é Experiment 23 Determination of the Equilibrium Constant for a Chemical Reaction Poon chemical substances reac, the reaction typically does not go to completion. Rather, the system goes to some intermediate state in which both the reactants and products have concentrations that do not change with time. Such a system is said to be in chemical equilibrium. When in equilibrium at a particular temperuture, « reaction mixture obeys the Law of Chemical Equilibsiurm, which imposes a condition on the concentrations of reactants and products. This condition is expressed in the equilibrium constant X, for the reaction, In this experiment we will study the equilibrium properties ofthe reaction between iron(TII) ion and thio- cyanate ion: FeM(ag) + SCNCaq) == FeSCN*(aq) w ‘When solutions containing Fe ion and thiocyanate ion are mixed, Reaction 1 occurs to some extent, form- ing the FeSCN* complex ion, which has a deep red color. As a result of the reaction, the equilibrium amounts ‘of Fe and SCN- will be less than they would have been if no reaction oceumred; for every mole of FeSCN* that is formed, one mole of Fe and one mole of SCN- will eact. According to the Law of Chemical Equilibrium, the equilibrium constant expression K, for Reaction 1 is formulated as follows: [FeSCN*] _ Tre SCNT @ ‘The value of K, in Fquation 2 is constant at a given temperature, This means that mixtures containing Fe ‘and SCN will rezet until Equation 2is satisfied, so that the same value of the X, will be obtained no matter ‘what inital amounts of Fe** and SCN" were used. Our purpose inthis experiment will be to find K, for this reaction for several mixtures mad up in different ways, and to show that K, indeed has the same value in each of the mixtures, The regction isa particularly good one to study because K, is of a convenient magnitude and the color of the FeSCN* ion makes for an easy analysis of the equilibrium mixture ‘The mixtures will be prepared by mixing solutions containing known concentrations of iron(ID nitrate, Fo(NO,},,and potassium thiocyanate, KSCN, The color ofthe FeSCN?* ion formed will allow us to detenmine its equilibrium concentration. Knowing the initial composition of a mixture and the equilibrium concentration of FeSCN*, we can calculate the equilibrium concentrations ofthe est of the pertinent species and then deter- mine K, Since the calculations required in this experiment may not be apparent, we will go through a step-by-step procedure by which they can be made. AS & specific example, let us assume that we prepare a mixture by mixing 10.0 mL. of 2.00 x 10° M Fe(NO,), with 10.0 mL of 2.00 x 10° M KSCN. As a result of Reection 1, some red FeSCN* ion is formed, By the method of analysis described late, its concentration at equilibrium Js found to be 1.50x 10M. Our problem isto find K, forthe reaction from this information. To do this we first need to find the inital number of moles of each reactant in the mixture, Second, we determine the number of moles of product that were formed at equilibrium. Since the product was formed atthe expense of reac~ tants, we ean calculate the aruount of each rexetant thet was used up. In the third step we find the number of moles of each reactant remaining in the equilibrium mixture, Fourth, we determine the concentration of each reactant, Finally, in the fifth step we evaluate K, for the reaction182 Exporiment 23. Dotorninaton ofthe Eculloram Constant fora Chemical Reaction Step 1 Step 2 Step 3 Step 4 Stop 5 Finding the Initial Number of Moles of Each Reactant, This requires relating the vol- ‘umes andl concentrations of the reagent solutions that wore mixed to the numbers of moles of cach reactant species in those solutions. By the definition of the molarity, M,. of a species A, les * “no Titers of solution, V or no. molesA=M,x¥ Using Equation 3, itis easy to find the inital number of moles of Fe and SCN. For each solution the volume used was 10.0 mL, or 0.0100 L. The molarity of each ofthe solutions Was 2.00% 107M, 50 Mg, =2.00x 10? M and Moy. = 2.00% 109M. Therefore, in the reagent solutions, we find thet initial no. moles Fe™*= M5, V = 2.00 x 10-* M x 0,0100 L = 20.0 x 10-* moles intial no. moles SCN" = May. X V= 2.00 x 10 M x 0,0100 L = 20.0 x 10- moles Finding the Number of Moles of Product Formed. Here ogain we can use Equation 3 to advantage. The concentration of FeSCN® was found to be 1.50 x 10M at equilibrium, The volume of the mixture at equilibrium is the sum of the two volumes that were mixed, and is 20.0 mL, or 0.0200 L. So, ‘0, moles FeSCN* rasente & Ve 50 x 104M x 0.0200 L = 3.00 10° moles ‘The number of moles of Fe and SCN* that were used up in producing the FeSCN® must also both be equal to 3.00 x 10-° moles since, by Equation 1, it takes one mote Fe and one ‘mole SCN* to make each mole of FeSCN*. Finding the Number of Moles of Each Reactant Present at Equilibrium. In Step 1 we determined that initially we had 20.0 x 10° moles Fe™ and 20.0 x 10-* moles SCN pres- cnt, In Step 2 we found that in the reaction 3.00 x 10° moles Fe and 3,00 x 10-6 moles ‘SCN- were used up. The number of moles present at equlibsium must equal the number we started with minus the number that reacted, Therefore, at equilibrium, ‘no, moles at equilibrium = initial no, moles ~ no, moles used up cequil. no. moles Fe™= 20.0 x 10-8 — 3,00 x 10° = 17.0 x 10 moles cequil, no, moles SCN = 20.0 x 10-* ~ 3,00 x 10-5 = 17.0 10 moles Find the Concentrations of All Species at Equilibrium. Experimentally, we obtained the ‘concentration of FeSCN directly. [FeSCN*] = 1.50 x 10+ M. The concentrations of Fe™* ‘and SCN” follow from Equation 3. The nomber of moles of each of these species at equi librium wes obtained in Step 3. The volume of the mixture being studied was 20,0 ml, ot 0.0200 L. So, at equilibriw, 7 no. moles Fe __ 17.0%10" moles [Fe = Mss De 850x104 M fo, moles SCN-_ 17.010 moles _ 9 gy ig Moow- = Yolume of solution “~~ 0.02001, = 50x10 M Finding the Value of K, for the Reaction. Once the equilibrium concentrations of all the reactants and products are known, one needs merely to substitute into Bquation 2 to deter mine K, 150x104 FFE ISCN |” WSOKIO-x(8sOxIO} “77% ® RYPPPT IPT AIT TTT TITIITAIAITETAFIFAAIE |SITCTW SSLPECSELELEDPE 8 9 8 2 ° 2 ® 3 [Experiment 28, Detomination ofthe Equi Constant fora GnemicalResetion 188 Step § Continued. In this experiment you will obtain data similar to that shown in this example. ‘The calculations involved in processing that data are completely analogous to those we have ‘made, (Actually, your results will differ from the ones we obtained, since the data in our example were obtained at a different temperature and so relate toa different value of K,) In carrying out this analysis we made the assumption that the reaction which occurred was given by Equation 1. There is no inherent reason why the reaction might not have been Fe*(aq) +2 SCN-(eq) 'e(SCN),"(aq) © If you are interested in matters of this sort, you might ask how we know whether we are actually observing ‘Reaction | or Reaction 5. The line of reasoning is the following, If Reaction 1 is occurring, K, for that reac- tion as we calculate it should remain constant with different reagent mixtures. If, however, Reaction S is going ‘on, K, 2s calculated for that reaction should remain constant. Inthe optional part of the Data and Calculations section, we will assume that Reaction 5 occurs and make the analysis of K, on that basis. The results of the ‘wo sets of calculations should make it clear that Reaction 1 is the one that we are studying. ‘Two analytical methods can be used to determine [FeSCN*] in the equilibrium mixtures, The more pre- cise method uses a specttophotometer, which measures the amount of light absorbed by the red complex at 447 nm, the wavelength at which the complex most strongly absorbs. The absorbance, A, of the complex is proportional to its concentration, M, and can be measured directly on the spectrophotometer: Asim © ‘Your instructor will show you how to operate the spectrophotometer, if available to your Irboratory, and will provide you with a calibration curve or equation from which you can find [FeSCN*) once you have dster- mined the absorbance of your solutions. Sec Appendix IV for information about spectrophatometers Tithe other analytical method a solution of known concentration of FeSCN* is prepared. The [FeSCN™) ‘concentrations in the solutions being studied! are found by compsting the color intensities ofthese solutions ‘with that of the known. The method involves matching the color intensity ofa given depth of unknown solu- tion with that for an adjusted depth of known solution. The actual procedure and method of calculation are discussed in the Experimental Procedure section. Tn prepating the mixtures in this expetiment we will maintain the concentration of H* ion at 0.5 M. The hydrogen ion docs not participate directly inthe reaction, bat its presence is necessary to avoid the formation of brown-colored species such as FeOH™, which would interfere withthe analysis of [FeSCN ‘wexnvoun sire uso nie GS Experimental Procedure peereee eee Label five regular test tubes (18 mm x 150 ram) 1 to 5, with labels or by noting theie positions on yout test tube rack, Pour about 30 mit 2.00 x 10% M Fe(NO,), in 1 MHNO, into a dry 100-mL beaker: Pipet 5.00 mL, ‘ofthat solution into cach test ube. Then add sbout 20 ml. 2.00 x 10"9M KSCN to another cry 100-miL beaker, Pipet 1,2, 3, 4, and $ mi from the KSCN beaker into cech of the corresponding tet tubes labeled | to 5. Then pipet the proper number of milliliters of water into each test tube to bring the total volume in each tube to 10.00 mL. ‘The volumes of reagents to be ade to each tube are summarized in Table 23.1, which you should complete by filliog in the required volumes of water. See Appendix IV for a discussion ofthe use of pipets Mix cach solution thoroughly with 2 glas string rod, Be sure to dry the siting rod aftr mixing each solution, Method I. Analysis by Spectrophotometric Measurement Place a portion of the mixture in tube I in a spectrophotometer cell, as demonstrated by your instructor, and ‘measure the absorbance of the solution at 447 nm. Determine the concentration of FeSCN* from the ealibra- tion curve provided for each instrument or from the equation furnished to you. Record the value on the Data184 Experiment 29. Determination ofthe Eaullvisn Constant fora Chemice! Reaction Table 23.4 1 Volume Fe(NO), solution (aL) 500 Voluzne KSCN solution (mL) 1.00 Volume #,0 (ml.) _ — i i page. Repeat the measurement using the mixtures in each of the other test tubes. For a discussion of how absorbance and concentration are related, see Appendix IV, Method II. Analysis by Comparison with a Standard Prepare @ solution of known [FeSCN*] by pipetting 10.00 mL. 0.200 M Fe(NO,), in 1 M HINO, into # test tube and adding 2,00 mL, 0.00200 M KSCN and 8.00 mi water. Mix the solution thoroughly with e stirring rod. Since in this solution [Fe] >> [SCN-], Reaction 1 is driven strongly to the right. You can assume with- out serious error that essentially ali the SCN added is converted to FeSCN*. Assuming that this is the case, calculate [FeSCN* in the standard solution and recor the value on the Data page: ‘The (FeSCN] in the unknown mixture in test tubes I to 5 can be found by comparing the intensity of the red color in these mixtures with that of the standard solution. This can be done by placing the test tube containing Mixture 1 next to atest tube containing the standard. Look down both test tubes toward a welle iliuminated piece of white paper on the laboratory bench, Pour out the standard solution into a dry, clean beaker until the color intensity you see down the tube con- taining the standard matches that which you see when looking down the tube containing the unknown. Use a well-lit piece of white paper as your background, When the colors match, the following relation is valid [FeSCN* > depth of unknown solution = [FeSCN*] x depth of standard solution (7) ‘Measure the depths of the matching solvtions with a rule and record them, Repeat the measurement for ‘Mixtures 2 through 5, recording the depth of each unknown and thet of the standard solution which matches it in intensity. DISPOSAL OF REACTION PRODUCTS. In this experiment, reactant concentrations are very low. 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A student mixes $,00 mL. 2.00 x 10°? M Fe(NO,), with $.00 ml. 2,00 x 10 M KSCN She finds that in the equilibrium mixtare the concentration of FeSCN* is 140 x 10+ M, Find K, for the reaction Fe (aq) + SCN (aq) => FeSCN™ (a, ‘Stop 1 Find the number of moles Fe* and SCN" initially present. (Use Eq. 3.) moles Fe; moles SCN- ‘Stop 2 How many moles of FeSCN* ae in the mixture at equilibrium? What is the volume of the equilibrium mixture? (Use Eq. 3.) mL; moles FeSCN* How many moles of Fe and SCN* aroused up in making the FeSCN7 moles Fe; mmoles SCN Stop & How many moles of Fe™ and SCN- romain in the solution at equilibrium? (Use Ig, 4 and the results of Stops I and 2.) moles F ‘moles SCN Step 4 What arc the concentrations of Fe", SCN, and FeSCN* at equilibrium? What isthe volume of the equilibrium mixcure? (Use Hg, 3 and the results of Step 3.) (Fe M; [SCN] = M; [FeSCN*] =___M ‘Step 5 Whot isthe velue of K, forthe reaction? (Use Fa, 2 and the results of Step 4.) (continued on following page}