Kinetics: Basics * The rate of reaction refers to the change in the amount or concentration of a reactant or product per unit time and can be found by: * Measuring the decrease in the concentration of a reactant OR * Measuring the increase in the concentration of a product overtime © Theunits of rate of reaction are mol dm™>s change in concentration Rate of reaction = dime taken Rate equation « The thermal decomposition of calcium carbonate (CaCO3) will be used as an example to study the rate of reaction CaCO5(s) + CaO (s) + CO2(g) * Therate of reaction at different concentrations of CaCOzis measured and tabulated —fale Note, that the [CaCO,] remains constant for all valuesRate of reactions table ter-TolePa RC TK Lea] tha Re) aL ea 2.00 « 107 6.67 « 10* 4.33 « 10° 6.67 10+ 4.00 6.60 « 40~* 6.67 «10+ * Adirectly proportional relationship between the rate of the reaction and concentration of CaCOsis observed when a graphis plottedRATE {CaCO,] 2.00 |-------------------- = 6.67 x10 GRADIENT = 41.00 RATE (x4073mol dm-3s~1) 4.00 2.00 3.00 ([CaCO,} (mol dm-9) Rate of thermal decomposition of CaCO over the concentration of CaCO; ‘< rate * Note that the gradient of the graph corresponds to [Gaqq,] and remains the same throughout * The rate of reaction for the thermal decomposition of CaCO; can also be written as Rate of reaction = kx[CaCO3]The proportionality constant kis the gradient of the graph andis also called the rate constant The rate equations the overall expression for a particular reaction without the'x’ sign Rate of reaction = k[CaCO3] Rate equations can only be determined experimentally and cannot be found from the stoichiometric equation Rate of reaction = k[AJ™ [B]" [A] and [B] = concentrations of reactants mand n= orders of the reaction For example, the rate equation for the formation of nitrogen gas (Nz) from nitrogen oxide (NO) and hydrogen (H2) is rate = KINO]? [Ho] 2NO (g) + 2H2 (g) > N2(g) + 2H20 (g) rate = k[NO]?[H2] As mentioned before, the rate equation of the reaction above cannot be deduced from the stoichiometric equation but can only experimentally be determined by: © Changing the concentration of NO and determining how it affects the rate while keeping [H2] constant © This shows that the rateis proportional to the square of [NO] Rate = ky [NO]? Then, changing the [Hz] and determining howit affects the rate while keeping [NO] constant This shows that the rate is proportional to [Hz] Rate = kz [Ha] Combining the two equations gives the overall rate equation (where k= ky +kz) Rate = KINO}? [H2]Rate of Reaction: Concentration & Pressure Concentration ‘* Themore concentrated a solutions, the greater the number of particles in a given volume of solvent * Anincrease in concentration causes in an increased collision frequency and therefore an increased rate of reaction e EFFECTIVE COLLISION REACTANT 2 REACTANT 14 The diagram shows a higher concentration of particles in (b) which means that there are more particles present in the same volume than (a) so the chances and frequency of collisions between reacting particles is increased causing an increased rate of reactionPressure * Aninctease in pressure in reactions that involve gases has the same effect as an increased concentration of solutions * When the pressure is increased, the molecules have less space in which they can move * This means that the number of effective collisions increases due to an increased collision frequency * Anincrease in pressure therefore increases the rate of reaction EFFECTIVE COLLISION REACTANT 2 REACTANT 1 The diagram shows a higher pressure in (b) which means that the same number of particles occupy a smaller volume, resulting in an increased collision frequency and therefore increased rate of reactionRate of Reaction: Experimental Calculations During a reaction, the reactants are used up and changedinto the products This means that as the reaction proceeds, the concentration of the reactants is decreasing and the concentration of the productsis increasing Because of this, the rate of the reactionis not the same throughout the reaction but changes The rate of reaction during the reaction can be calculated from a concentration-time graph. The isomerisation of cyclopropane to propene will be taken as an example H,C: 12 ode —— > ¢H,CH=CH,(g) HAC CYCLOPROPANE PROPENE REACTANT PRODUCT Isomerisation of cyclopropane * The concentrations of reactant (cyclopropane) and product (propene) over time canbe experimentally obtainedConcentrations of cyclopropane & propene table ime [cyclopropane] [propenel Cy) (mol dm-3) (mol dm-3) 4.50* When taking the measurements, the temperature should be kept the same at all times as a change in temperature will change the rate of reaction * Aconcentration-time graph for the concentration of propene as well as cyclopropane can b¢ obtained from the above results © Asanexample, the concentration-time graph far propene is shown below [PROPENE] (mol dm-3) 20 3 TIME (min) 40 The graph shows that the concentration of propene increases with timeCalculating the rate at the start of areaction © Atthe start of the reaction, the concentration-time curve looks almost linear * Therate at this point can therefore be found by treating the curve asa linear line and by using CHANGE IN AMOUNT OF REACTANTS OR PRODUCTS (mol dm?) RATE OF A REACTION = TIME (s) * Using the graph, the average rate of the reaction over the first 5 minutes for propenes:[PROPENE] (mol dm-3) 0 TIME (min) Line a shows the average rate over the first five minutes whereas line b shows the actual initial rate found by drawing a tangent at the start of the curve. The calculated rates are very similar for both methods _ 027 Rate = 399 = 0.0009 moldm-? s-!Calculating the rate as the reaction proceeds * The curve becomes shallower with time which means that the rate decreases with time * The rate of reaction can be calculated by taking short time intervals Eg, you can calculate the rate of reaction from 15 to 20 mins during which the concentration of propene increases from 0.68 to 0.83 mol dm~*: _ 0.83) - 0.68) Rate = (7200) — (900) = 0.0005 moldm~*s* * The smalierthe time intervals, the more accurate the reaction rate value is * Even more accurateis to find the rate of reaction at different concentrations of reactant or product at particular time points * Thiscan be done by drawing tangents at several points on the graph © Asan example, the rates of reaction at different concentrations of cyclopropane are calculated by drawing the appropriate tangents:RATE AT CONCENTRATION = 4.5 mol dm-3 Is = 1.00x 40°? mol dm-3s~4 45 25%60 44 = RATE AT CONCENTRATION = 1.0 mol dm-3 ; E 42 14 = 7. IS yea = 6.67* 10“ mol dm-3s-1 2 35x60 = 40 RATE AT CONCENTRATION =0.5 mol dm-3 4.04 52.5*60 Is = 3.30* 10™*mol dm-3s~* {[CYCLOPROPANE] 2 a 0.2 TANGENT) S fr “Hie AT POINT 2) “\ 5 at OF peter 0 410 20 30 40 50 TIME (min) The rate of reaction at 3 different concentrations of cyclopropane is calculated by drawing tangents at those points in the graphRate-concentration graph * The calculated rates can then be summarised ina table to show how the rate of reaction changes with changing concentration of the reactants or products Change in rate with decreasing concentration of cyclopropane table [cyclopropane] Rate (mol dm-3) Clom CR nero) es fos fe | a © This data can then be used to plot a rate-concentration graph + The graph shows that the rateis directly proportional to the concentration of cyclopropane © Ifyou double the concentration of cyclopropane the rate of reaction will double tooRATE OF DECREASE OF [CYCLOPROPANE] (40? mol dm-3s~*) 0 0.5 4.0 45 [CYCLOPROPANE] (mol dm-3) The graph shows a directly proportional correlation between the concentration of cyclopropane and the rate of reactionOrder of reaction « The order of reaction shows how the concentration of areactant affects the rate of reaction © Itis the power to which the concentration of that reactant is raised in the rate equation © The order of reaction canbe 0,1,20r3 © When the order of reaction of a reactants 0, its concentration is ignored * The overall order of reactionis the sum of the powers of the reactants ina rate equation * Forexample, in the following rate equation, the reactions: Rate = k[NO2][H2] © Second-order with respect to NO © First-order with respect to Hz © Third-order overall (2 +1) Half-life * The half-life (tia) is the time taken for the concentration of a limiting reactant to become half of its initial valueRate-determining step & intermediates * Therate-determining step is the slowest step ina reaction * Ifareactant appears in the rate~determining step, then the concentration of that reactant will also appear inthe rate equation + For example, the rate equation for the reaction below s rate = k[CH3B1] [OH] (CHsBr + OH” CH3OH + Br © This suggests that both CH28r and OH" take part in the slow rate-determii * Thisreactionis, therefore, a bimolecular reaction ing step © Unimolecular: one species involved in the rate-determining step step © Bimolecular: two species involved in the rate-determining step + The intermediate is derived from substances that react together to formitin the rate-determining © Forexample, forthe reaction above the intermediate would consist of CH3Br and OH” HOH zs HO pr H The intermediate is formed from the species that are involved in the rate-determining step (and thus appear in the rate equation)Kinetics: Calculations Order of reaction * The order of reaction shows how the concentration of areactant affects the rate of reaction Rate = k[A]™[B]" * When morniszero = the concentration of the reactants does not affect the rate * When the order of reaction (m orn) of a reactantis O, its concentration isignored * The overall order of reaction is the sum of the powers of the reactants ina rate equation * Forexample, in the reaction below, the overall order of reaction is 2 (1+1) Rate = k[NOz] [Clz] Order of reaction from concentration-time graphs * Inazero-order the concentration of the reactants inversely proportional to time © This means that the concentration of the reactant decreases with increasing time © The graphis straight line going downCONCENTRATION OF REACTANT (mol dm-3) TIME (s) Concentration-time graphs of azero-order reaction* Ina first-order reaction the concentration of the reactant decreases with time © The graphis a curve going downwards and eventually plateaus CONCENTRATION OF REACTANT. (mol dm-3) TIME (s) Concentration-time graphs of a first-order reaction+ Inasecond-order reaction the concentration of the reactant decreases more steeply with time © The concentration of reactant decreases more with increasing time compared to ina first-order reaction © The graphisa steeper curve going downwards CONCENTRATION OF REACTANT (mol dm-3) TIME (s) Concentration-time graphs of a second-order reactionOrder of reaction from initial rate * The progress of the reaction canbe followed by measuring the initial rates of the reaction using various initial concentrations of eachreactant + These rates can then be plotted against time ina rate-time graph « Inazero-order reaction the rate doesn't depend on the concentration of the reactant © The rate of the reaction therefore remains constant throughout the reaction © The graphis a horizontal line © Therate equationis rate = k REACTION RATE (mol dm-3s~‘) CONCENTRATION OF REACTANT, [A] (mol dr)« Ina first-order reaction the rate is directly proportional to the concentration of a reactant © Therate of the reaction decreases as the concentration of the reactant decreases when it gets used up during the reaction © Thegraphisastraightline © Therate equation is rate = k[A] ) REACTION RATE (mol dm-3s CONCENTRATION OF REACTANT, TA] (mol dm) Rate-time graph ofa first-order reaction* Inasecond-order reaction, the rate is directly proportional to the square of concentration of a reactant © The rate of the reaction decreases more as the concentration of the reactant decreases when it gets used up during the reaction o The graphisacurvedline © Therate equationisrate = k [A]? REACTION RATE (mol dm-3s-‘) CONCENTRATION OF REACTANT, [A] (mol dm?) Rate-time graphs of a second-order reactionOrder of reaction from half-life * The order of a reaction can also be deduced from its half-life (ty2) Fora zero-order reaction the successive half-lives decrease with time © This means that it would take less time for the concentration of reactant to halve as the reaction progresses The half-life of a first-order reaction remains constant throughout the reaction © The amount of time required for the concentration of reactants to halve will be the same during the entire reaction Fora second-order reaction, the half-life increases with time © This means that as the reaction is taking place, it takes more time for the concentration of reactants to halve 6 ZERO ORDER 3 |\ First ORDER 3 |\ second ORDER iE a - i a CONCENTRATION = =< E+-----4 — E Zz 1 an t a & & a Go = OL__ > Go = Zz Zz 8 tot 8 I 1 8 x > x > = > 41) (2) (1) t4(2) 441) t4(2) $ $ $ 4 gt TIME TIME TIMECalculating the initial rate * The initial rate can be calculated by using the initial concentrations of the reactants in the rate equation * Forexample, in the reaction of bromomethane (CH3Br) with hydroxide (OH") ions to form methanol (CH3QH) the reaction equation and rate are as follows CH3Br + OH” > CH3Br + Br (aq) Rate = k[CHsBr] [OH"] Where k= 1.75x10°2dm-?mol"!s! * If the initial concentrations of CH3Br and OH" are 0.0200 and 0.0100 mol dm" respectively, the rate of reactionis: Rate = k[CH;Br] [OH] Initial rate = 1.75 x10~? x (0.0200) x (0.0100) Initial rate = 3.50 x10" mol dm s"!Calculating Units + When you are asked to calculate the rate constant, k, fora reaction you must also be able to deduce the units * Thisis done by replacing the values in the rearranged rate equation with the units of that value « The units can then be combined or cancelledas required * For example, to calculate the units for the above reaction: (mol-dnv-¥s-1) UNITS OF k= —————___ (mol-div-3} (mol drm-3) " mol dm-3 mol “dm?s~4First Order Reaction Half-life * The half-life of a first-order reaction is independent of the concentration of reactants © Thismeans that despite the concentrations of the reactants decreasing during the reaction © The amount of time taken for the concentrations of the reactants to halve willremain the same throughout the reaction © The graphisa straight line going downwards + The rearrangement of the methyl group (CH;) in ethanenitrile (CH3CN) is an example of a first-order reaction with rate equation rate = KICHsCN] ‘CH;CN (g) + CH3NC (g) CH,-C=N ——> CH, ——> C=N-—CH, Rearrangement of the CH; group in CHsCN+ Experimental data of the changes in concentration over time suggests that the half-lifeis constant © Evenif the half-lives are slightly different from each other, they can still be considered to remain constant * This means that no matter what the original concentration of the CH;CNis, the half-life will always be around 10.0 minutes Half-life table Change in [CH3CN] (mol dm: 8.00- 4.00 10.0 4.00 -2.00 9.50 2.00 -1.00 9.258.00 7.00 6.00 5.00 4.004------- 3.00 {CH,CN1 (mol dm-3) 2.00-4-= S24 poe 4.004 ------------b----> 2710.0 | ty2= 9.50 0.00 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 TIME (min) Ina first-order reaction, the time taken for the concentration to halve remains constantWorked Example: Using the half-life of first-order reactions in calculations The changes in concentration of a reactant over time are recorded in @ the table below: Time (s) er rashaREe Ole TE Leo) Draw a graph of concentration against time using these experimental results Determine the first and second half-lives and hence determine the reaction order of the reaction.Answer * Step: Plot the concentration-time graph using appropriate scales and labels for the axis [REACTANT] («40 mol dm-3) TT I © 100 200 300 400 500 600 700 800 900 1000 4400 1200 1300 1400 4500 1600 TIME (s)* Step 2: Find the first and second half-lives by determining when the concentrations halve using the graph Step 2 table Change in [reactant] (Cx emma Tae) Half-Life (s) First half-life 5.80 — 2.90 470 -0=470 Second half-life 2.90 — 1.45 920 - 470 = 450 «Step 3: Determine the reaction order itis a first-order reaction as the successive half-lives remain reasonably constant (around 450, seconds) throughout the reactionCalculating the Rate Constant + The rate constant (4) of areaction canbe calculated using: © Theinitial rates and the rate equation © The half-life Calculating the rate constant from the initial rate * The reaction of calcium carbonate (CaCOs) with chloride (CI) ions to form calcium chloride (CaClz) willbe used as an example to calculate the rate constant from the initial rate andinitial concentrations * The reaction and rate equation are as follows: CaCOs(s) + 2CI- (aq) + 2H* (aq) + CaCl (aq) + CO2(g) + H20 (I) Rate = k[CaCOs3] [CI"] + The progress of the reaction can be followed by measuring the initial rates of the reaction using various initial concentrations of each reactantExperimental results of concentrations & initial rates table Initial rate of [CacoO,] [cr] tie Prelate Measurement (moldm3) (moldm%) (moldm-3) (mol dm-s-‘) | ot 0.0250 0125 0.0125 4.38 «10° | 3 10625 0250 0.0250 2.49 « 40°° * Tofind the rate constant (k) © Rearrange the rate equation to find k Rate = k[CaCOJ [Cl] —+ k= acon er] * Substitute the values of one of the experiments to find k(for example measurement 1) ee. 4.38 x 10° ~ (0.0250) x (0.0125) =1.40x10-2dm3 mols? * The values of measurement 2 or 3 could also have been used to find k(they all give the same result of 1.40x10-2dm3 mots")Calculating the rate constant from the half-life * The rate constant (k}can also be calculated from the half-life of a reaction * Youare only expected to deduce kfrom the half-life of a first-order reaction as the calculations for second and zero-order reactions are more complicated + Fora first-order reaction, the half-life is related to the rate constant by the following expression 0.693 tae + Rearranging the equation to find kgives: p= 0593 hie * So, fora first-order reaction such as the methyl (CHs) rearrangementin ethanenitrile (CH3CN) with a half-life of 10.0 minutes the rate constantis: 0.693, 10.0 x 60 1.16 x10" dm mols?Kinetics of Multi-Step Reactions + The reaction mechanism of a reaction describes how many steps are involved in the making and breaking of bonds during a chemical reaction « tis the slowest step ina reaction and includes the reactants that have animpact on the reaction rate when their concentrations are changed © Therefore, allreactants that appear in the rate equation willalso appear in the rate-determining step © This means that reactants that have a zero-order and intermediates will not be present in the rate-determining stepPredicting the reaction mechanism The overall reaction equation and rate equation can be used to predict a possible reaction mechanism of areaction For example, nitrogen dioxide (NOz) and carbon monoxide (CO) react to form nitrogen monoxide (NO) and carbon dioxide (CO2) The overall reaction equationis: NO; (g) + CO(g) + NO (g) + CO2(g) The rate equations: Rate = kINOz]? From the rate equationit can be concluded that the reaction is zero order with respect toCO(g) and second order with respect to NO2(g) This means that there are two molecules of NO2 (g) involved in the rate-determining step Apossible reaction mechanism could therefore be: Step: 2NO> (g) > NO (g) + NO3(g)_ slow (rate-determining step) Step2: NO3(g) + CO(g)-+NO2(g) +CO2(g) fast Overall: 2NO2(g) + NOx{g) + CO (g) + NO (g) + NOxtg) + NOz{g}+ CO2(g) = NOz2(g) + CO(g)—+NO(g) + CO2(g)Predicting the reaction order & deducing the rate equation * The order of a reactant and thus the rate equation can be deduced froma reaction mechanism given that the rate-cletermining step is known * Forexample, the reaction of nitrogen oxide (NO) with hydrogen (H2) to form nitrogen (Nz) and water 2NO (g) + 2H2 (g) > No(g) + 2H20 (1) * Thereaction mechanism for this reaction is * Step1: NO (g)+NO(g)—>NzO2(g) fast * Step2: N2O2 (g) + H2(g) > H20 (I) +N2O(g) slow (rate-determining step) * Step3: N20 (g) + H2(g)—N2(g)+H20 (I) fast * The second step in this reaction mechanism is the rate-determining step « Therate-determining step consists of 9 N2O, which is formed from the reaction of two NO molecules ° OneH; molecule * Thereactionis, therefore, second order with respect to NO and frst order with respect to Hy * So, therate equation becomes Rate = k[NO]? [H2] * Thereactionis, therefore, third order overallIdentifying the rate-determining step * The rate-determining step can be identined from a rate equation given that the reaction mechanism isknown * Forexample, propane (CH3CHCHs) undergoes bromination under alkaline solutions © The overall reactionis: (CH3CH2CHs + Br2 + OH” + CH3CH2CH2Br + H20 + Br © The reaction mechanism is: Wi te H-C—C-CF + H,0 H HH H HH Lot od _ SLOW nn —_~ H HH HHH H HH FAST =x bos zh dee HoH 4-BROMOPROPANE H RATE DETERMINING STEP | | + Br —— Gage CBr + Bro Reaction mechanism of the bromination of propane under alkaline conditions‘* The rate equationis Rate = k[CHsCH2CHs] [OH"] ‘* From therate equation, it canbe deduced that only CH3COCHs and OH are involved in the rate- determining step and not bromine (Br2) * Since only in step 1 of the reaction mechanism are CH;COCHs and OH involved, the rate- determining step is step lis the case for step lof the reaction mechanism Identifying intermediates & catalyst « Whenarate equation includes a species that is not part of the chemical reaction equation then this, speciesisacatalyst * Forexample, the halogenation of butanone under acidic conditions « The reaction mechanism is He CH,CH,COCH, + |, > CH,CH,COCH,| + HIThe reaction mechanism is STEP 4: STEP 2: STEP 3: STEP 4: ° *OH Il FAST. Il CH,—CH,—-C—CH, + H’ == = CH,—CH,—C—CH, *OH OH I SLOW | + CH;—CH,-C—CH, ——> CH,—-CH,-C=CH, + H OH “OH | FAST - CH;—CH,—C=CH, + Ip ——> CH;-CH,-C—CH,I + I *OH oO FAST ll i CHj—CH,—C—CH,I +I <== CHy-CH,-C—CH,I + HI Reaction mechanism of the halogenation of butanone under acidic conditionsThe rate equationis: Rate = k[CH3CH2COCH3] [H*] TheH* isnot present in the chemical reaction equation but does appearin the rate equation © H* must therefore bea catalyst Furthermore, the rate equation suggest that CH3CH2COCH and H* must be involved in the rate- determining (slowest) step The CH3CH,COCH; and H* appear in the rate-determining step in the form of anintermediate (which is a combination of the two species) i a CH;-CH,-C—CH, + H* == CH,-CH,-C—CH, INTERMEDIATE Intermediate is formedin the rate-determining step from the reaction of CH3CHCOCHs and H*Rate of Reaction: Experimental Calculations + The rate of areaction canbe studied by several experimental techniques, depending onthe reaction: + Formation of a precipitate © Therate could be measured by placing a conical flask of the reaction mixture over a black cross © Asthe reaction proceeds, a precipitate will be formed which will cover the cross © Time howlongit takes for the cross to disappear to determine the reaction rate * Change incolour © Use calorimetry to measure the amount of light absorbed by the mixture © Asthe reaction proceeds, the change in colour becomes more evident © Resultingin an increased light absorption incalorimetry + Production of H* ions © Use apH probe to measure the pH of the solution © Asthe reaction proceeds, more and more H' ions are produced © This causes the solution to become more acidic © The rate of reaction can be measured by measuring the changes in pH overtime + Electrical conductivity © Theelectrical conductivity of a liquid depends on the concentration of ions presentin the solution © Soifionsare being used up, the conductivity of the liquid will decrease © Therate of reaction can be determined by measuring the change in conductivity over time and hence the change inion concentrations over time + Production of gas © Use agas syringe to record the volume of gas produced © Oranupturned measuring cylinder ina trough of water to measure the volume of gas produced © Oramass balance to measure the change in mass as the gas escapes © Therate of reaction canbe determined by measuring the changesin volume or masses overtimeEffect of Temperature on the Rate Constant Athigher temperatures, a greater proportion of molecules have energy greater than the activation energy Since the rate constant and rate of reaction are directly proportional to the fraction of molecules with energy equal or greater than the activation energy, then at higher temperatures: © Therate constant increases © The rate of reaction increases The relationship between the rate constant and the temperature is given by the following equation: Ea Ink=InA- pr In k= natural logarithm of the rate constant A= constant related to the collision frequency and orientation of the molecules E,= activation energy (joules, J) R= gas constant (8.31) K™ mol") T= temperature (kelvin, K) Avaries only alittle bit with temperature, it canbe considered a constant E,and Rare also constantse Agraph of In k against i gives a line with an equation of the form y = mx +c T - a 1 Lnk= RS p+InA o y=ink -i oO X= iT = Ee (gradient o m=—R (gradient) o c=InA (y-intercept) + The equation shows that an increase in temperature (higher value of 7) gives a greater value of In k (and therefore a higher value of k) + Since the rate of the reaction depends on the rate constant (A) an increase in kalso means an increased rate of reactionW/T Kk) LINE OF BEST FIT Ink GRADIENT = se INTERCEPT = In A The graph of Ink over 1/Tis a straight line with gradient -E,/R oO Exam Tip You are not required to learn this equation however it is helpful in understanding the effects of temperature on the rate constant.Heterogeneous Catalysis In heterogeneous catalysis, the molecules react at the surface of a solid catalyst The mode of action of aheterogeneous catalyst consists of the following steps: Adsorption (or chemisorption) of the reactants on the catalyst surface © Thereactants diffuse to the surface of the catalyst © Thereactantis physically adsorbed onto the surface by weak forces © Thereactantis chemically adsorbed onto the surface by stronger bonds © Chemisorption causes bond weakening between the atoms of the reactants Desorption of the products © Thebonds between the products and catalyst weaken so much that the products break away from the surface For example, the adsorption of hydrogen molecules onto a palladium (Pd) surfaceTHE BONDS BETWEEN HYDROGEN ATOMS ARE WEAKENING BOND STRENGTHENING BETWEEN THE HYDROGEN AND PALLADIUM ATOMS HYDROGEN ATOMS MOVING TOWARDS PALLADIUM SURFACE The reactants are adsorbed on the catalyst surface causing bond weakening and eventually desorption of the productslronin the Haber process Inthe Haber process ammonia (NHs) is produced from nitrogen (Nz) and hydrogen (Ha) Aniron catalyst is used which speeds up the reaction by bringing the reactants close togetheron the metal surface This increases their likelihood to react with each other The mode of action of the iron catalystis as follows: © Diffusion of the nitrogen and hydrogen gas to the iron surface © Adsorption of the reactant molecules onto theron surface by forming bonds between the iron and reactant atoms = These bonds are so strong that they weaken the covalent bonds between the nitrogen atomsin Na and hydrogen atoms ina = But they are weak enough to break when the catalysis has been completed © The reaction takes place between the adsorbed nitrogen and hydrogen atoms which react with each other on the iron surface to form NH3, © Desorption occurs when the bonds between the NHs and iron surface are weakened and eventually broken © The formed NH; diffuses away from the iron surfacex Vx, ‘y i H HN N BNEW BONDS FORMING HOHEN ON ron brings the nitrogen and hydrogen closer together so that they can react and hence increases the rate of reactionHeterogeneous catalyst incatalytic converters + Heterogeneous catalysts are also usedin the catalytic removal of oxides of nitrogen from the exhaust gases of carengines * The catalysts speed up the conversion of: © Nitrogen oxides (NOy) into harmless nitrogen gas (N2) © Carbonmonoxide (CO) into carbon dioxide (CO2) + The catalytic converter has a honeycomb structure containing small beads coated with platinum, palladium, or rhodium metals which act as heterogeneous catalysts * The mode of action of the catalysts isas following © Adsorption of thenitrogen oxides and CO onto the catalyst surface © The weakening of the covalent bonds within nitrogen oxides and CO 2 Formation of new bonds between: = Adjacent nitrogen atoms to form Np molecules = COand oxygen atoms to form CO, molecules © Desorption of N2 and CO; molecules which eventually diffuse away from the metal surface CATALYST (PLATINUM, PALLADIUM. OR RHODIUM ON A HONEYCOMB) The metals in catalytic converters speed up the conversion of nitrogen oxides and CO into Nz and CO2 respectivelyHomogeneous Catalysis + Homogeneous catalysis often involves redox reactions in which the ions involved in catalysis undergo changes in their oxidation number © Asions of transition metals can change oxidation number they are often good catalysts + Homogeneous catalysts are used in one step and are reformed inalater step The iodine-peroxydisulfate reaction * This isa very slow reaction in which the peroxyaisulfate (Sz O32-) ions oxidise the iodide toiodine $2Og?" (aq) + 21 (aq) + 2804?" (aq) + Iz (aq) * Since both the $202 and | ions have anegative charge, it will require alot of energy forthe ions to overcome the repulsive forces and collide with each other * Therefore, Fe** (aq) ions are used as ahomogeneous catalyst * The catalysis involves two redox reactions © First, Fe ions are reduced to Fe** by I> 2Fe>* (aq) + 21" (aq) > 2Fe?* (aq) + |2 (aq) © Then, Fe2*is oxidized back to Fe%* by S052 2Fe3* (aq) + $2042" (aq) + 2Fe?* (aq) + 20,2" (aq) * Byreacting the reactants with a positively charged Fe ion, there are no repulsive forces, and the activation energy is significantly lowered * The order of the tworeactions does not matter © So, Fe" canbe first oxidised to Fe** followed by the reduction of Fes" to Fe®*UNCATALY SED REACTION CATALYSED REACTION S,0; + 27 Fe* —> Fe™* REACTION 4 ENTHALPY CHANGE AH Fe?*—> Fe > REACTION 2 = 28Q + PROGRESS OF REACTION The catalysed reaction has two energy ‘humps’ because it is a two-stage reactionNitrogen oxides & acidrain As fossil fuels contain sulfur, burning the fuels will release dilute sulfuric acid (H2SO.,) into the atmosphere which can cause acidic rain $03(g) + H2O(l) + H2SOq(aq) Nitrogen oxides can act as catalysts in the formation of acid rain by catalysing the oxidation of SO, toSO3 NO2(g) + SO2(g) +» SO3(g) + NO(g) The formed NO gets oxidised to regenerate NO» NO(g) + %O2(g) + NO2(g) The regenerated NO, molecule can again oxidise another SO, molecule to SOz which will react with rainwater to form H,SO, and soon Enzymes Enzymes are biological catalysts that are made up of proteins They increase the rate of reactions that take placeincells The active sites of enzymes are very specific and will only bind molecules (also called substrates) witha similar shape This is also known as the lock-and-key mode! © The substrate molecule fits inthe enzyme's active site like a key fits ina lock Because of this, enzymes are highly specific and will only speedup specific reactions