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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Statistical Report on the Determination of Chromium VI in an Aqueous Sample via Redox Titrimetry and Colourimetry Author: Inkiru Bernard Author ID: 620022618 Date of Submission: November 21, 2011 True Concentration of Solution #5: 0.1304M

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Table of Contents

Title

Page (s)

Abstract Introduction Analytical Methodologies Analytical Data Appendices Discussion and Conclusion References

3 4 5-6 7-15 16-18 19-21 22

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Abstract

The Determination of the Concentration of Chromium VI in an aqueous sample has a true concentration of 0.1304M. The sample was analyzed by Redox Titrimetry and by Colourimetry to see which analytical method was more precise in determining the concentration. After the data was accumulated and tabulated, a Q test was done to remove any data points that were deemed to be outliers. The remaining data was then averaged and their standard deviations found. The Titrimetry experimental mean was found to be 0.1301M with an estimated propagated error of 8.54x10-4 and a standard deviation of 5.35E-03. The Colourimetry experimental mean was found to be 0.1358M with an estimated propagated error of 1.96x10-1 and a standard deviation of 2.07x10-2. T-tests to compare both experimental means with the true value were carried out and the outcome being that the null hypotheses were retained. There was found to be no systematic errors only random errors causing the means to be different and their differences found to be not significant. A F-test to compare the variances of both methods to see which is more precise was carried and to test if the two means of significantly different. The result was that the null hypothesis was rejected as the variances were found to be significantly different. The subsequent T-test carried out showed that the two concentrations determined by the analytical methods were not significantly different and that the differences observed were due to the presence of random errors and not systematic error. Finally, F-Tests were carried out to compare the estimated propagated errors and the standard deviations calculated for both methods. The result was that the two results were significantly different with the estimated propagated error being the more precise method of error analysis. An appendix showing sample calculations of these tests is provided. These results were discussed and a conclusion made that Titrimetry was a more precise method for determining the concentration of an unknown sample in an aqueous environment. There were several recommendations made to the laboratory manager regarding ways to improve the analytical methods.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Introduction

A study was conducted by the Chemical Analysis I Wednesday laboratory group over two days on September 28 and October 5, 2011. The objective of the study was to ascertain the merits of the analytical methods of redox titration and colourimetry of an aqueous solution of an unknown sample of Chromium VI. This report will give an outline of the analytical procedures employed in both methods and will also give a full account of their known limitations. A detailed presentation of the analytical data acquired will be made. This will include data tables, error calculations along with the statistical tests mainly F, Q and T tests carried out on the data obtained. A thorough analysis of the data presented will be done which will highlight any problems encountered during the experiments. Finally, there will be recommendations made to the laboratory manager regarding ways to improve the analytical method used.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Analytical Methods Redox Titration Determination A secondary standard solution of Fe(II) was standardized against a potassium dichromate (Cr2O72-) primary standard by transferring 10cm3 of the Fe(II) solution to a 250cm3 conical flask. It was then diluted to 50cm3 with distilled water, and 30cm3 of 3 moldm-3 sulphuric acid, 7cm3 of 85% phosphoric acid added. Five drops of diethylamine sulphonate indicator was added which was used to titrate the mixture to a purple colour. The Chromium VI sample was then determined by adding an excess of Fe(II) to an aliquot of sample#119 (solution 5) and then the unreacted Fe(II) was titrated with the primary standard of dichromate solution. This was done by pipetting 10cm3 of the supplied sample (approximately 0.001 moles) into a 250 cm3 flask and diluted to 50cm3 with distilled water. 30cm3 of the standardized Fe(II) solution along with 30cm3 of 3 moldm-3 of sulphuric acid, 7cm3 of 85% phosphoric acid and 5 drops of diphenylaminesulphonate indicator. This was then titrated to a purple colour. From this the concentration of Chromium VI in this sample was calculated and the error in this determination computed from the both the error in the standardization concentration and the error in the back titration. This was done using the propagation of errors method. The concentration and its associated was recorded and tabulated for subsequent analysis. This analytical method had high selectivity as it was able to identify the Chromium VI in the sample easily but relatively lower sensitivity as it was unable to detect low concentrations of the analyte in the given sample; thus its applicability is useful in detecting the presence of an analyte within a sample but unsuitable for determining low concentrations. (C20 J Laboratory Manual)

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Colourimetric Determination. From a primary standard of potassium dichromate solutions (Cr2O72-), a set of five standard solutions of were prepared . These were of approximate concentrations 4,3,2,1 and 0 x 10-4 moldm-3 in Chromium VI. This was prepared from an intermediate standard of that was approximately 5 times the concentration of the maximum required working standard from the primary dichromate standard. The supplied solutions were diluted (x 500) such that the final analytical solutions will have a concentration that will fall near the middle of the calibration curve. The absorbance of the standards and the samples were determined using the spectrophotometer. The absorbances of the solutions were plotted against the standard concentrations by the least squares method. From this the concentration of the sample was calculated by back-calculations to account for the 500 dilution factor. The errors in the samples were accrued from the least squares calibration line and its associated parameters. The selectivity of the method seemed relatively high as it was able to detect the Chromium VI in the sample although the method seemed susceptible to interferences in the sample however the method has high sensitivity as it is able to detect very low concentrations of the analyte in very dilute solutions. Its applicability is suited to detect low concentrations of an analyte. (C20 J Laboratory Manual)

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Analytical Data The following tables will show the concentrations of Chromium VI determined from solution sample 5 for both the redox titration and colourimetry methods. Data omissions have been made from the original data pool due to the statistical Q test being performed as well as intuitive reasoning. The remaining data were tabulated, averaged and their standard deviations found. From those calculations, the F and T statistical tests were performed to test several null hypotheses formed. Those results were then tabulated and used to make important inferences that help to achieve the objective previously described. ALL of the statistical tests performed were done with a 95 % confidence limit. Table 1: Table showing the concentrations of Chromium VI from Redox Titration and Colourimetry from sample solution #5 with a true concentration of 0.1305moldm-3 Redox Titration Concentration Error 0.0962 0.1186 0.1250 0.1290 0.1300 0.1302 0.1305 0.1313 0.1346 0.1348 0.1374 0.1510 8.30E-04 8.04E-04 8.47E-04 8.40E-04 8.71E-04 8.90E-04 8.59E-04 8.67E-04 8.31E-04 8.44E-04 8.78E-04 1.00E-03 Colourimetry Error Concentration II 1.17E-02 0.0594 1.39E-03 0.0762 1.60E-03 0.1008 3.50E-03 0.1185 7.26E-03 0.1188 1.66E-03 0.1295 2.24E-03 0.1296 7.92E-03 0.1304 3.88E-03 0.1338 1.60E-03 0.1352 4.91E-03 0.1499 2.72E-03 0.1667 2.52E-02 0.1756 2.04E-01 0.2437

Concentration I 0.0743 0.1005 0.1159 0.1159 0.1191 0.1250 0.1294 0.1300 0.1339 0.1345 0.1499 0.1663 0.1776 0.2412

Error 3.48E-03 1.17E-02 1.39E-03 1.61E-03 7.25E-03 1.69E-03 7.91E-03 2.25E-03 1.59E-03 3.89E-03 4.91E-03 2.72E-03 2.51E-02 2.06E-01

Estimate of Errors in Analytical Methods: Redox Titration: 8.54x10-4 moldm-3 Colourimetry: 1.97x10-2 moldm-3
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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Table 2 : Table showing Colourimetry Data with Relative Errors of Data Pairs Calculated Concentration Concentration I II 0.0743 0.0594 0.1005 0.0762 0.1159 0.1008 0.1159 0.1185 0.1191 0.1188 0.1250 0.1295 0.1294 0.1296 0.1300 0.1304 0.1339 0.1338 0.1345 0.1352 0.1499 0.1499 0.1663 0.1667 0.1776 0.1756 0.2412 0.2437 Relative Error 15.72913 19.48943 9.862015 1.558781 0.185934 2.491066 0.106405 0.240257 0.037243 0.386263 0 0.176556 0.762381 0.735796

Table 3: Table Showing Average Colourimetry Values after Data Pairs with Relative Errors over 10% Deleted Concentration Concentration Average I II Concentration 0.1159 0.1008 0.108317 0.1159 0.1185 0.117193 0.1191 0.1188 0.118933 0.1250 0.1295 0.127241 0.1294 0.1296 0.129527 0.1300 0.1304 0.130187 0.1339 0.1338 0.133863 0.1345 0.1352 0.134859 0.1499 0.1499 0.149885 0.1663 0.1667 0.166539 0.1776 0.1756 0.1766 0.2412 0.2437 0.242464

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Table 4 : Table showing Average Titrimetry and Colourimetry Concentrations [Redox Titration] 0.0962 0.1186 0.1250 0.1290 0.1300 0.1302 0.1305 0.1313 0.1346 0.1348 0.1374 0.1510 [Colourimetry] 0.1083 0.1172 0.1189 0.1272 0.1295 0.1302 0.1339 0.1349 0.1499 0.1665 0.1766 0.2425

From the table above, by analysis, certain data points above to be outliers from the larger data pool. They have been singled out and a Q test carried out on them to determine if they are indeed outliers and if they are to remain in the data set. Variations of the Q test will be used depending on the size of the data set. The formulas for the Q-test are:

Q10(expt) = (xn - xn-1)/(xn - x1). Q11(expt) = (xn - xn-1)/(xn - x2). Q21(expt) = (xn - xn-2)/(xn - x2). Q22(expt) = (xn - xn-2)/(xn - x3).

(n = 3 7) (n = 8 10) (n = 11 13) (n = 14 25)

The following table will show the values suspected of being outliers and the tests carried out to determine if they are indeed outliers.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Table 5: Table showing Q tests Results (As seen in Appendix 1)

Titrimetry Value Qobs Qcrit Result 0.546 Rejected 0.477 Retained 0.477 Retained 0.576 Rejected

Colourimetry Value Qobs Qcrit Result 0.546 Rejected 0.576 Retained 0.576 Retained 0.576 Retained

0.0962 0.69954326 0.1186 0.39817151 0.1374 0.21102421 0.1510 0.62338047

0.2425 0.60608653 0.1655 0.32298137 0.1083 0.44949495 0.1766 0.44949495

Table 6: Table Showing Remaining Titrimetry, Colourimetry Data Averaged and their Standard Deviations Found

Titrimetry 0.1186 0.1250 0.1290 0.1300 0.1302 0.1305 0.1313 0.1346 0.1348 0.1374 Average Std. Dev 0.1301 0.00535056

Colourimetry 0.1083 0.1172 0.1189 0.1272 0.1295 0.1305 0.1339 0.1349 0.1499 0.1655 0.1766 0.1358 0.02068657

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Now, the average concentration of each method will be subjected to three T-Tests to test the null hypothesis that the differences observed in the values is due to the presence on only random errors and no statistical errors and that they are not significantly different. These will include: y y y Titrimetry vs True Value Colourimetry vs True Value Titrimetry vs Colourimetry

Titrimetry versus True Value (As seen in Appendix 2) True Value : 0.1304 M Titrimetry Avg : 0.1301M Using the T test that compares an experimental mean to a true mean, we use the formula:

This is used to test the null hypothesis that there is no significant difference between the sample mean and the population mean. T-Observed = 0.177291 T-Critical= 2.262157 for 9 degrees of freedom Result: The hypothesis is accepted as the T-observed is less than T-critical, so the Titrimetry experimental mean does not differ significantly from the population mean. The difference observed is due only to random errors as there are no systematic errors observed.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Colourimetry versus True Value True Value : 0.1304 M Titrimetry Avg : 0.1358 Using the T test that compares an experimental mean to a true mean, we use the formula:

This is used to test the null hypothesis that there is no significant difference between the sample mean and the population mean. T-Observed = 0.86575 T-Critical= 2.228139 for 10 degrees of freedom Result: The hypothesis is accepted as the T-observed is less than T-critical, so the Titrimetry experimental mean does not differ significantly from the population mean. The difference observed is due only to random errors as there are no systematic errors observed. .

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Before testing to see if there is a significant difference between the Titrimetry and Colourimetry average concentrations, we have to take a measure of the variances to see the degree to which they differ so one can be sure what method of calculating t is to be used. To do this we perform the F-Test, which is used to test whether two standard deviations differ significantly. F-Test : Titrimetry versus Colourimetry (As seen in Appendix 3)

F -observed = 14.9478585 F- critical = 3.317 Result: Hypothesis is rejected, as the F-observed is greater than the F-critical, therefore the difference between the two standard deviations is significant. Having performed the F-test and rejecting its hypothesis, we can now perform the T-Test to test the two experimental means.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Titrimetry versus Colourimetry Since the population standard deviations are not likely to be equal, then one can use the pooled standard deviations in order to test if they two experimental means differ significantly (Miller & Miller, 2000). The following formula is used to calculate the statistic T.

t = (x

-x

)/ (s12/n1 + s22/n2)

.where the degrees of freedom is calculated from the equation:

DOF = (s12/n1 + s22/n2)2 / {(s14/(n12(n1 - 1))) + s24/(n22(n2 - 1))}

T observed = 0.881968 T critical = 2.178813 Result: Since the T-observed is less than T-critical, the null hypothesis is retained, as there is no significant difference between the two experiments. The difference observed is due only to random errors as there are no systematic errors observed.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Standard Deviations versus Estimated Propagated Errors Two F-tests will be carried out on the estimated propagated errors of both the Titrimetry and Colourimetry methods to see if there is a significant difference between the values obtained. The formula for the F-test is:

Titrimetry Standard Deviations versus Propagated Errors

Estimated Propagated Error = 0.000854 Standard Deviation = 0.005351 F observed = 6.265808 F critical = 3.868 Result: The hypothesis has been rejected as F observed is greater than F- critical. This means the difference between the two methods of analysis is significant. y Colourimetry Standard Deviations versus Propagated Errors

Estimated Propagated Error = 0.19691 Standard Deviation = 0.020687 F observed = 9.518538 F critical = 3.621 Result: The hypothesis has been rejected as F observed is greater than F- critical. This means the difference between the two methods of analysis is significant.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Appendix 1. Model Q test Calculation Suspected Value = 0.0962 M Degrees of Freedom = 13 Data Set Size (n) = 13 When testing for that data set size, the formula used is: Q21(expt) = (xn - xn-2)/(xn - x2). (n = 11 13)

Q observed = (0.0962 0.1250)/(0.0962 0.1510) = 0.699 The critical value for 13 degrees of freedom is 0.546; therefore the null hypothesis was rejected.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

2. Model T-test Calculation True Value = 0.1304 M Titrimetry Mean = 0.1301 Standard Deviation: 0.005351 Data Size N = 10 Degrees of Freedom = 9 When comparing an experimental mean to a true value, the formula used is:

t = (0.1304 0.1301) * 10/0.005351 = 0.177291 With t- critical equal to 2.262157, the null hypothesis was retained.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

3. Model F-test Calculation Variance of Titrimetry = 2.86E-05 Variance of Colourimetry = 4.28E-04 Degrees of Freedom = (1) Titrimetry = 9 Using the formula: (2) Colourimetry = 10

F observed = (4.28E-04) / (2.86E-05) = 14.9478585 With F critical being 3.317, the null hypothesis was rejected as the values differ significantly.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Table of Results T- Test Test No. 1 2 3 T-observed 0.177291 0.86575 0.881968 Tcritical 2.262157 2.228139 2.178813 Hypothesis Retained Retained Retained Test No. 1 2 3 F- observed 14.9478585 6.265808 9.518538 F-Test F- critical 3.317 3.868 3.621 Hypothesis Rejected Rejected Rejected Test No. 1 2 3 4 5 6 7 8 Q-Test QQobserved critical 0.69954326 0.546 0.39817151 0.477 0.21102421 0.477 0.62338047 0.576 0.60608653 0.546 0.32298137 0.576 0.44949495 0.576 0.44949495 0.576 Hypothesis Rejected Retained Retained Rejected Rejected Retained Retained Retained

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

Discussion and Conclusion: From the raw data first tabulated, on first analysis, there were some data points that were clearly different from the data set at large. Before analyzing the Titrimetry data, there were datum pairs for the Colourimetry which had to be statistically tested before they could be averaged. The relative errors of the datum pairs from their means were calculated and those datum pairs with a relative error of over 10% were eliminated from the data set. The remaining datum pairs were then averaged and tabulated. A table of both the Titrimetry and Colourimetry was recorded and the data sorted from which the outliers could be identified. All statistical tests were performed at the 95% confidence limit. The values which were suspected outliers had the Q test performed on them. The resulting data was then averaged and the standard deviations found, from which the TTest and F-test were performed to test several hypotheses. From results table, many important inferences can be drawn. Firstly, the Titrimetry mean of 0.1301 was deemed to be not significantly different from the true mean of 0.1304. It was also inferred that any difference observed was due to the presence of random errors and not systematic errors. From the results of the F test which compared the precision of the Colourimetry and Titrimetry, it was seen that the there was significant difference between the two methods with the Titrimetry being the more precise method for determining the concentration of an unknown sample. From the result of this test, it was deemed that the s-pooled method for comparing the two experimental means was not applicable. The alternate method for which the degrees of freedom had to be calculated was done and the result of the T-test showed that the there was no significant difference between the experimental means of both analytical methods. The only difference was due to the presence of random errors and not due to systematic errors. Finally the estimates of the propagation of errors for both methods were compared to the standard deviation computed for each method. The results of the tests showed that there was significant difference between the methods witch the propagation method for calculating error deemed more acceptable. During the two weeks over which the experiments were carried out, there were several problems encountered by the students. There was a lot of confusion and delay in measuring the absorbance of the standards made up as there was a lot of miscommunication by the lab demonstrators in making up the standards. They were less than helpful in guiding the experiments and at that point, the random errors make have been introduced in the Colourimetry data. If improvements could be made in that regard, there could be major improvement in the data accrued. It can be hereby concluded
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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

that Titrimetry is a more precise method for determining the concentration of an unknown sample and the propagation of errors deemed to be a better method of calculating the errors in that determination. However, to improve this analysis, there can be a few changes made. These include: (i) carrying out the experiment over two successive days instead of two days over two weeks, (ii) having better trained laboratory demonstrators who properly guide students during the analyses and (iii) clearer guidelines so as to reduce the errors made by students during the determinations.

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INKIRU BERNARD, 620022618

STATISTICAL REPORT- 2011

TRUE CONCENTRATION: 0.1304M

References Chapter 20 and Chapter 24 Skoog, West, Holler and Crouch, Fundamentals of Analytical Chemistry, 2004 Brooks/Cole Thomson Learning Chapter 2 and Chapter 3 Miller & Miller, Statistics and Chemometrics for Analytical Chemistry,2000, Pearson Education Limited C20 J Laboratory Manual, 2011 Lectures 2,3,4,5 Statistics and Laboratory Management Module, Dr. Jillian Roberts, 2011

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