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Equilibrium Constant Report Example 4

The document describes an experiment to determine the equilibrium constant of the reaction between Fe3+ and SCN- ions. A calibration curve was created using standard solutions of known FeSCN2+ concentrations to determine molar absorptivity. Test solutions were prepared and their absorbances measured. Beer's law and the calibration curve were used to determine unknown concentrations and calculate the equilibrium constant, which was found to be 309.3, close to the accepted value of 271.49.

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94% found this document useful (17 votes)
15K views

Equilibrium Constant Report Example 4

The document describes an experiment to determine the equilibrium constant of the reaction between Fe3+ and SCN- ions. A calibration curve was created using standard solutions of known FeSCN2+ concentrations to determine molar absorptivity. Test solutions were prepared and their absorbances measured. Beer's law and the calibration curve were used to determine unknown concentrations and calculate the equilibrium constant, which was found to be 309.3, close to the accepted value of 271.49.

Uploaded by

jim gorman
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Determination of an Equilibrium Constant

Rhonda Shuler-Calvaresi, Sharline Paul, Gilbert Huizar, and Brittany Helaire


Abstract
The purpose of this laboratory experiment was to determine the equilibrium

constant of a chemical reaction using Fe3+ (aq) and SCN- (aq) (1). The experiment

equilibrium constant was derived from the average of the trial results. The average

equilibrium constant for [FeNCS2+] was calculated and was determined to be 309.3, while
the accepted standard equilibrium constant for [FeNCS2+] Kc =271.49; the error analysis
for the experiment was 14%; the standard deviation was 23.08 .

Introduction

The experiment was completed to determine the equilibrium constant of a chemical

reaction using Fe3+ (aq) and SCN- (aq). This chemical reaction created a state of chemical

equilibrium. The equilibrium state can be categorized by stating its equilibrium constant as
large, greater than one, or small, less than one , but not negative or zero. A large Kc

(equilibrium constant) means that at equilibrium, the concentrations of the products will
generally be greater than the concentrations of the reactants, meaning it is products

favored. A small Kc means that at equilibrium, the concentrations of the reactants will
generally be greater than the concentrations of the products, meaning it is reactants
favored. The relevant chemical equation for this lab is:

Fe3+(aq) + SCN-(aq) FeSCN2+(aq)

(1)
1

Once the equilibrium concentration of FeSCN+2 (aq) was determined, the equilibrium
concentrations of the reactants (Fe+3 (aq) and SCN (aq) can be calculated. The

stoichiometry was 1:1:1 (reactant: reactant: product); the moles of each reactant was used
up in the reaction equaled to the moles of product formed (equation 1). The initial

concentrations of the known reactants were subtracted to find the moles of reactant
remaining at equilibrium. When the chemical reaction reached equilibrium, the

concentrations of reactants and products no longer change with time (2). Concentrations
were measured, the value of the equilibrium constant was easily calculated. Finally, the
concentrations of each sample in the experiment were calculated; so, the equilibrium
constant was calculated.

Kc = [FeSCN2+]/[Fe3+ ][SCN-]

(2)

To find the value of Kc, it is necessary to determine the concentration of several solutions
at equilibrium. In this experiment, FeSCN2+ (aq) was a colored solution so that the

concentration was determined by measuring its absorbance using spectrophotometric


methods (3).

A spectrophotometric method of analysis involves using light waves. This method

requires a calibration curve using samples of known concentration. This can be done by

spectroscopy. Determining a calibration curve for FeSCN2+ (aq) was accomplished by using

a spectrophotometer, Figure 1. This was accomplished by using a

spectrophotometer, an instrument used to measure the amount of

light that passes through a sample (1). Spectroscopy pertains to the

Figure 1 Spectrophotometer
2

scattering of an object's light into colors. Light acts like a wave and has properties. The
different wavelengths of light can be seen in the different colors. The entire
electromagnetic spectrum as shown in the figure below:

Figure 2 Electromagnetic Spectrum

The visible light region of the spectrum is small compared to the range of wavelengths. The

reactants in the solutions absorbed the light waves. The greater the concentrations of these
ions, the greater the absorbance of the solution was. There were several factors that

affected the absorbance of light: concentration of the solution, thickness of the sample of
solution, and the probability of the light absorbance of the solution (4).

Once the absorbency of the solutions was determined Beers law was applied. Beer's

law stated that absorbance of a molecule or solution is:


A = a*b*c

(3)

where A was the absorbance, "a" was the absorptivity (in units of per molar per cm, M-1

cm-1), "b" was the path length (in units of centimeters, cm), and "c" was the concentration
3

(in units of molar, M). This explained why the absorbance was linearly proportional to the
factors that affected it, the thickness, the concentration, and the absorptivity, of a given

sample. When the chemical reaction reached chemical equilibrium, the forward and the

reverse reactions rates were equal. The concentrations of the entire samples become part
constant (3).

Beer's law equation stated the absorbance (A), the light absorbed that passed through a

sample of the solution had a concentration (c) of the absorbing solute. According to Beer's

law, the amount of light that was absorbed by the colored sample [FeNCS2+] in solution for
the given wavelength was directly related to the concentration of the sample. The

absorbance was first measured for several samples of standard solutions with known

concentrations. Using Beers Law equation (equation 3), the molar absorptivity constant
for FeSCN2+ (aq) was determined by measuring its absorbance at different known

concentrations of FeSCN2+ (aq). If absorbance is plotted versus concentration, the slope will
give the molar absorptivity constant per Beer's Law. If a solute obeys Beer's law, then the
equation (equation 3), when graphed "Absorbance versus Concentration," yielded a

straight line. This graph was the calibration curve for the solute. From the calibration

curve, the absorbance of the solute with an unknown concentration was determined. With

the equilibrium, spectroscopy, and Beers law, all these were related to by light absorbency
concentration used to find the equilibrium constant of the FeNCS2+ (aq) solution (5).

Procedure
Preparation for the Samples for the Calibration Curve
The spectrophotometer was turned prior to the preparing of the solutions so that it

had time to become warm. A set of standard of solutions was created according to Table 1

below.

Table 1 Preparation of Calibration Curve Samples

Sample

0.2 M Fe(NO3) in M HNO3) (mL)

0.001 M NaSCN ( in 0.1 M


HNO3)

0.1 M HNO3
(mL)

10.0

14

Blank
2
3
4
5

10.0
10.0
10.0
10.0
10.0

0
2
3
4
5

15
13
12
11
10

Six 25 mL volumetric flasks were first rinsed and dried to ensure that there was no residue
from previous experiments. The volumetric flasks were then labeled blank and 1-5 so that
the order would not be confused. Following Table 1, 0.0001 M Na was added to each

volumetric flask. A plastic graduated cylinder was used to measure this solution. It was not
cleaned after every used of the same liquid. The solution was poured carefully and slowly

into the volumetric flask to ensure that none of it was spilled. Then 10 mL of 0.2 M of

Fe(NO3)3 was added to each volumetric flask. Using the same plastic graduated cylinder
that was now cleaned and dried, the next solution was added to the volumetric flasks.

Careful consideration was taken while pouring the measured solution into the volumetric

flask, trying to not spill it. Finally l 0.01 M HNO3 was added to each volumetric flask diluting

each one to 25 mL (the fill line of the flasks). Again, the same plastic graduated cylinder was
used after it was cleaned and dried for the last solution that was added. Once more, while

pouring the solution from the plastic graduated cylinder into the volumetric flask, care was
taken to that none of it was spilled. When the volumetric flasks were stirred or flipped
over to mix the solution, careful consideration was taken into account because the lids

were not totally secured when placed on the volumetric flask. Each solution was stirred to
make sure that the equilibrium was established throughout the solution.

The solutions needed to be measured by the spectrophotometer. Six cuvets, a

special piece of glassware that holds solutions to be measured in a spectrophotometer,


were gathered so that some of the solution could be put into each cuvet. After carefully
mixing the solution, each solution was poured into a cuvet. Each cuvet was filled about

three-fourths of the way so that there would be enough of the solution to measure. Lids

were securely placed on top of each cuvet to ensure that they were not spilled. All six of the
cuvets were brought to the spectrophotometer so that their absorbance could be

measured. The first solution in the cuvet to be tested was the blank solution. A Kimwipe
was used to wipe down the sides of the cuvet to remove any liquid or fingerprints. The

blank solution used to calibrate the spectrometer, which is termed blanking. The cuvet was
handled only on the sides that were grooved since the clear sides were used to test for

absorbance. The cuvet was place in the compartment aligning the marks of the cuvet with

the compartment. For maximum absorption of the wavelength the spectrophotometer was
set at 447 nm. No adjustments were made for the remainder of the experiment. The

remainder of the solutions (1-5) was then tested in a similar fashion and their absorbency
was recorded.

After the data were gathered and record, they were plotted in an absorbance versus

concentration line slope equation. A calibration curve was created to determine the

accuracy and to determine if part one needed to be repeated. Once the R2 was established

to be close to one, then the next part of the experiment could be accomplished.
Preparations for the Test Solutions

Since the spectrophotometer was previously used, it was still warmed for this

section of the experiment. All the volumetric flasks and graduated cylinders were cleaned

and dried so that they could either be reused or put away. The test solutions were prepared
according to Table 2 in six clean 10 mL volumetric flasks in the identical fashion as the ones

in the previous section of this experiment. These new volumetric flasks were labeled blank

and 6-10.

Table 2 Preparation of Samples for the Test Solutions

Sample

0.002 M Fe(NO) in 0.1 M HNO3


(mL)

0.002 M NaSCN (in 0.1 M


HNO3) (mL)

0.1 M HNO3
(mL)

Blank
2
3
4
5

5
5
5
5
5

0
2
3
4
5

5
3
2
1
0

Molar concentrations for this part of the experiment were different from the first part. A
new blank solution was created and used to recalibrate the spectrophotometer for this

section of the experiment. Determining the absorbance of the test samples, procedures
were followed from the previous section.

All waste from both sections was disposed of in the properly marked containers,

Waste Salts. All equipment was cleaned with tap water and returned its proper place.

The data gathered from the second part of the experiment was used for the calculations of
Kc (1).

Experimental Data
The data collected in this experiment follows:

Table 3 Concentration and Absorbance Data for Standard Samples


FeNCS2+ M

Absorbance

Blank
0
0

2.5*10-8

0.076

5*10-8

0.214

7.5*10-8

0.306

1*10-7

0.422

1.25*10-7

0.548

The line slope equation gathered from the data from Table 1 was graphed; thus, provided
Graph 1 and calculated the line slope equation and R2 value : A=2674.3-.0154 and the
R2=.9957.

Absorbance vs. Concentration


0.6

Absorbacne (AU)

0.5

y = 2764.3x - 0.0154
R2 = 0.9957

0.4

0.3

0.2

0.1

0
0

0.00005

0.0001

0.00015

Concentration (M)

0.0002

Graph 1 Absorbance vs. Concentration Graph

Table 4 Concentration and Absorbance Data for Test Samples


FeNCS2+ M

Absorbance

Blank
0

4.110*10-7

0.098

9.1*10-7

.0236

1.3*10-6

0.347

1.7*10-6

0.451

10

2.0*10-6

0.535

10

Calculations
The following calculations were made for the test solutions #6 solution.

A. Standard Solutions to Establish Calibration Curve


[Fe(NO3)3] . 02
[NaSCN] . 001
Vol. NaSCN
Mol. SCN-

. 001

.001 = 1 10

[SCN-] (25.0 mL) . 025 1 106 = 2.5 108


[FeSCN2+] 2.5 108 1 = 2.5 108
Absorbance 0.076

B. Absorbance for Test Solutions


[Fe(NO3)3] . 002
[NaSCN] . 002
Vol. Fe(NO3)3 5
Mol Fe3+, initial 1 105
Vol. NaSCN 1
Mol SCN-, initial 2 106
Absorbance 0.098

C. Calculation of Kc

[FeSCN2+]eq 4.10 107


Mol. FeSCN2+eq 4.1 105
Mol. Fe3+, reacted (mol)

= =

.098+.0154
2764.3

= 4.102 107 105

Mol. Fe3+eq (mol) 4.102 105 .01 = 4.102 107


[Fe3+]eq (10 mL) 4.102 107 = 4.102 107 1: 1

SCN-, reacted 1 105 4.120 107 = 9.5898 106


SCN-eq 2 104 4.102 107 = 1.5 10
11

[SCN-]eq

1.589106
.01

= 1.58 104

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

Average Kc 309.3
Std. Dev. Kc 23.8
Then these calculations were repeated for the test samples #7-10.

Results and Discussion

One set of solutions with known molar concentrations of FeNCS2+ was prepared and

tested to create the calibration curve, a plot graph of absorbance versus concentrations.
This created a line graph of the slope intercept,
y = mx + b

(4)

The second set of FeNCS2+ (aq) solutions was prepared and mixed so that their molar

concentration could be determined. From this graph, the mass action expression of

equilibrium can be calculated. The data that was gathered was then placed in an Excel

spreadsheet so that absorbency versus concentration could be plotted. This graph

produced the equation 4. The new line slope equation that was formed from this data was
A=2764.3c-0.154

(5)

This equation (equation 5) was used to calculate [FeNCS2+], thus finding the Kc value and

the Kc average. The R2 = .9957; this number needed to be as close to the value of one (1) as
possible. First step was to calculate the absorbance of the standard solutions for the test

12

solution samples six through ten. With new absorbance values that could be substituted

into the equation 5 (Table 5 is for test sample #6), new calculations were made for the Kc.

Table 5 ICE Chart for [FeNCS2+]

Fe3+

SCN-

0.02

0.001

-x

-x

+x

0.02-x

0.001-x

1.59*10-4

4.102*10-5

9.59*10-4

FeNCS2+
0

With the concentrations of each ion, these values can be substituted into the Kc

equation (2). The average Kc =309.3. The accepted value is 271. The standard deviation for
the results is 23.08. This means that the data plotted will most likely lie in the range of

286.22-332.38. Looking at the Kc values, this statement is true for the values that were
calculated in this experiment. The relative standard deviation for this experiment was

7.46%. The relative standard deviation is the percent that each of the Kc values for each test

(6-10) will only be 7.46% away from each other. The relative or accepted analysis error is

for this experiment was14%; the acceptable error is 5% (1).

The significance of knowing an equilibrium constant was to be able to know if the

reaction is products favored or reactants favored. From a practical standpoint, producing a


given chemical product, it would be essential to know the Kc of a reaction so that the yield

13

of the product could be optimized. If Kc was very large, the concentration of the products

was much greater than the concentration of the reactants. The reaction essentially "goes to
completion." All or most of the reactants were used up to form the products. If Kc was very

small, the concentration of the reactants was much greater than the concentration of the
products. The reaction does not occur to any great extent. Most of the reactants remain

unchanged and there were few products produced. When Kc was not very large or not very
small (close to a value of 1), then approximately equal amounts of reactants and products

were present at equilibrium. The significance of the experimental results showed that the
Kc was large so that this reaction was products favored (6).

The errors that affected the results were due to several items: human factors and

equipment or instruments used. There were several different people who measure the

liquids. Each one with a different perspective on when volumes have been reached. Each

measurement was checked by all, but there was still the chance for errors. The cylinder was
to measure the liquids was not washed and dried after each use of the same solution. The

cylinder was plastic and not glass; plus, it was made of a cloudy and not clear plastic. Also,

The experiment called for the use of measuring pipettes, but in this experiment graduated

cylinders were used instead. This allowed for some larger errors to happen. The lids in the

first section of the experiment had to be held on as the solution was stirred. Some of the

solution might have leaked out of the volumetric flasks. Also, the lids had to be washed and
dried after each used. The cuvets that were used had to be checked very carefully since
quite a few of them were damaged with scratches and others defects. With all of these

opportunities for errors, the Kc values for the test solutions had a huge probability of being

erroneous. The data showed that the test #6 was right close to the accepted value

14

compared to tests #7-10. The accepted Kc value for FeNCS 2+ (aq) was 271.49. Most of the

test solutions fell into the range of 310-323. The standard deviation of the experiment was
23.08. This stated that most of the data plotted would be within 23.08 of the average Kc

value of 309.3. The error analysis for this experiment was 14%; while the accepted error
analysis is 5%. The standard deviation and the error analysis figures helped to reinforce
that mistakes were made while conducting this experiment.

One set of solutions with known molar concentrations of FeNCS2+ (aq) was prepared

and tested to create the calibration curve, a plot graph of absorbance versus

concentrations. This created a line graph of the slope intercept, y = mx + b. The second set

of FeNCS2+ (aq) solutions was prepared and mixed so that their molar concentration could

be determined. From this graph, the mass action expression of equilibrium can be

calculated. If some of the data was removed, then the graph and the data changed. If the

test results for sample #1(0.076) was removed from the graphing of the line slope, what
would happen to the values of R2 and the line slope equation? The plotted concentration
points that remained and were graphed creating points that were closer to the line. The

average Kc value decreased to 307.06, but the standard deviation increased to 31.67. The R2
value became .9993 thus moving closer to one.

Conclusion

This experiment was to determine the equilibrium constant of a chemical reaction

using Fe3+ (aq) and SCN- (aq). The concentration of [FeNCS2+] was taken from several

known standard concentrations and then graphed to form a line slope equation to

determine the Beers law equation and the R2 value to be applied to several unknown

15

concentrations and experimentally calculate the average Kc value which was derived from
several test solutions. The results of these measurements determined the equilibrium
constant for the formation of [FeNCS2+]. This was accomplished by using a

spectrophotometer to measure the light absorbency and the data from this was used to

graph a calibration curve to determine the molar absorptivity that was proportional to the
thickness of the sample, concentrations of the absorbing solution, and the absorptivity of

the samples. From which equilibrium concentrations were calculated with the Beers Law.
The average equilibrium constant for [FeNCS2+] was calculated and was determined to be
309.3 with the accepted standard Kc=271.49 [FeNCS2+]; the error analysis for the

experiment was 14% which could be derived from several factors: human error, using
graduated cylinders instead of measuring pipettes, scratched or irregular cuvets.; the
standard deviation was 23.08(1).

16

Works Cited
(1)

Beran, J. (2009). Laboratory manual for principles of general chemistry. (8th ed.,

(2)

Tro, N. (2008). Chemistry a molecular approach. (pp. 616-661). United States:

(3)

Miller, K. (2006, December 06). Determination of the equilibrium constant.

pp. 371-382). United States: John Wiley & Sons, Inc.

Princeton Hall.

Retrieved from
http://www.jackson.k12.ga.us/teachers/rbryan/AP_Chemistry_Online/LabReport
ExampleKeq.pdf
(4)

Kulesa, C. (1997, Febraury 11). What is spectroscopy?. Retrieved from

(5)

Lab #11:Determination of the equilibrium constant. (n.d.). Retrieved from

http://loke.as.arizona.edu/~ckulesa/camp/spectroscopy_intro.html

http://www.doctortang.com/AP%20Chemistry%20(Old)/Lab%2011%20Chemical
%20Equilibrium%20Constant.pdf

(6)

Determination of an equilibrium constant. (n.d.). Retrieved from


http://mhchem.org/223/pdfLabs223/DetEquilConst.pdf

17

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