K.K.R.

Seroje / General Chemistry II (2013)

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Determining the equilibrium constant of a reaction using spectrophotometry

King Karl R. Seroje*
National Institute of Physics, College of Science, UP Diliman, Quezon City , Phil. 1101

ABSTRACT
The equilibrium constant of reaction between ferric ion and thiocyanate that forms blood-red complex thiocyanoiron is determined. The equilibrium concentrations of both reactants and product are obtained using spectrophotometry. From the obtained equilibrium concentrations, the equilibrium constant is calculated. The average value obtained is 155, which is 85% deviated from the literature value of 1047. This is mainly accounted on the systematic error specifically on the possible contamination of reagents, which could not be corrected statistically (e.g. getting the average). Though the deviation is significant, the experiment is still successful in demonstrating Beer-Lamberts Law.

1. INTRODUCTION A chemical reaction has reached equilibrium when the rate of formation of both products and reactants are equal. In this instance, there is a constant ratio between the concentrations of products and reactants (both raised to their corresponding stoichiometric coefficients) called the equilibrium constant Keq, aA + bB cC + dD =
[][] . [][]

The concentration of the colored product can be determined using spectrophotometry and the initial concentrations of the reactants are already given. The goal of the experiment is to determine the equilibrium concentrations of the substances involved in the reaction. This equilibrium concentrations shall be used to calculate for the equilibrium constant Keq. 2. METHODOLOGY The spectrophotometer used was single-beam UVmini-1240. The apparatus was first calibrated using the solutions tabulated in Table 1 to determine the absorbity of the blood-red complex [Fe(SCN)]2+. Table 1. Volume of the substances for each solution.
Solution Blank Standard 1 Standard 2 Standard 3 Standard 4 Standard 5 0.002M FeCl3 (mL) 0 0.10 0.25 0.50 1.00 2.00 0.20M KSCN (mL) 1.00 1.00 1.00 1.00 1.00 1.00 0.100M HCl (ml) 9.00 8.90 8.75 8.50 8.00 7.00

(1) (2)

where A, B, C, D are the substances involved in the reaction with the corresponding stoichiometric coefficients a, b, c, and d. The square brackets signify the various concentrations of the species. As defined in equation (2), the concentration of products and reactants must be determined to get the equilibrium constant. Spectrophotometry is one of the methods to determine the concentration of a colored substance in a solution. According to BeerLamberts law, the light absorbance of a solution is linearly dependent on the concentration of the colored substance contained, A = bC,

(3)

where A is the absorbance, the absorbity of the colored chemical in the solution, b the path length of the light passing through the solution, and C the concentration of the colored substance. Thus, one expects a double in absorbance rate if the concentration of the colored substance is doubled. In this experiment, the subject of study is the reaction between aqueous iron (III) ion and thiocyanate ion to form a blood-red complex thiocyanoiron (III) ion:

Fe3+(aq) + 5H2O(l) + SCN-(aq) [Fe(H2O)5SCN]2+.

(4)

The part of the molecule of product that absorbs visible light is Fe(III)-SCN, which is called a chromophore. Hence, we can focus on the reaction: Fe3+ + SCN- [Fe(SCN)]2+.

Part of the calibration was to determine the wavelength of the light with highest degree of absorption in order to attain high sensitivity and minimizing possible deviations. Included in the calibration is the blank solution which is used to correct the discrepancies due to absorbance from other species. The absorbance from the blank solution must be the calibrated zero absorbance reading in the experiment. HCl is added to keep the volume of the solution constant. Moreover, addition of HCl enables dissociation of Fe3+ in FeCl3 that will assure the formation of the blood-red complex [Fe(SCN)]2+, which is the subject for spectrophotometry. After calibrating, the solutions tabulated in Table 2 were tested for absorbance in the spectrophotometer. 3. RESULTS AND DISCUSSION 3.1 Calibration Curve The wavelength of light with highest degree of absorbance is 464nm. The result of the calibration of spectrophotometer is shown in the following figure.

(5)

The corresponding equilibrium constant of this reaction is given as, = [[Fe(SCN)]2+ ] . [ 3+ ] + [ ]

(6)

*Corresponding author: kingkarlseroje@nip.upd.edu.ph

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The average equilibrium constant calculated is 155, which has approximately 85% deviation from the literature value of 1047. This significant deviation may be accounted mainly on the systematic error of the experiment, which could not be corrected statistically (such as getting the average). One of the systematic errors the author considers is the contamination of the reagents. This factor could greatly affect the outcome of the experiment, as can be shown mathematically. Due to contamination, the probability of getting higher absorbance read-out in calibration is high. Thus, when calibrating, Figure 1. Plot for the absorbance as a function of concentration. With the aid of linear regression, the best fit line encompasses a linear relationship depicted by the equation y = 3656.1x 0.0047 with correlation coefficient R2 = 0.9997. The equation is analogous to the Beer-Lamberts A=bC. Since the molar absorptivity and the path length b do not change, it is expected that the slope of the curve shown by figure 1 is equivalent to b. Also, the plot described by figure 1 is a function of concentration. Thus, relating to BeerLamberts law, = 3656.1 0.0047 + 0.0047 = 3656.1 = . A= bC
A =

(11) (12)

The calculated b (the slope of the regression) would be higher than the actual. Thus, using b, the calculated equilibrium concentration of the product would be lower,
A =[Fe(SCN)]2+eq. b

(13)

(7) (8)

Obtaining lower value of the product equilibrium concentration results in higher equilibrium concentration of the reactant as shown, [Fe3+]initial - [Fe(SCN)]2+eq= [Fe3+]eq, [SCN-]initial - [Fe(SCN)]2+eq= [SCN-]eq.

3.2 Absorbance of the Unknown Solutions Table 2 shows the unknown solutions used and their corresponding absorbance. Initial concentrations of Fe3+ was varied while keeping the concentration of SCN- constant. Table 2. Absorbance of unknown solutions.

(14) (15)

Thus, the computed equilibrium constant Keq would be of lower value than the actual,
[Fe(SCN)2+] =Keq. [ 3+ ][ ]

[Fe 3+]initial [SCN-]initial Absorbance Unknown 1 0.0006 0.001 0.29 Unknown 2 0.0008 0.001 0.39 Unknown 3 0.001 0.001 0.48 Solution
The equilibrium concentration of the reactants can be solved using the following equation
= [] [] [] = [] [] ,

(16)

(9) (10)

Another factor that contributes to deviation is the systematic error in measurements due to human and instrument limitation. Though this error could not be eliminated in actual experiments, this can be minimized such that it creates a low impact in the results. However, the students performing the experiment were cautious in doing measurements, which can be supported by the high precision of the results (closeness of data) as shown in Table 3. Thus, systematic error due to human limitation should have a low impact. 4. Conclusions and Recommendations The equilibrium concentration of the product was determined using spectrophotometry. It is observed from the gathered data that the absorbance is directly proportional to the concentration of the colored substance in the solution, which satisfies Beer-Lamberts Law. The average equilibrium constant of the reaction (155) has 85% deviation from the literature value of 1047. This can be accounted on the systematic error of the experiment, specifically on the high possibility of contamination of the reagents. The author, however, recommends for further study to use fresh reagents and be cautious not to contaminate them. Though the percent deviation is significant enough to conclude that the experiment has failed, the Beer-Lamberts Law was still observed. Thus, the experiment is successful in demonstrating the law.

where R is the reactant substance with stoichiometric coefficient x and P is the product with stoichiometric coefficient y. In this case, the second term of the right side of equation (10) is [[Fe(SCN)]2+]eq, which is equivalent to C in equation (3). The equilibrium constant Keq can be obtained using equation (6). Thus, tabulating the results gives the following table. Table 3. Calculated equilibrium concentrations for each solution, with the corresponding equilibrium constants.

Solution Unknown 1 Unknown 2 Unknown 3

[Fe 3+]eq 0.0005 0.0007 0.0009

[SCN-]eq [FeSCN2+]eq 0.0009 0.0009 0.0009 8.1 x 10

-5 -4 -4

K eq 155 156

1.1 x 10

154 1.3 x 10 Average: 155

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References
Whitten, K.W., Davis, R.E., Peck, M.L., and Stanley, G.G. Chemistry Eighth Edition, Thomson Brooks/Cole, USA. 2007. Brown, T.L., LeMay Jr, H.E., Bursten, B.E., Burdge, J.R. Chemistry The Central Science Ninth Edition, Pearson Education, Inc., USA. 2004. Silverstein, R.M., Bassler, G.C., and Morrill, T.C. Spectrometric Identification of Organic Compounds Fourth Edition, John Wiley & Sons, USA. 1981 Petrucci, R.H., Harwood, W.S., and Herring, F.G. General Chemistry: Principles and Modern Applications Eighth Edition, Pearson Education, Inc., South Asia. 2004 Skoog, D., West, D.M., and Holler, F.J. Fundamentals of Analytical Chemistry Eighth Edition, Thomson Brooks/Cole, USA. 2004

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APPENDIX

[C]: molar concentration of the product C [D]: molar concentration of the product D

A.

WORKING EQUATIONS

[A]: molar concentration of the reactant A [B]: molar concentration of the reactant B

Solving for initial concentration

a: stoichiometric coeffient of A b: stoichiometric coeffient of B

M1V1 = M2V2

c: stoichiometric coeffient of C d: stoichiometric coeffient of D

Where: M1: initial molar concentration V1: initial volume of solution with molarity of M1 M2: final molar concentration V2: final/total volume of solution with molarity of M2 Solving for the equilibrium concentrations For [Fe3+]: [Fe3+]eq= [Fe3+]initial - [Fe(SCN)2+] Where [Fe3+]eq: equilibrium concentration of Fe3+ [Fe3+]initial: initial concentration of Fe3+ [Fe(SCN)2+]: equilibrium concentration of [Fe(SCN)2+]

Beer-Lamberts Law

A= bC

For [SCN-]: [SCN-]eq= [SCN-]initial - [Fe(SCN)2+] Where: [SCN-]eq: equilibrium concentration of SCN [SCN-]initial: initial concentration of Fe(SCN)2+

Where: A: measured absorbance : wavelength dependent molar absorptivity coefficient b: path length (in cm) C: analyte molar concentration %diff= y= mx+b B. where: b=m=slope A= y values C= x values

Percent Deviation
|actual value theoretical value| x

100%

SAMPLE CALCULATIONS

Solving for initial concentrations Given: M1 of KSCN= 0.002M V1 of KSCN= 0.20mL= 2.0 x 10-4

Solving for Keq Given a theoretical equation: aA + bB cC + dD Keq=

[][] [] []

V2= 10mL= 0.010L

For: [SCN-] M1V1 = M2V2 (0.002M)(2.0 x 10-4)= M2(0.010L)

Where: Keq: equilibrium constant

M2= 4.0 x 10-5M

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= Solving the concentrations using Beer-Lamberts Law Given: A= 0.128 b=m=slope= 3656.1 y-intercept= -0.0047 from the equation: A= bC and y= mx+b A= bC + b
b

8.06 x 105M 0.005)(0.009)

=155

Solving for Percent Deviation

%diff= =

|actual value theoretical value| x

100%

=C C

|1047 155| x 1047

100% = 85.2%

0.29+0.0047 = 3656.1

C= 8.06 x 10-5M

Solving the equilibrium concentration of [SCN -] Given: [SCN-]initial1=0.001 M [SCN-]change1= [Fe(SCN)]2+eq= 8.06 x 10-5M

[SCN-]eq1= [SCN-]initial1- [SCN-]change1 = 0.001 M - 8.06 x 10-5M = 0.0009 M

Solving the equilibrium concentration of [Fe3+]

Given: [Fe3+] initial1= 0.0006 M [Fe3+]change1= [Fe(SCN)]2+eq= 8.06 x 10-5M

[Fe3+]eq1=[Fe3+] initial1- [Fe3+]change1 = 0.0006 M 8.06 x 10-5M = 0.0005 M

Solving for the Equilibrium Constant (Keq)

Keq1=

[Fe(SCN)2+ ] [ 3+][ ]