EXPERIMENT 5

Spectrophotometric Determination of the Equilibrium Constant of a Reaction

Cruz, S.M.M, Zaragosa, Z.G.C Institute of Chemistry, College of Science University of the Philippines, Diliman, Quezon City 1101 Philippines Abstract UV-Vis spectrophotometry is the quantitative analysis of the measurement of the transmittance of light at the UV to visible region as a function of wavelength. It quantitatively gives the absorbance of a material under a specific wavelength that is related to the materials concentration by the BeerLamberts law. The equilibrium constant of the reaction between iron (III) chloride and potassium thiocyanate is determined in this study by determining the absorbance of the blood red iron thiocyanate complex ion present in the solution formed by the reaction at equilibrium. In the study, the spectrophotometer was first set to 466nm for maximum absorbance and was calibrated in order to determine the equation that will be used for determining the concentration of the blood red complex ion formed by the reaction at equilibrium. The concentration sought from the equation will be used to determine the equilibrium constant of the reaction. The study yielded an equilibrium constant value of 408.57 which is higher than the theoretical range for the equilibrium constant values due to certain errors.

Keywords: transmittance, absorbance, spectrophotometry, wavelength, complex ions.

Introduction A spectrophotometer is a device that is capable of measuring the absorbance of a substance under a specific wavelength. It is composed of the spectrometer that produces light for any color or wavelength, and the photometer that is responsible for measuring the intensity of the light. A spectrophotometer is composed of different parts that have different purposes. The first part is the light source that gives light composed of all wavelengths. The light source can either be a tungsten halide lamp or a deuterium lamp. The next part of the spectrophotometer is the monochromator that is responsible for filtering out different wavelengths of light in order to allow the light with a specific wavelength to pass through. The filtered light will then be passed through the sample holder which contains the cuvette containing the solution with the analyte. Then the transmitted light will then be detected by the transducer and will finally give the absorbance of the solution. The absorbance of the solution can be determined by using the wavelength at which the solution absorbs the most and by getting the negative logarithm of the transmittance or the ratio between the transmitted light after absorption of the light by the solution (transmitted light) and the initial transmitted light of the light source (incident light)(eqn.1). Eqn.1 a = absorbance T = Transmittance, By using the absorbance, the molarity of the analyte can be determined using the BeerLamberts Law (eqn.2). By using this equation, the equilibrium concentration of the analyte can be obtained because the Beer-Lamberts law relates the absorbance of the colored solution by using

the maximum wavelength at which the solution absorbs the most to the concentration of the compound that contributed to the color of the solution that absorbed the light passed unto it. The Beer-Lamberts law states that the absorbance is equal to the product of the molar absorptivity coefficient, path length, and the concentration of the analyte. Eqn. 2 a = absorbance, = molar absorptivity coefficient in b = path length (in cm.) , c = analyte concentration ( in M ). The resulting concentration will then be plugged in an equation yielding the equilibrium constant of a reaction. The equilibrium constant is the ratio of the concentration of the products raised to their respective stoichiometric coefficients and that of the reactants raised to their respective stoichiometric coefficients (eqn.3). Eqn.3/c.eqn.1 for the reaction ,

0.1M HCl up to mark for the preparation of the 0.2M KSCN. The 0.2M KSCN produced were then diluted by adding 2.5mL of 0.2 M KSCN on a 250mL volumetric flask filled with about 50mL of 0.1M HCl and then diluted up to mark with 0.1M HCl in order to produce 0.002M KSCN. A 0.002M FeCl3 was prepared by weighing 1.61 grams of FeCl3 and was placed in a 50mL volumetric flask with about 10mL 0.1M HCl. Then the FeCl3 was dissolved and then diluted up to mark with 0.1 M HCl. For the production of 0.002M KSCN, 1mL 0.2M KSCN was added to a 100mL volumetric flask partially filled with 0.1M HCl and then the solution was diluted up to mark with 0.1M HCl to produce a 0.002M KSCN solution. After preparing the stock solutions, they were then used to prepare the standard solutions and the unknown solutions. Table.1 Standard solutions Standard Solution Blank 1 2 3 4 5 0.2 M 0.002 KSCN FeCl3 (mL) (mL) 1.0 0 1.0 0.1 1.0 0.25 1.0 0.5 1.0 1.0 1.0 2.0 0.1M HCl (mL) 9.0 8.9 8.75 8.5 8.0 7.0

Methodology Solution preparation Stock solutions were prepared for the preparation of the standard solutions that were used to calibrate the spectrophotometer and to establish the equation of the best fit curve. A 1000mL, 0.1M HCl was prepared by adding 82.64 mL of concentrated HCl on a 1L volumetric flask with about 100mL water inside then was diluted up to mark and then shook to produce a 1L 0.1M HCl solution. A 0.2M KSCN solution was then produced by weighing 1.94 grams of KSCN and were placed in a 100mL volumetric flask filled with about 20mL of 0.1 M HCl and then dissolved and diluted with

Standard 1 to 5 and the blank solution were prepared by adding the indicated amounts (table.1) in a 6-in test tube then were covered with parafilm and then shook in order to prevent the evaporation of the solution. And then the solutions were kept for spectrophotometric analysis.

Table.2 Unknown Solutions Solution Blank 1 2 3 0.002 KSCN (mL) 5.0 5.0 5.0 5.0 0.002 FeCl3 (mL) 0 3.0 4.0 5.0 0.1 M HCl 5.0 2.0 1.0 0

For the unknown solutions, the cuvette was rinsed thrice with distilled water and twice or thrice with the unknown solution. Then after rinsing, the unknown solutions were then placed in the cuvette and the cuvette was placed in the sample holder and the absorbance was then determined. Results and Discussion In the experiment, the researchers prepared the stock solutions first by preparing 0.1M HCl from concentrated hydrochloric acid (HCl) that will serve as the solvent to prevent the hydrolysis of Fe3+ into a light brown solution due to the formation of pentaaquahydroxoiron(III) Fe(H2O)5(OH)2+ (c.eqn.2b) because this ion will form if the solvent used was water. The formation of this complex will result first from the hydration of Fe3+ to [Fe(H2O)6]2+ (c.eqn.2a) and then the hydrated complex ion will then be hydrolysed to form the light brown solution of pentaaquahydroxoiron (III). Formation of this ion was prevented in order to obtain the absorbance of the solution with the analyte only because the formation of this ion will result to a greater absorbance because another color interferes with that of the analyte and the presence of that other color also absorbs light thereby yielding a much lower transmittance and a larger value for the absorbance. After preparing the solvent, 0.2M KSCN, 0.002 M FeCl3 were then prepared by weighing the right amount of KSCN and FeCl3 solids and dissolving them in 0.1M HCl. The prepared 0.2M KSCN was then diluted to 0.002M KSCN in 0.1M HCl. And from these stock solutions, the standard and unknown solutions were prepared by using the amounts listed in tables 1 and 2. c.eqn.2: a. Fe3+(aq) + 6H2O(l) [Fe(H2O)6]3+ (aq) H3O+(aq) +

The unknown solutions were then prepared by also combining the indicated amounts (table.2) in a 6-in test tube then were covered with parafilm and shook for the contents to mix. And the resulting solutions were kept for spectrophotometric analysis. Spectrophotometry The spectrophotometer was prepared by adjusting the wavelength of the light that will be used to test the absorbance. By using standard 5, the wavelength at which the solution has the greatest absorbance was measured and will then be used for the other solutions. For testing the solutions, the blank solution was first tested by rinsing the cuvette with distilled water twice and then with the blank solution twice. After rinsing, the blank solution was poured. After pouring, the cuvette was placed in the sample holder by placing the cuvette and slowly pushing the lifter in order to place the cuvette in place. Then the sample holder was covered and the absorbance was recorded. After the blank solution, the cuvette was rinsed with distilled water then with the standard solution twice and the cuvette was placed in the sample holder and the sample holder was closed. The absorbance was then recorded and the process was repeated for all the remaining standard solutions. For the unknown solutions, the cuvette was first rinsed thrice with distilled water and then rinsed with the blank solution twice. The blank solution was then placed in the cuvette and the cuvette was placed in the sample holder. The sample holder was then closed and the absorbance was then determined.

b. [Fe(H2O)6]3+ (aq) + H2O(l) [Fe(H2O)5(OH)]2+(aq)

Figure.1 Color Wheel with Wavelengths After preparing the solutions that will be used, the spectrophotometer was prepared by first determining the wavelength at which the solution absorbs the most by using standard 5 in order to have the maximum absorbance because absorbance is directly proportional to the concentration and standard 5 has the maximum concentration of the analyte. The wavelength at which the solution absorbs the most must be in the range of the wavelength for the complementary color of the color of the solution because the color of the solution shows the color that it reflects and the color that goes farthest from it will be the color it absorbs the most and also its complementary color. Since the solution is orange; therefore, the wavelength must be present in the range of the wavelength for color blue because its complementary color is blue. (figure.1) The wavelength at which the solution absorbs the most is at 466nm which is within the range of the wavelength for blue because the wavelength corresponding to blue is 430nm to 490 nm thereby making the experimental wavelength valid (figure.1). The analytical wavelength must be used in order to yield the maximum absorbance and the correct concentration because not using the analytical wavelength will yield lower absorbance that will then yield a lower concentration of the analyte. Table.3a Calibration Data Solution 1 2 3 4 5 Absorbance 0.440 0.479 0.582 0.713 1.090 Corrected Absorbance 0.042 0.081 0.184 0.315 0.692

After adjusting the wavelength of the light that will be used to determine the maximum absorbance, the spectrophotometer was then calibrated in order to determine the equation of the best fit curve that will be used in order to determine the equilibrium concentration of the analyte in the blank solutions. In calibrating the spectrophotometer, the blank solutions were first used because it is a replication of the nature of the system without the analyte. It is used in order to determine the absorbance contributed by the solution without the analyte because there is no assurance that the solution does not absorb light and also because the cuvette also absorbs light but it must be close to zero in the experiment because the blank solution used is clear and not colored. This is also done in order to yield only the absorbance of the analyte once the absorbances of the solution with the analyte is obtained. The absorbance of the analyte only can be called as the corrected absorbance and it is obtained by getting the difference of the solution with the analyte and the blank solution (eqn.4). Eqn.4 Upon obtaining the absorbance of the blank solution, the standard solutions with very large amount of KSCN were used in order to determine their respective absorbance. KSCN was added in large amounts in order to drive the reaction forward and to safely make an assumption that the initial Fe3+ concentration is estimated to be the equilibrium concentration of [FeSCN]2+ because they have a 1:1 ratio in the chemical equation (c.eqn.1) and because the initial amount of Fe3+ is so small and that of SCN- is so large that the reaction almost went to completion. (The initial concentration of the reagents used was computed in the appendix under computations section by using eqn.6).

[Fe3+]init 0.00002M 0.00005M 0.0001M 0.0002M 0.0004M

[SCN-]init 0.02M 0.02M 0.02M 0.02M 0.02M

[FeSCN]2+eq 0.00002M 0.00005M 0.0001M 0.0002M 0.0004M

The equilibrium concentration of [FeSCN]2+ are listed in table.3a wherein the equilibrium concentration of [FeSCN]2+ is equal to the initial concentration of Fe3+ because the initial concentration of Fe3+ is so small and that of KSCN is so large that the reaction was assumed to go to completion. The value for the equilibrium concentration of FeSCN2+ will then be used for determining the best fit curve by assigning it as the value for x in the beer-lamberts law (eqn.2). The value for y will be the corrected absorbance of the analyte which is [FeSCN]2+. The corrected absorbance is obtained from the difference of the absorbance of the solution and that of the blank solution (eqn.4) and the obtained absorbance of the blank solution in the experiment was 0.398 while the absorbance recorded for each of the

standards including the corrected absorbance are listed in table.3a. The slope of the best fit curve is the product of the molar absorptivity coefficient and the path length (eqn.2). And the path length used in the experiment was 1cm. The absorbance of the blank solution, for other spectrophotometers, are used to adjust the absorbance that will be used for the standard solutions and unknown solutions. The absorbance of the blank solution will be used to as to make it the zero mark wherein the absorbance of the blank solution will be the basis for obtaining the absorbance of the standard solutions by getting only the absorbance of the analyte only and without the other ions or compounds present in the solution.
y = 1704.13x + 0.0003632 R = 0.9962

Absorbance vs. [FeSCN]2+eq

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0

y Linear (y)

0.00005 0.0001 0.00015 0.0002 0.00025 0.0003 0.00035 0.0004 0.00045

Figure.2 Absorbance vs. [FeSCN]2+eq (table.3b) By getting the graph of the corrected absorbance vs [FeSCN]2+ (table.3b.), the equation of the best fit curve that will be used for the determination of the equilibrium concentration of [FeSCN]2+ in the unknown solutions can be obtained by linear regression. The graph of the corrected absorbance vs [FeSCN]2+eq is presented in figure.2 and the graph shows that the data yielded by the experiment is almost linear because it has a linearity coefficient of 0.9962 and the equation of the best fit curve has a slope of 1704.13 and a yintercept of 0.0003632; therefore, the equation of the best fit curve would be y = 1704.13x + 0.0003632(eqn.5). Eqn.5: The slope obtained from the equation of the best fit curve gives the product of and b according to eqn.2 because absorbance was assigned to be y and the concentration was assigned to be x; therefore, in the form y=mx+b, m would be the product of the molar absorptivity coefficient and the path length wherein the path length used was the length of the cuvette where the light passed through. The path length used in the experiment was estimated to be 1cm. because the length of the cuvette where the light source would hit is equal to 1cm. Since the path length is 1cm and the slope is equal to the product of the molar

absorptivity coefficient and the path length; therefore, the molar absorptivity coefficient is 1704.13 M-1cm-1 (Further computations are in the appendix under computations section.). The yintercept b in the equation represents the correction factor because the experiment has different errors. The theoretical molar absorptivity is 3550 M-1cm-1 and the experimentally determined molar absorptivity coefficient is 1704.13 which have a 52% error because of different sources of errors Table.4 Absorbance of Unknown Solutions Unknown Solution 1 2 3 Absorbance 0.663 0.740 0.813

that caused deviations from the theoretical value which are listed in table.8. As observed, the obtained value for the molar absorptivity is lower than the theoretical molar absorptivity coefficient which means that the changes in the experimentally determined absorbances were lower than that of the theoretical absorbances. Since the slope is equal to the change in the absorbance with respect to the change in concentration; therefore, errors were yielded that caused only a small change in the absorbances over a change in the molarity of [FeSCN]2+eq. [Fe3+]init 6x10-4 8x10-4 1x10-3 [SCN-]init 1x10-3 1x10-3 1x10-3

Corrected absorbance 0.260 0.337 0.410

After the calibration, the concentration of [FeSCN]2+ was then determined by testing their absorbance and substituting their respective absorbance to the equation yielded in the calibration process to solve for the concentration of [FeSCN]2+ with that specific absorbance. The processes in obtaining the absorbance of the standard solutions were the same as that in obtaining the absorbances of the unknown solutions but this time with a smaller concentration of KSCN and by using a new blank solution that will be used to obtain the corrected absorbance. The concentration of KSCN was decreased in this part in order for the equilibrium between SCNand Fe3+ to be established and to yield a small change in concentration in the reactants and the products rather than creating a reaction that was assumed to go to completion because a reaction that is assumed to have gone to completion can have a reactant concentration that is equal to zero at equilibrium thereby yielding a very large amount of K that approaches infinity as the concentration of the reactants approaches 0. Since Keq is needed in the unknown solutions; therefore, only a small change must be present in order for the reactants concentration to be present and not very small. Since the concentration of a reactant was changed

and so as the volume used; therefore, a new blank solution must be prepared in order to establish the absorbance of the solution without the analyte itself and to replicate its nature within the solution. The new absorbance of the blank solution obtained in the experiment was 0.403. By using the absorbance measured in all of the unknown solutions, the corrected absorbance that will be used in the obtained equation of the best fit curve was obtained by getting the difference in the recorded absorbance of the solution with the analyte and the absorbance of the blank solution (eqn.4). And the corrected absorbances of the solutions are listed in table.4. (Further computations are in the appendix under the computations section.). Ex: 0.663-0.403 = 0.260 By using the corrected absorbances of the unknown solutions and the equation of the best fit curve, the value for x or the concentration of the analyte at equilibrium was obtained (c.eqn.5). The obtained concentrations of [FeSCN]2+ at equilibrium are listed in table.5. (further computations are located in the appendix under computations section.). Ex: (0.260) = 1704.13(x) + 0.0003632

0.2596 = 1704.13x x = 1.52x10-4 M. Table.5 Obtained [FeSCN]2+eq Solution 1 2 3 Absorbance 0.260 0.337 0.410 [FeSCN]2+eq 1.52x10-4 1.98x10-4 2.40x10-4

Table.6 Equilibrium Concentration of Reactants and Products with Keq. Solution 1 2 3 [FeSCN]2+eq 1.52x10-4 1.98x10-4 2.40x10-4 [SCN-]eq 8.48x10-4 8.02x10-4 7.6x10-4 [Fe3+]eq 4.48x10-4 6.02x10-4 7.6x10-4 Keq 400.1 410.1 415.5

Upon obtaining the equilibrium concentration of [FeSCN]2+, the value for the equilibrium constant Keq can be computed using eqn.3. To solve for the equilibrium concentration of the reactants, an ICE table must be created and the initial concentrations must first be determined. The initial concentration of the reactants used in the experiment was obtained using eqn.6 and the resulting initial concentrations are listed in table.4. After determining the initial concentrations, the equilibrium concentrations can be calculated by creating the ICE table (table.7) and the resulting equilibrium concentrations in the experiment are listed in table.6. By substituting the equilibrium concentrations listed in table.6 in eqn.1, the equilibrium constant can be obtained and the obtained equilibrium constants for the three different unknown solutions were then averaged to obtain the Keq for the reaction (eqn.7). (Further computations are located in the appendix under computations section.) Eqn.6: Eqn7: Keq Average = Ex: (Keq1) [Fe3+]init = = 6x10-4M

[SCN-]init = [FeSCN]2+eq = Table.7 ICE Table

= 1x10-3M = 1.52x10-4

Initial Change Equilibrium

Fe3+ 6x10-4 -x 0.0006 x

SCN1x10-3 -x 0.001-x

[FeSCN]2+ 0 +x x

Since [FeSCN]2+eq = x = 0.000152M ; therefore, x = 0.000152M [Fe3+]eq = 0.0006M 0.000152M = 0.000448M [SCN-]eq = 0.001M 0.000152M = 0.000848M Keq1 = Keq1 = = 400.10

= [reactant]init or

By applying this process for unknown solutions 2 and 3, the resulting Keq were 410.1 and 415.5 respectively. The process for solving Keq2 and Keq3 are located in the appendix under the computations section. Upon obtaining Keq1, Keq2,

and Keq3, the average Keq can be obtained by getting the mean value of the three equilibrium constants. And the resulting average equilibrium constant is 408.57. Keqtotal = = 408.57

The range for the theoretical values of Keq is between 140 and 280. The experimentally yielded Keq is quite larger than the theoretical range for about 191.8% to 45.9% percentage difference due Table.8 Sources of Errors. Source 1. Bubbles present in the path of the light in cuvette 2. The solution was contaminated (with color) 3. Fingerprints were present in the path of the light in the cuvette

to different errors present within the experiment. One of the major contribution to this huge difference in the value is because the KSCN used was contaminated because upon preparing the KSCN, a pink solution became visible and disappeared because the solution was diluted. It was a factor that could have affected the huge deviation of the experimental value from the theoretical range of values. Other factors that might have affected the experiment are listed in table.8.

Determinate or Indeterminate Determinate, random error.

Effect Bubbles present in the cuvette will yield a lower path length that will cause a decrease in the read absorbance. Absorbance will increase because the other solution will also absorb light. Absorbance will increase because the glass will become opaque and the light will scatter resulting to a lower transmittance and higher absorbance. Absorbance will decrease because a portion of the path of the light creates a clear way that allows the light to pass through easily. Some laboratory apparatuses have errors when it comes to measurements. The lack of accuracy in some of the measurements needed yields errors especially when measurement needed cannot be measured accurately. An open spectrophotometer can read a lower amount of absorbance because some of the light present in the spectrophotometer scatters and escapes while some light from the atmosphere enters the chamber where the cuvette is placed. The path length was just estimated to be 1 cm but not equal to 1cm because a part of that centimetre

Determinate, random error Determinate, random error

4. Cuvette was not placed Determinate, random error properly 5. Inaccuracy of measurements Determinate, systematic error

6. The spectrophotometer was not closed properly.

Determinate, random error

7. The path length is not Determinate, systematic error exactly equal to 1cm.

8. Cuvette was not rinsed with the solution to be tested prior to the spectrophotometric analysis. 9. Absorbance was not measured at the analytical wavelength

Determinate, random error

Determinate, random error

does not contain the solution. And because of this, the computed concentration of FeSCN2+ is smaller than the supposed value. The solution that will then be analysed can be contaminated with other reagents that must not participate in the solution analysis because presence of some other reagents may cause an increase of a decrease in the absorbance. The absorbance that the spectrophotometer will yield will be lower than the absorbance that it must yield; therefore, the concentration that will be computed will be lower than the concentration that must be yielded.

Conclusion / Recommendation The experiment yielded a value for the equilibrium constant that is far from the range of values of the equilibrium constant. The deviation that happened in the experiment may have occurred due to different sources of errors. One of those errors is the fact that the measuring apparatuses used are not perfectly calibrated to measure the exact amount especially the tip of the pipette. Another possible reason is that a pink solution was first obtained upon preparing the KSCN solution which caused a deviation in the absorbance read by the spectrophotometer which affected the concentration computed. Another possible reason is that small bubbles are present in the cuvette which are not that noticeable yet it can be seen when viewed closely that could have caused a lower absorbance due to the lower path length of the light. The result of the experiment was quite a failure because the computed value for the equilibrium concentration of FeSCN2+ was higher than its supposed equilibrium concentration because the equilibrium constant value determined in the experiment is higher than the theoretical value. The deviation of the concentration of FeSCN2+ than the predicted value of FeSCN2+ may come from different errors present within the experiment. The actual concentration of the

reactants may be lower or higher than the theoretical concentration because the initial concentration used in computing the equilibrium constant of the reaction was theoretically determined while the equilibrium concentration used in computing the equilibrium constant was determined experimentally. The errors present in the concentration of the reactants used to yield the FeSCN2+ experimentally may have yielded a higher or lower concentration of FeSCN2+ than the expected concentration of FeSCN2+ thereby causing errors in the computation for the equilibrium constant because the errors in the initial concentration of the reactants were not considered. The experiment could have yielded closer results if random errors were easily prevented and when the solutions were prepared accurately. But accurate concentrations are not easily created because systematic errors are present and it contributes errors to the experiment itself which can cause only a small deviation from the theoretically predicted value. The experiment could have also yielded closer results if more time was allotted in preparing the solutions and when the reagents used were not contaminated with other reagents because contamination of reagents affects the overall outcome of the experiment. And the experiment

could have been better if random errors like the bubbles can be prevented and can be removed and determined easily because the presence of some unexpected disturbances can cause a deviation in the experimental value from the theoretical value. As an overall conclusion, the experiment was not that successful because of the huge deviation of the equilibrium constant from the theoretical range of equilibrium constants. A failure was present due to different factors that can affect a certain procedure or a certain part in the experiment. By carefully performing the experiment for accuracy and precision, by carefully preventing errors by applying different procedures at a slower rate than normal, and by using uncontaminated reagents and by preparing the stock solutions carefully, then the experiment could have been successful. References: [1] Petrucci, R., et al. General Chemistry: Principles and Modern Applications (10th ed.). Toronto, Ont: Pearson Canada. 2011, pp 656-685 [2] Brown, T., Lemay, et al. Chemistry, The Central Science (11th ed.). Jurong, Singapore: Pearson Education South Asia PTE.2009, pp 626-707 [3] Silberberg, M.. Chemistry: The Molecular Nature of Matter and Change. Boston: McGraw-Hill 2006, pp 723-756 [4] http://pages.towson.edu/ladon/chemeq. html [5] Chemical Equilibrium. (n.d.). Retrieved from http://www.chem1.com/acad/webtext/che meq/ [6] 15.2a Equilibrium Constants. (n.d.). Retrieved from http://sowl.cengage.com/ebooks/vining_owlbook_ prototype/ebook/ch15/Sect15-2-a.html [7] http://msdiehl.com/resources/notes5.pdf [8] Spectrophotometry. (n.d.). Rice University -- Web Services. Retrieved from http://www.ruf.rice.edu/~bioslabs/methods /protein/spectrophotometer.html [9] Christian, G. D. (1971). Analytical chemistry. Waltham, Mass: Xerox College Pub. [10] Skoog, D. A., West, D. M., & Holler, F. J. (1996). Fundamentals of analytical chemistry. Fort Worth: Saunders College Pub. [11] Spectrophotometry for Quantitative Analysis. (n.d.). Retrieved from http://glencoe.mcgraw-

hill.com/sites/dl/free/0310402656/147061/ Beers_Law_Spectrophotometry.pdf [12] Chemical Equilibria. (n.d.). chemguide: helping you to understand Chemistry - Main Menu. Retrieved from http://www.chemguide.co.uk/physical/equil ibmenu.html [13] Civil and Environmental Engineering. (n.d.). Retrieved from http://research.ce.udel.edu/~imhoff/cieg33 7/file_downloads/Spectrophotometry_hand outs.pdf Appendix: A. Answers to questions: 1, Discuss the significance of the HCl in the solution preparation. HCl was used as a solvent in the experiment in order to prevent the hydrolysis of Fe3+ because Fe3+ hydrolyses into a base once water is used as a solvent and the resulting hydrolysed Fe3+ has a color and will contribute to the absorbance of the solution thereby yielding an absorbance due to the analyte and the hydrolysed Fe3+ rather than the analyte alone. 2. The concentration of FeSCN2+ in the standard solution is equal to the concentration of SCN-, the limiting reactant. Is this condition always true? If not, what is(are) the condition(s) for this to be true? The stated condition is not always true because equilibrium is established between the reactions of the two species. It can only be true whenever the limiting reactant is present in very small amounts and whenever the excess reactant is present in large amounts so that the reaction can be safely assumed that it went to completion because the amount of the formed FeSCN2+ is almost the same as the initial amount of SCN- and that SCNis present only in very small amounts that is almost negligible or almost near zero. 3. Solutions containing Fe3+ are colored, thus absorb at the visible region. Explain why the absorbance readings in the experiment correspond only to the absorption of the complex, FeSCN2+.

The absorbance recorded corresponds to that of the complex FeSCN2+ because a blank solution was first used in order to determine the absorbance contributed by the solution without the analyte itself. An autozero was then performed in order to change the basis of the absorbance being recorded and now choosing the absorbance of the blank solution to be the zero or the basis or the starting point of measuring the absorbance. Since the basis is then the blank solution; therefore, the absorbance that will be yielded will only be that of the complex ion FeSCN2+ because the basis of the absorbance is already the solution itself without the analyte. 4. Can distilled water which has zero absorbance be used as blank instead of the Fe3+ solution? No, because the nature of the solution without the analyte must be replicated in order to determine the absorbance of the solution without the analyte and there is no assurance that the solution without the analyte does not absorb light. 5. Account for the difference between the literature value and the experimentally determined value of the equilibrium constant. The literature value for the equilibrium constant lies in the range of 140-280 while the experimentally determined equilibrium constant is 408.57 which is higher than the given range. The large deviation of this equilibrium constant from the range of constants occurred due to different errors both random and systematic that are listed in table.8. B. Sample Calculations: Calibration: Initial concentrations and [FeSCN]2+eq: [reac]init = [FeSCN]2+eq [Fe3+]init

Standard Solution Blank 1 2 3 4 5 Blank: [SCN-]init = [Fe3+]init =

0.2 M KSCN (mL) 1.0 1.0 1.0 1.0 1.0 1.0

0.002 FeCl3 (mL) 0 0.1 0.25 0.5 1.0 2.0

0.1M HCl (mL) 9.0 8.9 8.75 8.5 8.0 7.0

= 0.002M = 0M

S1: [SCN-]init = [Fe3+]init = S2: [SCN-]init = [Fe3+]init = S3: [SCN-]init = [Fe3+]init = S4: [SCN-]init = [Fe3+]init = S5: [SCN-]init = [Fe3+]init = = 0.002M = 0.0004M = 0.002M = 0.0002M = 0.002M = 0.0001M = 0.002M = 0.00005M = 0.002M = 0.00002M

Corrected absorbances: Absorbance of Blank solution: 0.398 Solution 1 2 3 4 5 S1: 0.440-0.398 = 0.042 S2: 0.479-0.398 = 0.081 S3: 0.582-0.398 = 0.184 S4: 0.713-0.398 = 0.315 S5: 1.090-0.398 = 0.692 Equation of the best fit curve: Data: Y = Corrected Absorbance 0.00002M 0.042 0.00005M 0.081 0.0001M 0.184 0.0002M 0.315 0.0004M 0.692 By linear regression, the best fit curve can be obtained. And the resulting equation of the best fit curve is: X = ([FeSCN]2+eq) Absorbance 0.440 0.479 0.582 0.713 1.090

Keq determination: Initial concentrations: Solution Blank 1 2 3 Blank : [SCN-]init = [Fe3+]init = U1: [SCN-]init = [Fe3+]init = U2: [SCN-]init = [Fe3+]init = U3: [SCN-]init = [Fe3+]init = = 0.001M = 0.001M = 0.001M = 0.0008M = 0.001M = 0.0006M 0.002 KSCN (mL) 5.0 5.0 5.0 5.0 0.002 FeCl3 (mL) 0 3.0 4.0 5.0 0.1 M HCl 5.0 2.0 1.0 0

= 0.001M = 0M

Graph:

Determination of [FeSCN]2+eq Absorbance of Blank = 0.403

Absorbance vs. [FeSCN]2+eq

0.8 0.6 0.4 0.2 0 0 y = 1704.1x + 0.0004 R = 0.9962 y Linear (y) 0.0005

U1: 0.663 0.403 = 0.260 U2: 0.740 0.403 = 0.337 U3: 0.813 0.403 = 0.410 Absorbance 0.663 0.740 0.813 Corrected absorbance 0.260 0.337 0.410

U1: Initial Change Equilibrium [FeSCN]2+eq1 = 0.000152M U2:

Fe3+ 0.0008 -x 0.0008-x

SCN0.001 -x 0.001-x

[FeSCN]2+ 0 +x x

[FeSCN]2+eq = x = 0.000198M [Fe3+]eq = 0.0008M 0.000198M = 0.000602M [SCN-]eq = 0.001M - 0.000198M = 0.000802M

[FeSCN]2+eq2 = 0.000198M U3: U3: = 410.1

[FeSCN]2+eq3 = 0.000240M [Fe3+]eq and [SCN-]eq U1: Initial Change Equilibrium Fe3+ 0.0006 -x 0.0006-x SCN0.001 -x 0.001-x [FeSCN]2+ 0 +x x Fe3+ 0.001 -x 0.001-x SCN0.001 -x 0.001-x [FeSCN]2+ 0 +x x

Initial Change Equilibrium

[FeSCN]2+eq = x = 0.000240M [Fe3+]eq = 0.001M 0.000240M = 0.000760M [SCN-]eq = 0.001M - 0.000240M = 0.000760M

[FeSCN]2+eq = x = 0.000152M [Fe3+]eq = 0.0006M 0.000152M = 0.000448M [SCN-]eq = 0.001M - 0.000152M = 0.000848M Average Keq = 415.5

= 400.1 Keq = 408.57 U2: % Difference Range = | ( )|

)|

C. Tables and Figures Table.3b Absorbance vs. [FeSCN2+]eq data x ([FeSCN2+]eq) 0.00002M 0.00005M 0.0001M 0.0002M 0.0004M y (Absorbance) 0.042 0.081 0.184 0.315 0.692