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SPECTROPHOTOMETRIC DETERMINATION OF THE EQUILIBRIUM CONSTANT OF A REACTION

ABSTRACT This experiment aimed to determine the equilibrium constant of the formation of the [Fe(SCN)]2+ complex ion based on the concept of spectrophotometry. The systems equilibrium concentration was determined through the use of Beer-Lamberts law, which relates the concentration of the substance being studied in the solution to the amount of light it absorbs. In this study, the absorbance of solutions containing varying amounts of FeCl3, KSCN, and HCl were measured using a single-beam UV-Visible spectrophotometer. The values obtained were then used to compute for the equilibrium concentrations of the chemical species and their corresponding Keq values. The experimental result showed that the Keq for the reaction is 173.87 which is off to the literature value of 169 by 2.88%. Basing on the minimal percent error, it can be concluded that the experiment was successful. INTRODUCTION Spectrophotometry is the science that deals with the quantitative study of the electromagnetic spectrum, particularly the intensity of light [1]. By using the ability of atoms to absorb light energy of specific wavelength, it can be used in the calculation of the concentration of an unknown solution [2]. A spectrophotometer is the primary device used in spectroscopy. It is capable of measuring the absorbance of a solution by quantifying the amount of light passing through a solution placed in a specialized tube called cuvette [3]. One important principle involved in spectroscopy is the Beer-Lamberts Law. It directly relates the concentration of a colored substance in a solution to the amount of light it absorbs [4]. A=bC (1) path length (cm), and C is the analyte molar concentration. However, this equation has a lot of limitations. First, the solutions to be analyzed must be highly diluted. Second, reagent of high purity must be used. And third, the temperature must be constant [4]. In this study, varying amounts of Fe3+ ions were reacted with a constant amount of SCNions with the addition of HCl to produce the blood-red complex, [Fe(SCN)]2+. Fe3+(aq) + SCN-(aq) [Fe(SCN)]2+(aq) (2)

Using the absorbance of solutions having known concentrations, the standard calibration curve of the solution was calculated. The said reaction is 1:1 and it was also assumed that it went to full completion. Thus, the initial concentration of the limiting reactant, Fe3+, is equal to the equilibrium concentration of [Fe(SCN)]2+. [Fe3+]i = [Fe(SCN)]2+eq (3)

Where A is the absorbance, is the molar absorptivity coefficient (M-1 cm-1), b is the

Furthermore, a plot of A vs. [Fe(SCN)]2+eq was made. Using linear regression, the equation of the line fit to the scatter plot was calculated.

A = b C + error

(4)

Based on Equation (4), the absorbance was treated as a function of the equilibrium concentration of [Fe(SCN)]2+. The slope of the line is the product of and b and the error was found to be the y-intercept of the line. The unknown solutions were used in the determination of the Keq of the reaction. Using the Beer-Lamberts Law, the equilibrium concentration of [Fe(SCN)]2+ was obtained. The equilibrium concentrations of Fe3+ and SCN- were obtained with the use of the following equations: [Fe3+]eq = [Fe3+]i - [Fe(SCN)]2+eq (5) [SCN-]eq = [SCN-]i - [Fe(SCN)]2+eq (6) These equations were obtained from the ICE table below. Table 1. ICE Table of Concentrations Fe3+ SCN[Fe(SCN)]2+ I [Fe3+]i [SCN-]i 0 C -x -x +x E [Fe3+]i - x [SCN-]i - x +x For this system, the Keq for each solution was obtained from the equation: Keq = [FeSCN2+]eq (7) 3+ [Fe ]eq[SCN ]eq The mean Keq for the reaction was calculated by averaging all the Keqs obtained from each solution. This value was then compared to the literature value to get the percent error. % error =
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the Beer-Lamberts Law. It also aimed to calculate the percent difference between the experimentally derived Keq and the literature value.

METHODOLOGY Preparation of Stock Solutions

Preparation of Standard Solutions

Preparation of Unknown Solutions

Determination of the Absorbance of Solutions

Waste Disposal Figure 1. Flowchart of the Procedure of the Experiment Preparation of Stock Solutions The following stock solutions were prepared: 1.100mL of 0.1M HCl solution from concentrated HCl solution, 2.250mL of 0.1M HCl solution from the 1.0M HCl solution, 3.50mL of 0.1M KSCN solution, 4.100mL of 0.002M KSCN (in 0.1M HCl), 5.50 mL of 0.2 M FeCl3solution, 6.100 mL of 0.002 M FeCl3(in 0.1M HCl). An analytical balance was used in the measurement of the masses of the KSCN crystals and FeCl36 H2O salts. Preparation of Standard Solutions General

(8)

This experiment geared towards a more comprehensive understanding of the concept of chemical equilibrium. Specifically, it aimed to determine the equilibrium constant, Keq, for the formation of [Fe(SCN)]2+ based on the concept of spectrophotometry, particularly

The stock solutions were then used to prepare the standard solutions, or solutions having known concentrations. These solutions were used to determine the standard curve of the solution. Table 2 shows the volumes of the reagents used in the preparation of the standard solutions. Table 2. Volumes of the Reagents Used in the Preparation of the Standard Solutions Solution 0.10 M 0.002 0.10 M KSCN FeCl3 HCl Blank 1.0 0 9.0 S1 0.2 0.1 8.9 S2 1.0 0.25 8.75 S3 1.0 0.5 8.5 S4 1.0 1.0 8.0 S5 1.0 2.0 7.0 The standard solutions were placed in 6-inch test tubes which were then covered with Parafilm. Note that the volume of the solutions was maintained at 10 mL. Preparation of the Unknown Solutions The stock solutions were also used in the preparation of the unknown solutions. These solutions were used to determine the experimental Keq value of the reaction. Table 3 shows the volumes of the reagents used in the preparation of the unknown solutions. Table 3. Volumes of the Reagents Used in the Preparation of the Unknown Solutions Solution Blank U1 U2 U3 0.10 M KSCN 5.0 5.0 5.0 5.0 0.002 FeCl3 0 3.0 4.0 5.0 0.10 M HCl 5.0 2.0 1.0 0

Determination of the Absorbance of the Solutions A single-beam UV-Vis Spectrophotometer was used in the measurement of the absorbance of the solutions, indicating that it was necessary to perform autozero in the calibration. The path length of the cuvette used was 1 cm. Also, the wavelength of the maximum absorbance was pre-measured by the lab instructor and was found to be 466 nm. Waste Disposal All of the solutions were disposed in the Inorganic Waste container except for the HCl solutions. They were disposed in the Acid Waste container. RESULTS AND DISCUSSION In this experiment, the system that is under observation is the reaction between Fe3+ and SCN- to produce FeSCN2+ complex, which is blood-red in color (Equation (2)). However, the blood-red color of the solutions as not observed due to the very small concentration of Fe3+ brought about by dilution. Instead, an orange solution was seen. Also, the addition of HCl in the solution brought about a competing reaction between the Fe3+ and HCl ions forming a colorless FeCl4- complex ion. Fe3+ + Cl- FeCl4(9)

Similarly, the unknown solutions were placed in 6-inch test tubes which were then covered with Parafilm. Note that the volume of the solutions was maintained at 10 mL.

Solutions containing Fe3+ ions are colored and so are absorbed in the visible region. However, due to the formation of a colorless complex, the absorbance readings in this experiment correspond only to the absorption of FeSCN2+.

The recorded values of the absorbance of each standard solutions used in the calibration were transferred in a scatter plot with it corresponding trend line shown in Figure 2.
1 0.8 0.6 0.4 0.2 0 0

Table 4 shows the recorded values of the absorbance and also the equilibrium concentration of [Fe(SCN)]2+eq in each unknown solution. The absorbance gathered from the experiment is no need to be corrected because the blank solution has been set as zero while calibrating the machine. The value of Keq for the three unknown samples was solved using Equation (7). The average Keq is taken as the computed Keq value for the experiment. The average Keq was calculated to be 173.87. It was then compared to the literature value of 169 and the percent difference was found to be 2.88 %. The percent error is considerably low and this can be attributed to the following: (1) touching of the clear side of the cuvette; (2) tissue contaminants in the cuvette surface; (3) wrong preparation of stock solutions; (4) impurity of the reagents used; and (5) abrupt changes in the temperature of the solution. CONCLUSION AND RECOMMENDATION The spectrophotometric determination of the equilibrium constant of the formation of the [Fe(SCN)]2+ion was done using a UV-Vis spectrophotometer and by applying the BeerLamberts Law. Using linear regression, the standard calibration curve of the solution was found to be A= 2284.3C + 0.0058 having an R2 of 0.996. The computed R2 value was very close to 1 suggesting that the resulting data will be very near the theoretical results. The empirical value of Keq obtained was 173.87 which was off to the literature value by 2.88%. Based from these results, it is concluded that the experiment was a success. REFERENCES

absorbance

y = 2284.3x + 0.0058 R = 0.996 0.0002 0.0004 0.0006

concentration

Figure 2. Calibration Curve Using linear regression, the equation of the trend line was found to be: A = 2284.3C + 0.0058; R2= 0.996 The R2 value is almost equal to 1 which suggested that the experimental data followed its supposed linear behavior. Knowing this, it can already be expected that a minimal percent error to be calculated in the determination of the Keq. The minimal errors in this part might have come from accidentally touching the clear side of the cuvette. Touching it will leave contaminants such as oil and dirt. As a result, some of the light during the measurement of the absorbance reflected back leading to a larger absorbance value. In the calibration part, water cannot be used as a blank solution because the test solution absorbs so much light relative to distilled water that the usable scale is compressed, and the accuracy is very poor. Table 4. Absorbance of Unknown Solns Solutions Absorbance [Fe(SCN)]2+eq U1 0.0006 0.00008 U2 0.0008 0.00011 U3 0.001 0.00013

[1] Dodd, R. E.; Chemical Spectroscopy; Elsevier Pub. Co.: Amsterdam, NY,1962. [2] Department of Chemistry, University of Kentucky; Photometry; n.d.; Retrieved from: http://www.chem.uky.edu/courses/che554/ 1_Photometry/Photometry_Chpt1.pdf last May 26, 2013. [3] Rice University; Principles of Spectrophotometry; 2012; Retrieved from: http://www.ruf.rice.edu/~bioslabs/methods /protein/spectrophotometer.htmllast January 20, 2013. [4] Bettelheim, F. A. et. Al.; Laboratory Experiments for General, Organic and Biochemistry; 8thed.; Thomson Brooks/Cole: Belmont, CA, 2007. [5] Institute of Chemistry. General Chemistry II Laboratory Manual. Quezon City: University of the Philippines Diliman, 2011. Print.

APPENDIX Calculations [Fe3+]i M1V1=M2V2 Standard 1: M2 = (.002)(0.1)/10 = 0.00002 M Standard 2: M2 = (.002)(0.25)/10 =0.00005 M Standard 3: M2 = (.002)(0.5)/10 = 0.0001 M Standard 4: M2 = (.002)(1)/10 = 0.0002 M Standard 5: M2 = (.002)(2)/10 = 0.0004 M [SCN]init Standard 1-5 = M2 = (0.2)(1)/10 = 0.02 M [FeSCN2+]eq = [Fe3+]i Unknown Solutions Absorbance Calibration Curve

[Fe3+]init M1V1=M2V2 Unknown 1: M2 = (.002)(3)/10 = 0.0006 M Unknown 2: M2 = (.002)(4)/10 =0.0008 M Unknown 3: M2 = (.002)(5)/10 = 0.001 M [SCN-]init M1V1=M2V2 Unknown 1-3: M2 = (.002)(5)/10 = 0.001 M [FeSCN]2+ x = (y 0.0005)(2885)-1 Unknown 1 = (0.192-.0005)(2885)-1 = 0.00008 Unknown 2 = (0.253-.0005)(2885)-1 = 0.00011

Unknown 3 = (0.304-.0005)(2885)-1 = 0.00013 Unknown 1 Fe Initial Change Eq Unknown 2 Fe Initial Change Eq 0.0008 SCN FeSCN 0.0006 -8.19 x10-5 0.000518 SCN 0.001 -8.19 x10-5 0.000918 FeSCN 0 +8.19 x 10-5 8.19x 10-5

0.001 0 -0.000109 0.000108581 0.000108581 0.0006914 0.000891419 0.000108581

Unknown 3 Fe Initial Change Eq 0.001 SCN FeSCN

0.001 0 -0.000131 0.000130911 0.000130911 0.0008691 0.000869089 0.000130911

Keq= [FeSCN]/[Fe][SCN] Keq1 Keq2 Keq3 172.1106365 176.170372 173.3190363

Average = (Keq1 + Keq2 + Keq3)/3 = 173.87 % difference = [theo-actual]/theo * 100% = [169-173.87]/169 * 100% = 2.88%