UNCERTAINTY PROPAGATION MODULE

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INTRODUCTION
GOAL To introduce the students to the principles of uncertainty propagation in analytical measurements. SKILLS Propagation of uncertainty, method of least squares, data rejection, statistics. TEXT REFERENCES 1] On Class A glassware absolute uncertainty, see Daniel C. Harris, Exploring Chemical Analysis, 2nd edition, Freeman, 2001, pp.40-44. or Daniel C. Harris, Exploring Chemical Analysis, 3rd edition, Freeman, 2004, pp.38-42. On uncertainty propagation, see Daniel C. Harris, Exploring Chemical Analysis, 2nd edition, Freeman, 2001, pp.61-65 or Daniel C. Harris, Exploring Chemical Analysis, 3rd edition, Freeman, 2004, pp.58-62. On statistics and the least squares model, see Daniel C. Harris, Exploring Chemical Analysis, 2nd edition, Freeman, 2001, pp.73-89 or Daniel C. Harris, Exploring Chemical Analysis, 3rd edition, Freeman, 2004, pp.7186.

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PROCEDURE For all milk-related procedures, record available absolute uncertainties associated with all the equipment used (balances, volumetric glassware, and instruments). In the absence of any other information, use the following rule for the estimation of the associated uncertainty: Analog devices: Digital devices: 1/3 of the smallest division. 1/2 of the last digit. Since you cannot interpolate between two digits as you can between two graduations, the proper number of significant figures is still to the last digit.

If any of the volumetric glassware used is not labeled with the absolute uncertainty value associated, then refer to the appropriate tables in the textbook. Class A volumetric glassware is exclusively used in the lab. Using the uncertainty propagation rules outlined in Appendix A of the lab manual, calculate the uncertainty associated on the standard solutions prepared, as well as on the sample(s) to be measured.

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From the numbers obtained by the propagation of uncertainty, identify what are the likely sources of errors, and what process is responsible for the highest source of uncertainty. Justify your answers with numbers.

COMPLEMENTARY INSTRUCTIONS FOR REPORT

There are four sources of uncertainty that should be tabulated in your report. 1) 2) 3) 4) Ancillaries for preparation of standards and samples (glassware and balance) Regression uncertainty (if applicable) Instrumental uncertainty (if applicable) Operator uncertainty The report can take the following form. (I) Tabulate the uncertainty at the source for item used in the preparation of the standards and samples (i.e., pipettes, burettes, volumetric flasks and balances). Apply the rules of uncertainty propagation to obtain the corresponding uncertainty of each standard and well as the stock solution. If applicable, for each absorbance value of the standards there is a corresponding uncertainty due to the instrumental readout uncertainty (read in %T; must be converted to A through use of the rules of uncertainty propagation. See Appendix A). Tabulate the results and indicate the x and y uncertainties on each data point (uncertainty bars forming the uncertainty rectangle). (II) Determine the linear regression coefficients (i.e., slope, intercept) and the associated uncertainties. Plot the calibration curve including the uncertainties on the data as well as the line of regression (if applicable). (III) Determine the uncertainty of the estimation of concentration based on the experimental absorbance of your sample using Equation 3A (p. 101 in the Laboratory Manual). Make sure to use the mean absorbance value of your replicate sample measurements for this calculation. This value is the uncertainty associated with the use of the linear model (if applicable). (IV) To determine the contribution of the readout uncertainty on concentration estimate, use the linear model and propagate the uncertainty of the readout to the uncertainty of the estimated concentration. To simplify the equation, neglect the contributions of the uncertainties of the slope and intercept (if applicable). (V) To determine the contribution of the operator uncertainty, use the sample standard deviation of the replicate absorbance measurements and propagate the uncertainty through the linear model. Neglect the contributions of the uncertainties of the slope 95

and intercept (if applicable). On any other type of measurement, use the standard deviation of the mean of the replicates. In the case of single sample measurements (e.g. Kjeldahl), this step is not applicable. (VI) Compare the magnitude of the sources of uncertainty (if you have more than one). Identify the main source of the uncertainty and suggest potential improvements. Do not forget to propagate the uncertainty to the final answer, e.g. grams Lactose per 100 g milk, g Cl- per liter of milk, etc. (VII) Statistically compare your results with the published mean value (posted on MyCourses) for your analyte in milk. State clearly your conclusion and provide an explanation in case of statistical disagreement. (VIII) Statistically compare your results with the pooled student results (also posted on MyCourses) for your analyte in milk. State clearly your conclusion and provide an explanation in case of statistical disagreement. (IX) Statistically compare the pooled student results with the published mean value for your analyte in milk. State clearly your conclusion and provide an explanation in case of statistical disagreement. (X) Draw a global conclusion from all of the above. Hint: Ask yourself if a) your result is an outlier due to an experimental error, b) the milk sample provided (everyone has the same batch) is or is NOT representative of what is expected in general for milk and if not, is there any evidence that the experimental procedure is flawed and can induce bias in the results.

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