concentrated acid than using 1 mol dmv nitric acid 189Figure 4 Selection of calls and batteries 190 Or eR RSLs By the end of this spread, you should be able to ... Apply the principles of electrode potentials to modern storage cells. Explain thata fuel cell uses the energy from the reaction of a fuel voltage. Explain the changes that take plac at each electrode in a hydrogen-oxygen fuel cell, oxygen to createa Electrochemical cells Electrochemical cells are used widely in everyday ife as a source of electrical energy. ‘Al cols work on the same principle - having two redox equilibria with diferent electrode potentials. For example, a simple cell can be set up based on zine and copper (see also spread 2.2.10), The redox equilibria in this cell are shown below together with their standard electrode potentials. The equilirium with the more negative electrode potential is the negative terminal of the cell Zn?(aq) + 26 = Zn(s) E*=-0.76V negative terminal Cut(aq) +2e- == Cus) = E® = 40.34V__ positive terminal The half-equations below show the reactions that take place at each electrode in the cell * The more negative zinc system provides the electrons, so the movement of the zine equilibrium is from right to left. © The half-equations are added together and electrons cancelled to give the equation for the overall call reaction: Znls) — Zn*aa) + 26 Curaq) + 26° —+ Culs) (Overall: Zn(g) + CuP*(aq)—> Culs) + Zn**(aq) “The standard potentials can be used to work out the e.m.. of the cell: E® (positive terminal) - E* (negative terminal) 0.34 -(-0.76) =1.10V Modern cells and batteries Electrochemical cells are used as our modem-day cells and batteries. Cells can be divided into three main types: +. Non-rechargeable cells - provide electrical energy unti the chemicals have reacted 10 such an extent that the voltage falls. The cell is then ‘fat’ and is discarded. 2 Rechargeable cells - the chemicals in the call react, providing electrical energy. The cell reaction can be reversed during recharging - the chemicals in the cell are regenerated and the cell can be used again. Common examples include * nickel and cadmium (Ni-Cad) batteries, used in rectiargeable batteries « lithium-ion and lithium polymer batteries, used in laptops. 2. Fuel calls - the call reaction uses external supplies of a fuel and en oxidant, which are consumed and needs to be provided continuously. The cell will continue to provide cloctrital energy so long as there is @ supply of fuel and oxidant. Gennes Imexams, you will not be expected to recall a specfc storage cel. However, you might be expected to make predictions about a given cel, Al relovant electrode potentials and other data wil be supplied.Ure cy Seer Fuel cells Fuel cells have been around for over 180 years! In 1842 Sir Willam Grove, a Welsh physicist, invented the first fuel cel, He mixed hydrogen and oxygen in the presence of an electrolyie and produced electricity and water. The invention, which later became known as a fuel cell, didn't produce enough electricity to be useful atthe time, Modern fuel cells are based on hydrogen, or hydrogen-rich fuels such as methano, CHAOH. The hydrogen-oxygen fuel cell ‘A uel call uses eneray from the reaction ofa fuel with oxygen to create a voltage. ‘© The reactants flow in and products flow out while the electrolyte remains in the cell ‘© Fuel cells can operate virtually continuously 80 long as the fuel and oxygen continue to flow into the cel. Ful cells do not have to be recharged. Figure 2 shons a simple hydrogen-oxygen fuel call wth an alkaline electrolyte. : t “The redox equllioria are shown below. The more negative of the two systems is the negative terminal of the cell 2H,Ol) +26” = H,(g) + 20H aq) E°=-0.83V negative terminal 160,19) + H,0() + 2e" = 20H (ea) £°=4040V positive terminal Hin “The more negative hydrogen system provides the electrons. This equilibrium is reversed when writing the hal-equations at each electrode: The haif equations are added together ‘and electrons cancelled to give the equation for the overall cel reaction: Hig) + 20+ (aq) —> 2H,00) + 28 ¥20,{g) + 2H,O()) + 2e- —> 20H (aq) Overall: H,(g) + %0.(g} —> 1,01) £5; = ™ positive temmina) =E {negative termina) = 0,40 - -0.83) =1.23V Other fuel calls have been developed ~ these are based on hydrogen-rich fuss methanol, natural gas and petrol Energy out Figure 2 Hydrogen-onygen tue! al such as Questions 1 What are the three main types of | Figure 3 Space shuttia launch, The electrochemical cell? ‘lect is provided by 2 What are the electrode reactions hydrogen ‘uel calls ~ the water produced and the overall reaction in an 6 used by the eraw for inking alkaline hydrogen fuel cell? 191Les By the end ofthis spread, you should be ableto ... Cutline the development of fuel cell vehicles (FCVs) that use hydrogen gas and hydrogen-rich fuels, State the advantages of FCVs over conventional petrol or diesel-powered vehicles. Understand how hydrogen might be stored in FCVS, Consider limitations of hydrogen fuel cells % Comment about the contribution ofthe ‘hydrogen economy’ to future energy and imitations. Development of fuel cell vehicles In the previous spread, we discussed the hydrogen fuel cell. In the future, a ‘hydrogen economy’ based on fuels cells may well contribute greatly to our ever-increasing energy needs. A current focus is the development of fuel cells as an alternative to the use of finite cik-based fuels in cars. ‘Scientists in the car industry are developing fuel cell vehicles (FCVs) ~ these use hydrogen gas or hydrogen-ich fuels. Hydrogen-rich fuels include methanol, natural gas and petrol. These are mixed with ‘water and converted into hydrogen gas by an onboard ‘reformer’. The reformer operates ‘at 250-300°C to generate the hydrogen gas — for example: Figure 1 Liqud-hyckogen-powored car, CH,OH + HO—+ 3H, + 00, “Test car (BNW 735) being fled with Feuid hydrogen fuel -the fuel tanks in the car boot. A converted carcan unfor Alternatively, fuel cells have been developed in which methanol isthe fuel rather than 300 klometres on fl tank of quid hydrogen. There are obvious advantages of a methanol fuel cel compared with use of thydrogen hydrogen gas: + aliquid fue! is easier to store than hydrogen gas ‘© methanol can be generated from biomass, ‘The hydrogen can then be fed into fuel cells Methanol-based fuel cells are in the early days of development. They currently generate only a small amount of power. Note also that carbon dioxide is produced as a waste emission. Advantages of fuel cell vehicles Fuel cel vehicles have advantages over conventional petrol and diesel vehicles. Less pollution and less CO, * Combustion of hydrocarbon fuels produces CO:, which contributes to the greenhouse effect. Incomplete combustion produces toxic carbon monoxide, which must be Figure 2 Vethano}-powered bus in New York cty, Methanolisa iqud usedesa removed by catalytic converters (see AS Chemistry spread 2.4.6). hydrogen carrerferfuelcals. Methanol * Hydrogen-rich fuels produce oniy small amounts of CO, and'air pollutants. {uel ols wi reduce the dependence on petrl and imerove urban ar quatty Greater efficiency * A petrol engine is less than 20% efficient in converting chemical energy by the combustion of petrol. Much of the chemical energy is wasted as heat. ‘* Hydrogen fuel call vehicles are 40-60% efficient in converting the fue!'s energy. This means that {uel consumption drops by more than half compared with a petrol- or Glesel-powered car. 192CY ned od Storage of hydrogen Cacti) The most obvious problem in storing hydrogen is that itis a gas with a very low bolling point. Gases are far more difficult to store than liquids such as petrol and diesel. Car manufacturers are developing several strategies for the storage of hydrogen. * Hydrogen can be stored as a liquid undeer pressure. This in itself creates logistical problems. Even under pressure, a very low temperature is required and liquid , hydrogen will need to be stored in a giant ‘thermos flask’ to prevent it from boiling, '* Hydrogen can be adsorbed onto the surface of a solid material in a similar way that a catalyst is able to hold gases to its surface, * Hydrogen can be absorbed within some solid materials oP a"! = ea oie *. R Pee, Mek uaieky eS Figure 3 Storage cf hycrogen by adsorption and absorption — large amounts of hydrogen ‘can be stored in a small volume at iow pressure and close to room temperature Limitations of hydrogen fuel cell ‘There are logistical problems in the development and use of hydrogen fus! cals. ‘+ The large-scale storage and transportation of hydrogen poses problems. A cost- effective and energy-efficient infrastructure needs to be in place to deliver large quantities of hydrogen fuel over long distances. © The feasibility of storing a pressurised liqua, * Current “adsorbers' and ‘absorbers’ of hydrogen have a limited ifetime. * Current fuel calls have a limited lifetime, requiring reguiar replacement and disposal folowing high production costs. Fuel calls use toxic chemicals in their production. The hydrogen economy The ‘hydrogen economy’ may contribute largely to future energy needs, but many limitations need to be resolved. ‘+ The use of hydrogen 2s a fuel has to be accepted politically and by the general publi + There are logistical problems in the handling and maintenance of hydrogen systems. '* Hydrogen is an ‘energy carrier’ and not an ‘energy source’. Hydrogen must first be manufactured, ether by electrolysis of water or by reacting methane (a finite fue) with steam. The danger is that more energy may be used in making the hydrogen than is saved by its use. One strategy isto use renewable forms of energy, such as the wind or solar power, to generate the hydrogen. Questions 1 How does a methanol fuel call work? 2 Outline the main methods available for storing hydrogen in stan fuel call vahicles. 193