Chemical Equilibrium Determination of an Equilibrium Constant

Objective:
The purpose of this experiment is to determine the value of the equilibrium constant for a reaction.

Safety Tips:
Wear safety goggles at all times in the laboratory.

Background:
In many chemical reactions, reactant(s) are not completely converted to product(s). Instead, the reaction goes to some steady state in which the concentrations of both products and reactants do not change with time. The reaction is said to be "at equilibrium". At this point in the reaction, the rate of the forward reaction and the rate of the reverse reaction are equal. The reaction system has reached "dynamic equilibrium" in that chemical conversion is still occurring, but at an equal rate in both the forward and reverse directions. Consider, as an example, the reaction

aA + bB cC + dD
where A, B, C, and D indicate reactants and products; a, b, c, and d are coefficients in the balanced chemical equation; and the double arrow indicates that the reaction can proceed in either direction. Note that this double arrow is not to be confused with symbols for resonance. The equilibrium constant expression for a reaction is obtained by raising each molar concentration term to a power equal to the coefficient in the chemical equation, multiplying the molar concentrations of the products together, and dividing this by the product of the molar concentrations of the reactants. The equilibrium constant, symbolized by Kc, is the value obtained in the equilibrium constant expression when equilibrium concentrations are placed in the expression. The value of Kc is a constant for a particular reaction at a certain temperature. This means that if arbitrary quantities of A, B, C, and D are mixed, the reaction will proceed until the numerical values of the concentrations of these species satisfy Equation (1). For the reaction above the equilibrium constant expression has the form

Kc =

[C ]c [ D] d [ A] a [ B]b

Equation (1)

The molar concentration of the reactants and products is indicated by writing the formulas of the reactants and products in square brackets. The subscript c on the equilibrium constant indicates that it is defined in terms of molar concentrations. This experiment is a study of the equilibrium established when iron (III) ions (Fe3+) and thiocyanate ions (SCN-) are combined in aqueous solution:

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

For this reaction, Equation (2) becomes

Equation (2)

[( FeSCN ) 2+ ] Kc = [ Fe 3+ ][SCN ]

Equation (3)

The iron (III) thiocyanate ion, (FeSCN)2+, has a deep, blood-red color in solution. The intensity of this color is directly related to the concentration of iron (III) thiocyanate ion in solution. This allows the equilibrium concentration of (FeSCN)2+ to be determined by spectroscopy. In order to determine the equilibrium concentration of (FeSCN)2+ by spectroscopy, radiation of one wavelength (typically the wavelength () where absorbance is maximum and symbolized by max) will be passed through a solution and the quantity of light absorbed will be proportional to the concentration of the absorbing species in the solution. As the concentration of a solution increases, the amount of light absorbed increases. This relationship between concentration (c) and absorbance (A) is known as Beer's Law. Beer's Law is given as:

A = abc

Equation (4)

The symbol (a) represents the solution's molar absorptivity coefficient or constant and (b) the path length that the light travels through the solution , usually 1 cm. Absorbance does not have units. When b is in centimeters and c is in moles per liter, a has the units L mol-1 cm-1. The value of the molar absorptivity constant is unique for each absorbing species. Its value can be derived using Beer's Law or from a Beer's Law calibration curve. The molar absorptivity constant is equal to the slope of the line in a Beer's Law calibration curve. An illustration of a Beer's Law calibration curve is given in Figure 1. Note that the line passes through the origin. Beer's Law calibration curves are made experimentally by preparing a series of solutions, each with a known concentration of the absorbing species in an appropriate solvent. These solutions are referred to as standards. The absorbance of each solution is measured at the same wavelength and a calibration curve showing the relationship between the absorbance and the concentration of each standard is prepared. A typical calibration curve is shown in Figure 1. This calibration curve was prepared by plotting A (absorbance at max) versus the concentration of the standard solutions. In addition to determining the value of the molar absorptivity constant, this plot can be used to determine the unknown concentration of a solution by measuring the absorbance of the solution at the same wavelength used to measure the absorbance of the standards. For example, if A (absorbance) of the unknown were found to be equal to 0.40, the concentration according to the calibration curve would be 0.004 M. See Figure 1.
Absorbance vs. Concentration

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.001 0.002 0.003 0.004 0.005 Concentration (M) 0.006 0.007 0.008 0.009 0.01

Absorbance

Figure 1: Beer's Law Calibration Curve

In this experiment the absorbing species will be (FeSCN)2+ ions. (FeSCN)2+ ions absorb light in the blue to blue-green (430-490 nm) region of the spectrum, giving a red appearance to its solutions. The maximum absorbance (max) for this compound is at 447 nm. Neither Fe3+ nor SCN- ions absorb significantly in this region. A spectrophotometer will be used to measure the absorbance of the absorbing species, (FeSCN)2+ ions. In the first part of the experiment five standard solutions of known concentrations of (FeSCN)2+ will be prepared using 0.050 M HNO3, 0.0020 M KSCN and 0.100 M Fe(NO3)3 solutions. Notice that this is a large excess of Fe3+ ions. By mixing different known concentrations of SCN- ions with large excesses of Fe3+ ions, the equilibrium in this reaction is driven far to the right consuming almost all of the SCN-. At this point the concentration of (FeSCN)2+ is essentially the same as the initial concentration of SCN-, therefore SCN- is considered the limiting reactant. The absorbance of each solution at 447 nm will be measured and then a Beer's Law calibration curve will be prepared by plotting Absorbance versus concentration of (FeSCN)2+ ions. In the second part of the experiment five equilibrium solutions will be prepared using 0.050 M HNO3, 0.0020 M KSCN, and 0.0020 M Fe(NO3)3 and the absorbance of each solution will be measured at 447 nm. Note that in this portion of the experiment the Fe3+ is not in large excess. After determining the absorbance of each solution, the calibration curve prepared in Part I will be used to determine the concentration of (FeSCN)2+ ions in each solution. This will be the concentration of (FeSCN)2+ ions at equilibrium. From equilibrium concentrations of the absorbing (FeSCN)2+ ions, the stoichiometry of the reaction, and the initial concentrations of Fe3+ ions and SCN- ions, the equilibrium concentrations of Fe3+ and SCN- ions can be determined. The equilibrium concentrations of (FeSCN)2+, Fe3+, and SCN- ions can be substituted into the equilibrium constant expression (Equation (3)) and a numerical value of Kc can be determined for this reaction. Note: HNO3 is added to each solution to keep the Fe3+ in solution and prevent the formation of solid Fe(OH)3. The HNO3 is not considered a reactant.

Example For a hypothetical reaction, A + B C, only C absorbs at a given wavelength. Mixing 4.0 mL of 0.0010 M solution of A with 6.0 mL of 0.0020 M solution of B produces a solution that absorbs at the wavelength maximum of C. Using this absorbance and a Beer's Law calibration curve, the concentration of C at equilibrium was found to be 8.0x10-5 M. The equilibrium concentrations of A and B can be calculated as well as the value of Kc because the initial concentrations of reactants and product are known as well as the equilibrium concentration of C. Calculate the initial concentrations of A and B using M1V1 = M2V2:

(4.0 mL)(0.0010 M A) = (10.0 mL) M 2 (6.0 mL)(0.0020 M B) = (10.0 mL) M 2

The initial concentration of C is 0.

M 2 = 4.0 x10 4 M A M 2 = 1.2 x10 3 M B

Calculate the equilibrium concentrations of A and B:

initial change equilibrium

A 4.0x10-4 M - 8.0x10-5 M 3.2x10-4 M

B 1.2x10-3 M -8.0x10-5 M 1.1x10-3 M

C 0 + 8.0x10-5 M 8.0x10-5 M

Calculate the value of Kc:

[C ] [8.0 x10 5 ] Kc = = = 2.3 x10 2 4 3 [ A][ B] [3.2 x10 ][1.1x10 ]

Procedure:
Part A. Initial Set-up of the Spectrophotometer 1. The spectrophotometer needs to warm up for at least 15 minutes prior to any use. If the spectrophotometer has not been turned on when you enter the laboratory, turn it on. The spectrophotometer must be calibrated prior to the analysis of your samples. Your instructor will explain in detail how to carry out this calibration for the model spectrophotometer you will be using. The basic steps for calibrating a spectrophotometer are as follows: a) b) c) Set the desired wavelength (447 nm in this experiment). Make sure the sample holder is empty. Set the 0% T (infinite absorbance) by adjusting the zero knob. Set the 100% T (zero absorbance) by first placing a cuvette full with your solvent (nitric acid in this experiment) into the sample holder. This is your blank solution. Adjust the instrument's reading to 100 %T with the 100 %T control knob. The instrument is now calibrated for the SELECTED wavelength. Set the spectrophotometer to read absorbance and collect readings on your samples.

2.

3.

d) e)

Part B. Preparation of Standard Solutions 1. Set up two burets. Fill one buret with 0.00200 M KSCN solution and the other with 0.050 M HNO3 solution. Label each buret. Record the exact molarity of KSCN on the report form. Obtain 60 mL of 0.100 M Fe(NO3)3 in a beaker. Make sure you get the correct Fe3+ solution. Obtain 5 clean, dry beakers. Label the beakers '1', '2', '3', '4', and '5'. Use the buret to add the appropriate amounts of 0.00200 M KSCN solution and 0.050 M HNO3 solution listed in the table below into each beaker. Use a volumetric pipet to dispense the appropriate amount of 0.100 M Fe(NO3)3 solution into each beaker. Mix thoroughly. NOTE: This is a large excess of Fe3+, so the limiting reactant is SCN- ions. Beaker 1 2 3 4 5 0.00200 M KSCN 5.00 mL 4.00 mL 3.00 mL 2.00 mL 1.00 mL 0.100 M Fe(NO3)3 5.00 mL 5.00 mL 5.00 mL 5.00 mL 5.00 mL 0.050 M HNO3 15.00 mL 16.00 mL 17.00 mL 18.00 mL 19.00 mL

2. 3.

Part C. Determination of Absorbances of the Standard Solutions 1. 2. Follow your instructor's directions in operating the spectrophotometer to obtain the absorbance of each solution at 447 nm. Obtain two matching cuvettes. Use the same cuvette for each reading so that the path length and reflectance are identical for each measurement. (NOTE: the two matching cuvettes have a mark on the side that must be aligned with the arrow on the edge of the cuvette holder.) Fill one clean cuvette full of 0.050 M HNO3 and use this as a "blank" to set the transmittance equal to 100% at 447 nm. See spectrophotometer instructions in Part A. Rinse the other cuvette 3 times with small amounts of the solution whose absorbance is to be determined. Fill the cuvette about full with solution 1. Use a Kimwipe to wipe the outside of the cuvette to remove any solution or fingerprints.

3. 4.

5. 6.

Determine the absorbance on the spectrophotometer. Record the absorbance on the report form. Repeat steps 4 and 5 for solutions 2-5. Record the absorbance of each solution on the report form.

Part D. Preparation of Equilibrium Solutions and Measurements of Absorbances 1. 2. Obtain 5 clean, dry beakers. Label the beakers '1', '2', '3', '4', and '5'. Obtain 60 mL of 0.00200 M Fe(NO3)3 solution in a beaker. Make sure you get the correct Fe(NO3)3 solution. Use the burets from Part B to add the appropriate amounts of 0.0020 M KSCN solution and 0.050 M HNO3 solution listed in the table below into each beaker. Use a volumetric pipet to dispense the appropriate amount of 0.00200 M Fe(NO3)3 into each beaker. Mix thoroughly. NOTE: the Fe3+ is not in large excess as in Part B. Beaker 1 2 3 4 5 3. 0.00200 M Fe(NO3)3 5.00 mL 5.00 mL 5.00 mL 5.00 mL 5.00 mL 0.00200 M KSCN 2.00 mL 2.50 mL 3.00 mL 3.50 mL 5.00 mL 0.050 MHNO3 3.00 mL 2.50 mL 2.00 mL 1.50 mL none

Measure the absorbance of each solution at 447 nm as done in Part C and record on the report form.

Calculations:
Part B. Preparation of Standard Solutions and Part C. Determination of Absorbances of Standard Solutions 1. Calculate the initial concentration of SCN- ions (in 25 mL) and the final concentration of (FeSCN)2+ ions (in 25 mL) for solutions 1-5 and record on the report form. (NOTE: because of the large excess of Fe3+ ions, the final concentration of (FeSCN)2+ ions is essentially equal to that of the intial concentration of SCN- ions.) Prepare a plot of absorbance (y-axis) versus concentration of (FeSCN)2+ ions (x-axis). Draw the best straight line through the data points. This is your Beer's Law calibration curve.

2.

Part D. Preparation of Equilibrium Solutions and Measurements of Absorbances 1. 2. Calculate the initial concentration of SCN- ions and Fe3+ ions (in 10 mL) for solutions 1-5 and record on the report form. Use the Beer's Law calibration curve prepared in Part C and the absorbance values from step 3 in Part D to determine the equilibrium concentration of (FeSCN)2+ in each solution and record on the report form. See background for information about using a Beer's Law calibration curve to find the unknown concentration of a solution. Using the initial concentrations of SCN- ions and Fe3+ ions and the equilibrium concentration of (FeSCN)2+ ions, calculate the equilibrium concentrations of SCN- and Fe3+ ions (see example in background). Calculate the value of Kc for solutions 1-5 and the average value of Kc for this reaction.

3.

4.

Chemical Equilibrium Determination of an Equilibrium Constant Laboratory Report

Name ______________________________ Date _______________________________
Parts A and B. Preparation of Standard Solutions and Determination of the Absorbances of the Standard Solutions Molarity of KSCN __________ M Solution Initial [SCN-] Molarity of Fe(NO3)3 __________ M Final [(FeSCN)2+] Absorbance

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Calculation workspace:

Part D. Preparation of Equilibrium Solutions and Measurements of Absorbances Molarity of KSCN __________ M Initial [SCN-] ___________ ___________ ___________ ___________ ___________ Initial [Fe3+] __________ __________ __________ __________ __________ Molarity of Fe(NO3)3 __________ M Absorbance _________ _________ _________ _________ _________

Solution 1 2 3 4 5

Calculation of Equilibrium Concentrations and Kc. Solution [(FeSCN)2+] at equilibrium Initial [SCN-] [SCN-] at equilibrium Initial [Fe3+] [Fe3+] at equilibrium 1 2 3 4 5

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Kc Average Kc

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Calculation workspace:

Chemical Equilibrium Determination of an Equilibrium Constant Pre-Lab Questions

Name ______________________________ Date _______________________________
1. a) Calculate the initial concentrations of SCN- ions and Fe3+ ions when a solution was prepared by mixing 5.00 mL of 0.00200 M KSCN, 6.00 mL of 0.220 M Fe(NO3)3, and 14.00 mL of 0.050 M HNO3. (NOTE: the final volume of this solution is 25.00 mL.) [SCN-]

[Fe3+]

b) If you assume this reaction is driven to completion because of the large excess of Fe3+, what is the concentration of (FeSCN)2+ that would be formed?

2.

A student prepared this equilibrium solution by mixing the following solutions: 2.00 mL of 0.00250 M Fe(NO3)3, 5.00 mL of 0.00250 M KSCN, and 3.00 mL of 0.050 M HNO3. (NOTE: the final volume of this solution is 10.00 mL.) The absorbance of this equilibrium solution was measured at 447 nm and from a Beer's Law calibration curve, the equilibrium concentration of (FeSCN)2+ was determined to be 3.6 x 10-5 M. a) Calculate the initial concentrations of Fe3+ and SCN- ions. [SCN-]

[Fe3+]

b) Calculate the equilibrium concentrations of Fe3+ and SCN- ions. Fe3+ initial + SCN (FeSCN)2+

change

equilibrium

c) Calculate the value of Kc for this reaction.