SPECTROPHOTOMETRIC DETERMINATION OF EQUILIBRIUM CONSTANT OF A REACTION

R. M. DE VERA
INSTITUTE OF CHEMISTRY, COLLEGE OF SCIENCE UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: JULY 24, 2013 INSTRUCTORS NAME: LISA MARIE S. RAMIREZ

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ABSTRACT The equilibrium constant expression, Keq, of the complexation reaction of aqueous iron(III) ion and thiocyanate forming FeSCN2+ was determined using spectrophotometric analysis. Using the wavelength of 466 nm, prepared solutions were tested in spectrophotometer at room temperature. The molar absorpitivity coefficient of FeSCN2+ was known using standard solutions. A calibration curve was constructed using values obtained from standard solutions, and then the calibration curve with an equation y=2040.8x-0.038 was then used for determining the concentration of FeSCN2+ in unknown solutions at equilibrium. The concentration of FeSCN2+ at equilibrium was then used determine the concentration of Fe3+ and SCN- at equilibrium in unknown solutions. The concentration of FeSCN2+, Fe3+ and SCN- was plugged in the equilibrium constant expression to know the Keq. The value of molar absorptivity constant obtained was 2040.8 M-1cm-1. The results showed that experimental Keq of the reaction for three solutions were near to each other. The average Keq of the reaction was 391.28, the percent yield was 139.7% to 279.5%. _________________________________________________________________________________________________________________

INTRODUCTION Equilibrium constant, Keq, is a number that expresses the concentration of products and reactants at equilibrium in a reversible chemical reaction at a given temperature. The Keq determines the position of equilibrium in a system [4]. The Keq of a reaction can be determined using spectrophotometry. Spectrophotometry is a process using electromagnetic radiation (light) to measure an unknown analyte concentration by relating the amount of light

absorbed by the solution. UV-Vis spectrophotometer, the apparatus used in the experiment, measures the absorbance of a solution. Using the measured absorbance, the concentration of an analyte can be calculated using Beer-Lamberts law (eqn. 1) [1]. A= bc (1)

Where, A, , b and c are absorbance, molar absorptivity coefficient, path length

and concentration of colored substance in solution respectively. In the experiment, the Keq of the complexation reaction of aqueous iron(III) ion and thiocyanate (eqn. 2) was determined. Fe3+(aq) + 5H2O(l) + SCN-(aq) [Fe(H2O)5SCN]2+ (2)

can be obtained using Beer-Lamberts law. The concentration of FeSCN2+ at equilibrium in unknown solutions can now be obtained using Beer-Lamberts law by substituting values of from calibration, measured absorbance and known path length. The concentration of FeSCN2+ at equilibrium can now be used to get the concentration of other ions in the solution and know the Keq (3)[2]. [ [ ] [ ] ]

The complexation reaction formed [Fe(H2O)5SCN]2+ , a deep, blood-red complex, this complex is responsible for the changes in color in varying concentrations and for the absorbance measured. The amount of light that is absorbed will determine the color of the solution. The solution with the greatest concentration of [Fe(H2O)5SCN]2+ was color orange, in the color wheel (Fig. 1) orange complementary color is blue. The color blue has wavelength value of 435 to 500 nm. Lambda max is the wavelength at which a solution can absorb maximum light.

This experiment is done to determine the Keq of the complexation reaction of aqueous iron(III) ion and thiocyanate using spectrophotometer.

METHODOLOGY Stock solutions were prepared for the preparation of standard solutions. One liter of 0.1 M HCl was prepared using 8.33 mL of concentrated HCl diluted using distilled water in a 1000 mL volumetric flask. Fifty milliliters of 0.2 M KSCN was prepared by diluting 0.97 g KSCN using 0.1 M HCl in a 50 mL volumetric flask. Using 1.0 mL of 0.2 M KSCN, 100 mL of 0.002 M KSCN was prepared by diluting it in a 100 mL volumetric flask using 0.1 M HCl. Fifty milliliters of 0.2 M FeCl3 was prepared by diluting 1.62 g FeCl3 using 0.1 M HCl in a 50 mL volumetric flask. Using 1.0 mL of 0.2 M FeCl3, 100 mL of 0.002 M FeCl3 was prepared b diluting it in a 100 mL volumetric flask using 0.1 M HCl. Standard solutions were prepared in 6-inch test tubes as described in table 1.

Fig. 1 Color Wheel

The UV-Vis spectrophotometer was calibrated first to obtain . With known concentration of FeSCN2+ and absorbance measured calibration curve can be made and

Table 1. Components of Standard Solutions Solution 0.002 M 0.20 M 0.10 M FeCl3,(mL) KSCN,(mL) HCl,(mL) Blank 1 2 3 4 5 0 0.10 0.25 0.50 1.00 2.00 1.00 1.00 1.00 1.00 1.00 1.00 9.00 8.90 8.75 8.50 8.00 7.00

Using the values obtained from measurement of absorbance and the concentrations, calibration curve was constructed. Using the calibration curve the concentration of ion species in the equilibrium was determined and was used for calculating the Keq. RESULTS AND DISCUSSION In solution preparation, in standard solutions, it was observed that the color of the solution varies with concentration of Fe3+. The solution was darker in higher Fe3+ concentration. The formation of FeSCN2+, a chromophore, was responsible for color. In standard solutions, the concentration of FeSCN2+ was known because the amount of SCN- was much excess that the formation of FeSCN2+ was very limited with the amount of Fe3+ and the reaction was assumed to be complete [4]. Thus, the number of moles of FeSCN2+ in the solution was equal to the number of moles of Fe3+. The absorbance of standard solutions was then measured. Lambda max is the wavelength at which a solution can absorb maximum light. The lambna max (466 nm) was important to be used to obtain the maximum absorbance of the solution. The importance of blank solution is for the autozero. After autozero, the absorbances of other ions in the solution are ignored. After autozero, the standard solutions absorbances can be measured and the absorbance measured will be equal to corrected absorbance because autozero was performed [5]. After obtaining the concentration of and absorbance in standard solutions (Table 2.1), calibration curve was made to know the equation of best fit curve FeSCN2+

Unknown solutions were prepared in 6-inch test tubes as described in table 2. Table 2. Components of Unknown Solutions
Solution

Blank 1 2 3

0.002 M FeCl3, (mL) 0 3.0 4.0 5.0

0.20 M 0.10 M HCl, KSCN, (mL) (mL) 5.0 5.0 5.0 2.0 5.0 1.0 5.0 0.0

In calibration of UV-Vis spectrophotometer, the absorbances of standard solutions were measured. The cuvette filled with the blank in standard solutions was placed inside the spectrophotometer and autozero was performed. The cuvette was then filled with standard 1 and the absorbance was recorded. The absorbance of standard 2, 3, 4 and 5 were also measured and recorded. In determination of the equilibrium constant for the formation of [FeSCN]2+, the cuvette filled with the blank solution in unknown solutions was placed inside the spectrophotometer and autozero was performed. The absorbance of unknown 1, 2 and 3 was measured and recorded.

and know the value of . Beer-Lamberts Law states that absorbance is proportional to concentration, so using the absorbance and concentration of FeSCN2+ a linear relationship was observed(Fig.2). The absorbance is dependent variable so the y-axis labeled as absorbance and the concentration is the independent variable so x-axis was labeled [FeSCN2+] [2]. Table 3. Calibration Data Solution S1 S2 S3 S4 S5 Absorbance 0.015 0.057 0.157 0.37 0.78 [FeSCN2+], M 0.00002 0.00005 0.0001 0.0002 0.0004

temperature where the test was conducted or errors in preparing the solutions. As shown in the figure 2, line was not a perfect line, this can be caused the solutions were not much diluted. Diluted solutions were important to be used because if the solutions are not diluted, light scattering in the solution may occur and this can cause significant difference on the value absorbance measured [3]. y = 2040.8x - 0.038 (4)

= slope/b=2040.80 M-1/1cm (5) In determining the Keq of the complexation reaction of complexation reaction of aqueous iron(III) ion and thiocyanate, the absorbance measured (Table 2) was used to compute for the [FeSCN2+] (eqn 6) at equilibrium. Using ICE table, values for [Fe3+] and [SCN-] at equilibrium was obtained (table 5). By using the ICE table, we assume that the solutions follows the Le Chateliers Principle that additional reactants will shift the equilibrium to the right and will favor the formation of more products [4]. [FeSCN2+] = A -(-0.0385)/2040.8 (6)

1 0.8 0.6 0.4 0.2 Absorbance 0 0 0.0001 0.0002 0.0003 0.0004 0.0005 [FeSCN2+]eq,M y = 2040.8x - 0.0385 R = 0.9993

Table 4. ICE table Unknown 1 [Fe3+],M [SCN-], M 1x10-3 -x 1x10-3 x [FeSCN2+], M 0 +x x

Figure 2. Calibration Curve The slope of the line is equal to b, the product of molar absorptivity coefficient and path length. By knowing the equation best fit curve using linear regression, the slope of the line was obtained (eqn 4). The slope of line is equal to 2040.8, from this can be calculated. The path length was 1 cm, so plugging it to the equation slope= b (eqn 5), of FeSCN2+ is 2040.8 M-1cm-1. The theoretical value of is 3550 M-1cm-1, the percent yield was 57.49%. The difference may be caused by the

Initial 6x10-4 Change -x Equilibrium 6x10-4 -x

Since [FeSCN2+] at equilibrium is 1.5x10-5 M, therefore x=1.5x10-5 M. Thus, the concentrations of Fe3+ and SCN- at equilibrium are 4.5x10-4 M and 8.5x10-4 M respectively. With the concentrations of the reactants and products the Keq was obtained (eqn 7).

and unwanted reactions in the solution were more likely occurred. CONCLUSION AND RECOMMENDATION Using the absorbance of unknown 2 and 3 plugged in equation 6 and the resulting concentration plugged in table 4, the Keq for unknown 2 and 3 was determined. The Keq values for Unknown 2 and 3 are 384.15 and 398.28 respectively. Complete calculations can be seen at appendix sample calculations. The average of experimental Keq for the formation of FeSCN2+ was 391.28 at room temperature. The range of theoretical Keq values is 140 to 280. The experiment percent yield was 139.7% to 279.5%. Possible reason for the difference of the experimental values and theoretical value is that Keq changes in different temperatures, because the temperature where the experiment was conducted was not exactly 25 C, this could have caused significant change in the value of Keq. Other factor was stray lights were ignored. Light scatters in all direction when it hit particles. This is why this experiment can only be done using diluted solutions, to prevent the scattering of light. Another possible source of error was the possible formation of FeCl4- and Fe(H20)5(OH) which competes in the equilibria. Another possible source is that the light used was not actually monochromatic light, it was only assumed that the light used was monochromatic so we can apply Beer-Lamberts Law [5]. Other sources of errors are prepared solutions were not placed inside the testing rooms at least twenty minutes before the test thus, the temperature of the solutions do not have equal temperatures. Prepared solutions were stored for a long time, contaminations The experimental values for Keq of the complexation reaction of aqueous iron(III) ion and thiocyanate in unknown solutions was 390.96, 384.15 and 398.74 respectively. The absorbance of unknown 1,2 and 3 solutions were 0.267, 0.349 and 0.439 respectively. Using these absorbance the concentration of FeSCN2+ in unknown 1 (1.497x10-5 M), unknown 2 (1.8988x10-5 M) and unknown 3 (2.3398x10-5 M) were obtained by Beer-Lamberts law. These concentrations were used to determine the concentrations of Fe3+ and SCN- at equilibrium in unknown 1, unknown 2 and unknown 3. The average Keq for unknown solutions was 391.28, the percent error was 39.7% to 179.5%. The results showed that in different concentrations of reactants present initially, the value of Keq in all reactions are near to each other. It means that the Keq do not depends on the initial concentration of reactants. The experiment was success to show this phenomena, however, the average experimental Keq was not inside the range of theoretical values Keq of FeSCN2+. The experiment results can be improved if the HCl will not be used to acidify the solution. Other acids can be used like HNO3. This is because Cl- react to Fe3+ which can competes the equilibria. In addition, a double beam spectrophotometer can be used, this kind of spectrophotometer is more accurate than single beam spectrophotometer.

REFERENCES [1] Petrucci, R.H., Harwood, W. S. General Chemistry 7th ed. Prentice-Hall, Inc. New Jersey. 1997. [2] General Chemistry II Laboratory Manual. Institute of Chemistry, University of the Philippines, Diliman. 2013. [3] Roby, D., New Mexico Wastewater Laboratory Certification Study Guide. New Mexico Environment Department. New Mexico.2007. [4] Chemical Equilibrium. (n.d.). Retrieved from http://www.chem1.com/acad/webtex t/chemeq/ [5] J. D. J. Ingle and S. R. Crouch, Spectrochemical Analysis, Prentice Hall, New Jersey (1988)

c. The product of 1st hydrolysis of Fe3+ is brick red colored rust. d. Because the product of hydrolysis of Fe3+ is colored, the absorbance of the solution will increase.
B. Sample Calculations Determination of FeSCN2+ concentrations in standard solutions [Fe3+]initial [FeSCN2+] [ S1: [ ] [ S2: [ ] [ S3: [ ] [ S4: [ ] [ S5: [ ] [ ] ] ] ] ] ]

Appendix A. Answers to question Solution Preparation 1. Why should the solutions be prepared with 0.10 M HCl used as solvent? HCl was used as solvent in solution preparations to prevent the formation of Fe(OH)3. a. At higher pH, Fe3+ hydrolyses forming Fe(OH)3 b. The balance equation of 1st hydrolysis of Fe3+. Fe3+(aq) + 3OH-(aq) Fe(OH)3(s )

Determination of Initial Concentrations of Fe3+ and SCN- in unknown solutions U1:

[ [

] ]

Determination of equilibrium concentrations of Fe3+ and SCN- in Unknown Solutions U1: Fe3+ + SCN- FeSCN-

U2: [ [ U3: [ [ ] ] ] ]

Unknown 1

[Fe3+],M

Initial 6x10-4 Change -x Equilibrium 6x10-4 -x

[SCN-], M 1x10-3 -x 1x10-3 -x

[FeSCN2+], M 0 +x 0.0001497

x = 0.0001497 M [Fe3+]eq= 6x10-4 M 1.49x10-4 M = 0.00045 M [SCN-]eq= 1x10-3 M - 1.49x10-4 M = 0.00085 M U2: Fe3+ + SCN- FeSCNUnknown 2 [Fe3+],M [SCN], M 1x10-3 -x - 1x10-3 -x [FeSCN2+], M 0 +x 0.00018988

Determination of Concentration of FeSCN2+ at equilibrium in Unknown Solutions Uising the equation of best fit curve y = 2040.8x - 0.038 A=2040.8c-0.038 [ U1: [ U2: [ U3: [ ] 0.00023398 M ] M ] . M ]

Initial 8x10-4 Change -x Equilibrium 8x10-4 x x= 0.00018988 M

[Fe3+]eq= 8x10-4M 1.89x10-4M= 0.00061 M [SCN-]eq= 1x10-3 M 1.89x10-4M=0.00081 M U3: Fe3+ + SCN- FeSCNUnknown 3 [Fe3+],M [SCN], M 1x10-3 -x 1x10-3 -x [FeSCN2+], M 0 +x 0.00023398

Initial 1x10-3 Change -x Equilibrium 1x10-3-x

x= 0.00023398 [Fe3+]eq= 1x10-3M -2.34x10-4M= 0.000766 M [SCN-]eq= 1x10-3M-2.34x10-4M= 0.000766 M Determination of the Keq [ [ U1: 390.9588365 U2: 5 U3: 398.7394135 Average Keq Keq= (390.958836+384.151295+398.739413)/3= 391.2831817 ] [ ] ]

C. Data Sheet Standard Solutions Solution S1 S2 S3 S4 S5 Absorbance 0.015 0.057 0.157 0.37 0.78 [FeSCN2+], M 0.00002 0.00005 0.0001 0.0002 0.0004

Unknown Solutions Data

Solution U1 U2 U3 Absorbance 0.267 0.349 0.439 [FeSCN2+]eq,M 0.0001497 0.00018988 0.00023398 [Fe3+]I,M 0.0006 0.0008 0.001 [Fe3+]eq,M 0.00045 0.00061 0.000766 [SCN-]I,M 0.001 0.001 0.001 [SCN-]eq,M 0.0008503 0.00081012 0.00076602 AVERAGE Keq,M 390.9588365 384.1512951 398.7394135 391.2831817