Le Chatlier’s principle Lab Introduction This experiment will give you an opportunity to determine the equilibrium constant for the formation of Fe(SCN)2+. Moreover, the experiment will require you to use Le Chatelier’s principle. Concept of the experiment: When the reaction between Fe3+ and SCN- (thiocyanate) ions in aqueous solution comes to equilibrium, the system consists of the reactants and Fe(SCN)2+. Fe3+(aq) + SCN-(aq) ↔ Fe(SCN)2+(aq) The product is a complex ion that has a coordinate covalent bond between the iron atom and an atom (probably the S atom) from the thiocyanate anion. The color of this complex ion (redish-orange in the visible spectrum of light) is so intense that thiocyanate ions can be used to detect very small quantities of Fe3+. Interestingly, Fe(SCN)2+ appears to exist solely in solution. Solid compounds containing this ion have never been isolated. The objective of this experiment is to determine the equilibrium constant for this reaction. The equilibrium constant is given by the expression: [Fe(SCN)2+] K= ----------------------[Fe3+][SCN]where the concentrations of the substances are those at equilibrium. If these concentrations are measured or inferred, K can be calculated easily. Because the reactants are essentially colorless, whereas the complex ion is deeply colored (redish-orange), you will use a spectrophotometer to monitor the # transmittance, %T, due to the complex ion. The absorbance, A, (calculated from: 2-log%T ) is proportional to the concentration, c of the species that absorbs the light – in this case, Fe(SCN)2+ according to Beer’s law, A = kc. After our previous laboratory – “Spectrophotometer Lab”, you already know a great deal about using this law. After the concentration of Fe(SCN)2+ has been measured by way of absorbance, the concentrations of the reactants can be inferred from their starting concentrations and the concentration of the complex ion. There is a problem, however. To determine k, we must determine the absorbance’s of a series of solutions with known amounts of the complex ion. How can known amounts of Fe(SCN)2+ be obtained? After all, this substance is an active participant in the equilibrium with Fe3+ and SCN- ions. Stoichiometric quantities of the reactants will not yield a known amount of the product. This difficulty can be avoided. Le Chatelier’s principle indicates that a net reaction from left to right (that is, in the forward direction) can be achieved when more of a reactant is added. As more and more of the same reactant is added, more and more of the product forms. It is possible to add so much of this reactant that essentially all of the other reactant is converted to the product. You will use limiting quantities of Fe3+ and overwhelming amounts of SCN- to achieve this result. The amount of Fe(SCN)2+ that is formed will then be essentially identical to the starting amount of the limiting reactant. In this manner, you will prepare a series of solutions with known concentrations of Fe(SCN)2+. You will calculate the absorbance’s of these solutions at 450 nm (blue-green portion of the visible spectrum), the wavelength of maximum absorbance. When these absorbances are plotted against the concentrations of Fe(SCN)2+ on a graph, k can be determined from the slope of the straight line using linear regression. You will do this on Excel. Once k has been determined, working under these conditions will no longer be advantageous. In fact, you will determine the equilibrium constant K under conditions in which substantial amounts of both of the reactants ant the product are present. Doing the calculations You will have to account for every dilution in order to do the calculations in this experiment. In the determination of k (runs 1-5), you will need to construct a graph in which absorbance appears on the vertical axis and the concentration of Fe(SCN)2+, in moles per liter, appears on the horizontal axis. This will be done in Excel. Report k in Table 1. Print your graph – including the equation for a straight line…..be sure to set the yintercept to 0. You will you calculated product and reactant concentrations to determine K, the equilibrium constant, for this reaction. You will then ultimately report the average K for runs 6-15. Le Chatlier’s principle Lab Procedure **NOTE: Use instructions provide by the instructor – DO NOT USE INSTRUCTIONS IN CHEMLAB! To remove the instructions on the screen, and free-up more working area, perform the following operation: click on the OPTIONS tab; then click on LAB ONLY. The instructions “disappear” and all of the area is now lab space.** Determining k in Beer’s law 1) Obtain spectrophotometer from equipment menu and select 450nm. 2) Right click on the spectrophotometer and select chemicals. 3) From the chemicals menu add 1mL of 0.0001 M Fe(NO3)3 Note: this chemical appears as (0.000M) Iron (III) nitrate – Fe(NO3)3 in the chemicals window………..this is a slight bug in the software where not enough places past the decimal place are reported. Use 0.0001 M Fe(NO3)3 for your calculations. 4) From the chemicals menu add 5 mL of 1M KSCN. 5) From the chemicals menu add 4 mL of 0.1M HNO3 6) Right click on the spectrophotometer, select spectrophotometer procedures – insert sample. 7) Record % Transmission from the spectrometer. 8) Right click on the spectrophotometer, select spectrophotometer procedures – remove sample. 9) Right click on the spectrophotometer and select empty to clear the contents of the cuvet. 10) Repeat above procedure for remaining samples 2-5 as follows: Run # 1 2 3 4 5 0.0000001 M Fe(NO3)3 (mL) 1.0 2.0 3.0 4.0 5.0 1 M KSCN (mL) 0.1 M HNO3 (mL) 5.0 5.0 5.0 5.0 5.0 4.0 3.0 2.0 1.0 0 Determining the equilibrium constant Do not use the 0.0001 M solution of Fe(NO3)3 in this part of the experiment. Use the 0.0025 M solution of this substance instead. Note: this chemical appears as (0.003M) Iron (III) nitrate – Fe(NO3)3 in the chemicals window………..this is a slight bug in the software where not enough places past the decimal place are reported. Use 0.0025 M Fe(NO3)3 for your calculations. Do not use the 1 M KSCN solution in this part of the experiment. Use the 0.0025 M solution instead. Note: this chemical appears as (0.003M) Potassium Thiocyanate – KSCN in the chemicals window………..this is a slight bug in the software where not enough places past the decimal place are reported. Use 0.0025 M KSCN for your calculations. Repeat the above spectroscopic procedures above for concentrations of reactants as follows: (record % transmittance for each run). Note: Add HNO3 first, then the other two reactants – otherwise the software will not give the correct transmittance data! Run # 6 7 8 9 10 11 12 13 14 15 0.0025 M Fe(NO3)3 (mL) 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 0.0025 M KSCN (mL) 1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0 0.1 M HNO3 (mL) 5.0 4.5 4.0 3.5 3.0 4.0 3.5 3.0 2.5 2.0 Le Chatlier’s principle Lab Name:__________ Section:_________ Observations Data: Determining k in Beer’s law Table 1 Run 1 2 3 4 5 [Fe(SCN)2+] (mol/L) %T A (2-log(%T)) 1.0 x 105 83.22 0.080 k – from regression (L/mol) Representative calculation for run 1: [Fe(SCN)2+] = 0.0001 M x (1.0ml / 10mL) = 1.0 x 105 According to Beer’s law, A = kc. When your absorbances are plotted against the concentrations of Fe(SCN)2+ on a graph, k can be determined from the slope of the straight line using linear regression. You will do this on Excel. Report k in Table 1. Print your graph – including the equation for a straight line…..be sure to set the yintercept to 0. Table 2 Run %T A (2-log(%T)) 6 7 8 9 10 11 12 13 14 15 75.31 0.123 Starting [Fe3+] (mol/L) 3.6 x 10-4 Starting [SCN-] (mol/L) 3.6 x 10-4 [Fe(SCN)2+] (mol/L) Equilibrium [Fe3+] (mol/L) 1.5 x 10-5 3.4 x 10-4 Equilibriu m [SCN-] (mol/L) 3.4 x 10-4 Representative calculation for run 6: [Fe3+] = [SCN-] = 0.0025 M x (1.0mL / 7.0mL) = 3.6 x 10-4 M (starting) [FeSCN2+] = A/k = 0.123 / (8.1 x 103 L/mol) = 1.5 x 10-5 M Equilibrium [Fe3+] = [SCN-] = 3.6 x 10-4 M – 1.5 x 10-5 M = 3.4 x 10-4 K = [Fe(SCN)2+]/([Fe3+][SCN-]) = 1.5 x 10-5 / ((3.4 x 10-4)(3.4 x 10-4)) = 1.3 x 102 K 1.3 x 102 Representative calculation for run 7: [Fe3+] = 0.0025 M x (1.0mL / 7.0mL) = 3.6 x 10-4 M (starting) [SCN-] = 0.0025M x (1.5mL/7.0mL) = 5.4 x 10-4 M (starting) [FeSCN2+] = A/k = 0.181 / (7.98 x 103 L/mol) = 2.26 x 10-5 M Equilibrium [Fe3+] = 3.6 x 10-4 M – 2.26 x 10-5 M = 3.37 x 10-4 Equilibrium [SCN-] = 5.4 x 10-4 M – 2.26 x 10-5 M = 5.17 x 10-4 K = [Fe(SCN)2+]/([Fe3+][SCN-]) = 2.26 x 10-5 / ((3.37 x 10-4)( 5.17 x 10-4)) = 1.3 x 102 Report average K for your set of data: Average K for runs 6-15 = _____________ Discussion