MassTransfer13.

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1/16/14

HETEROGENEOUS KINETICS: MASS TRANSFER ACROSS A BOUNDARY LAYER INSTRUCTIONS FOR STUDENTS
SAFETY I2, molecular o! "e, # $ %$l& 'o( c a"! a #e)ere rr 'a"'* Corrosive, causes burns and is harmful by inhalation and through skin absor tion. !ublimes at room tem erature to yield dangerous levels of va or1. "rotective gloves and safety goggles must be used #hile handing iodine$iodide solutions. Io! "e+Io! !e a,ueou# #olu' o" # $ %$l& 'o( c a"! a #e)ere rr 'a"'* %armful by inhalation and through skin absor tion&. "rotective gloves and safety goggles must be used #hile handing iodine$iodide solutions. KI, -o'a## um o! !e, # m l!l& 'o( c a"! ca" cau#e rr 'a' o". 'mmediately #ash #ith co ious amount of soa and #ater u on contact to the skin3. GOALS "art ( ) *etermine the diffusion$limited reaction rate for the reduction of tri$iodide, '3$, to iodide, '$, under different flo# conditions in solutions of differing viscosities. 1. +inear otential s#ee s of the electrical otential of a latinum #orking electrode #ill be done to obtain the rate of tri$iodide reduction at different rotation s eeds. The same e, eriments #ill be carried out in an a-ueous solution and a ./01v/v2 glycerol/%&3 solution. "art 4 ) 5valuation and data analysis. &. 6rom a +evich lot (iL vs. 2, calculate the diffusion coefficient of '3$ in %&/ and in ./01v/v2 glycerol/%&3. 3. 7se the !tokes$5nstien e-uation to evaluate the e, erimentally determined diffusion coefficients. 4. "lot an estimate of the concentration of reactant, '3$, at the surface of the electrode as a function of a lied otential.

INTRODUCTION %eterogeneous catalysis and diffusion through a boundary layer are fundamental conce ts of chemical engineering and the understanding of both is a necessity in good reactor design. 5,am les of heterogeneous catalysis reactors are innumerable8 t#o classic e,am les are the automobile catalytic converter and hydrogenation of a carbon$carbon double bond over a latinum catalysis. %ere the reduction reaction of tri$iodide to iodide at a latinum electrode #ill be investigated under different flo# conditions and in solutions of differing viscosities. This e, eriment is designed to hel students understand diffusion across a boundary layer from a bulk solution to a reactive surface. !uch a case is often resented in both trans ort henomena and reactor design courses. *iscussions of this case can be found in Trans ort "henomena by 4ird, !te#art and +ightfoot4 1cha ter 19, ages ..1$..42 and in 6undamentals of Chemical :eaction 5ngineering by *avis and *avis. 1cha ter 6, ages 194$1;/2. SCENARIO <ou and your research team have been charged #ith the task of develo ing of a ne# reactor for removing contaminants from an industrial #aste stream. The a-ueous #aste stream is one of varying viscosity due to fluctuation in glycerol content ) varying from traces to a ro,imately ./0 glycerol. "rior to tackling the design of the reactor you need to evaluate the change in the diffusion coefficient of a dilute analyte and the change in the diffusion boundary layer at the catalytic surface in a-ueous solutions of differing viscosities. To do so you #ill conduct electrochemical e, eriments #ith a latinum rotating disk electrode to analy=e a mock #aste stream of iodine and iodide of kno#n concentrations. <ou are to e, erimentally determine the diffusion coefficient of '3$ in #ater and again in a ./0 1v/v2 glycerol/%&3 solution. Com are the e, erimental value of '3$ in #ater to the ublished value of 1.1,1/$. cm&/s and use the !tokes$5instein e-uation to determine the accuracy of your e, erimental value of the diffusion coefficient in ./0 glycerol. 'n addition, an analysis of the concentration of reactant s ecies at the reactive surface as a function of reaction driving force 1a lied otential2 #ill be hel ful in understanding the system. THEORY (t reducing otentials, otentials belo# the o en circuit otential, a-ueous tri$iodide is reduced to iodide at a latinum electrode, reaction 112. 112 7 on dissolution in %&3 nearly all '& is com le,ed by iodide ions and is resent as '3$.

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The reaction rate of 112 is de endent on the a lied electrode otential ) the greater the difference bet#een a lied otential and the standard otential of the redo, cou le 1in this case / >2 the greater the reaction rate. (t significantly large otential differences the reaction rate is limited by mass diffusion of reactant across the boundary layer as the concentration of reactant at the electrode surface is =ero. %ere a t#o$electrode cell #ill be used to study the change in diffusion$limited reaction rate of the reduction of tri$iodide to iodide. ( t#o$electrode cell is com rised of a #orking electrode, the electrode that is actively controlled and monitored, and a counter electrode. 'n this case both the #orking and counter electrodes are latinum, the #orking electrode a rotating disk and the counter sim le latinum #ire. The rotating disk electrode is a commonly used system for studying electrochemical reactions as the flo# conditions are #ell kno#n and redictable. ( rotating disk electrode 1:*52 is ?ust that, a disk electrode encased in an inert, rotective shell attached to a rotating shaft. @hen an :*5 is rotated in a stationary fluid the velocity on the surface of the disk is =ero in both the radial and normal a,is and, if the no$sli condition is assumed, the velocity in the angular direction is vAr, #here is the rotation s eed in radian er second. This is not to say that there is only angular fluid flo# in the bulk solution as the rotation of the electrode dra#s fluid to#ards the electrode surface in the normal direction and radially out#ard in the lane of the electrode. The flo# attern created by a rotating disk electrode in motion is sho#n in figure 1.

Figure 1. RDE flow pattern.

Convective trans ort 1or convective diffusion2 redominates at large distances from the electrode surface to the boundary layer at the electrode surface. The boundary layer ad?acent to the electrode surface has no velocity in the radial or normal direction and only velocity in the angular direction. (lso, the concentration of dissolved s ecies is uniform in the radial and angular dimension and is only a function of the normal distance to the electrode. The current roduced at the #orking electrode is essentially the reaction rate and the current density, the current er area at the electrode, is the flu, of reactant. 5-uation & describes the current density as a function of reactant concentration and diffusion coefficient using 6ickBs la# and 6aradayBs la#. CA C A CA i = nFD A = nFD A 1&2 x @here n is the number of electrons transferred in the reaction, F is 6aradayBs constant, D( is the diffusion coefficient of ( in the solvent 1#ater2, is the thickness of the boundary layer and C( is the concentration of s ecies (. The su erscri ts and indicate the bulk solution and the electrode surface res ectively. (t the diffusion$limited current density 1and remember current density is essentially a reactant flu,2 the concentration of reactant at the electrode surface a roaches =ero and,

 CA iL = nFD

132

#here i+ is the limited current density in am eres er area. The diffusion$limited current at a rotating disk is described by the +evich e-uation belo#.
& 3 1 & 1 6 iL = /.6&/nFD A CA

142

#here is the kinematic viscosity and is the rotation s eed in radian er sec. ( diffusion coefficient * for analyte ( in solvent can be e,tracted from a data set of limiting currents at different rotation s eeds. @ith the +evich e-uation and e-uations & and 3 the boundary layer thickness, diffusion coefficient of ( in solvent and the concentration of s ecies ( at the electrode surface can all be determined for reduction of tri$iodide on a latinum :*5. A//ARATUS The ma?or com onents of the a aratus are8 (utolab otentiostat. Controls the electrical otential bet#een #orking and counter electrodes, also measures the current roduced in the electrochemical cell. "latinum rotating disk electrode 1:*52. ( latinum disk encased in Teflon, the #orking electrode. "latinum #ire, the counter electrode. >ariable s eed rotator. %olds, rotates and rovides electrical connection to the :*5.

CHEMICALS 'odine$'odide a-ueous solution. T#o solutions #ill be rovided8 12 'odine$'odide a-ueous solution in 1//0 %&3 #ith C'&D A /.&.4 g/liter, CE'D A 16.6 g/liter. &2 'odine$'odide a-ueous solution in ./0 1v/v2 glycerol/%&3 #ith C'&D A /.&.4 g/liter, CE'D A 16.6 g/liter. >iscosity, A ..;/9 centi ose and density, A 1.1&.9 g cm$3 F &/C 6. /ROCEDURE 1. Thoroughly rinse the electrodes #ith distilled #ater. &. "our a ro,imately ./ ml of iodide/iodine solution into a 1// ml glass beaker. 3. 5lectrochemical cell set$u 8 T#ist the cleaned latinum :*5 onto the rotator.

Connect the #orking electrode #ires 1@5 and !2 to the rotator. Connect the reference 1:52 and counter electrode 1C52 #ires in series. "lace the latinum counter electrode into the iodine$iodide solution. !ecure the electrode #ith a clam . Make sure that the electrode GalligatorB cli is not in or touching the solution. +o#er the latinum :*5 #orking electrode into the iodine/iodide solution.

4. 5ngage the o#er button on the (utolab otentiostat and o en the otentiostat control soft#are, H"5!. 5nsure that the (utolab 'nterface in enabled 0 double click on the (utolab icon in the lo#er righthand toolbar in @indo#s, the #indo# should indicate that status of the interface. .. 'n H"5!, under the FILE menu select O-e" -roce!ure. 'n c8/(utolab select the GIo! "e l "ear #1ee-B rocedure. 5nsure that the follo#ing arameters on "age 1 are set. /re'rea'me"' 6irst conditioning otential 1>2 8 / *uration 1s28 / 5-uilibrium time 1s2 Mea#ureme"' Iumber of scans8 1 Cell off after measurement , !tandby otential 1>2 8 / /o'e"' al# 4egin otential 1>28 / 5nd otential 1>28 $1./ !te otential 1>28 /.///4. !can rate 1>/s28 /.//. 6. !et the rotator s eed to the a ro riate r m 11//, 4//, ;//, 16//, &.//2. Turn on the rotator. J. 'n H"5!, ush START to begin the linear otential s#ee . (fter the s#ee has finished save data by selecting Sa)e 1or2 !a'a in the F le menu of the Da'a /re#e"'a' o" 3 "!o1. 9. 5, orting data *ouble click on the data curve and click on the DATA button in the o $u #indo#. T#o columns of data should a ear in a second o $u #indo#. This data can be co ied to an e,cel s readsheet #ith the CO/Y menu in the to left hand corner. Make sure to correctly label the voltage and current data columns in your s readsheet. ;. :e eat the linear s#ee at all rotation s eeds listed in 6. REFERENCES 1. 'odine M!*!, !igma$(ldrich, &//6 &. 'odine$'odide M!*!, !igma$(ldrich, &//6 .

3. "otassium iodine M!*!, !igma$(ldrich, &//6 4. 4ird, !te#art and +ightfoot, Trans ort "henomena &nd 5dition, @iley K !ons, Ie# <ork, &//&. .. *avis and *avis, 6undamentals of Chemical :eaction 5ngineering, McHra# %ill, Ie# <ork, &//&. 6. 6orsythe, @.5. 11;.4L&//32. !mithsonian "hysical Tables 1;th :evised 5dition2. 1 . 3&12. Enovel. 3nline version available at htt 8//###.knovel.com/knovel&/Toc.?s M 4ook'*AJ36K>ertical'*A0