Application of Statistical Concepts in the Determination of Weight Variation in Samples

Kristia Bernadine Licudine Alcantara John Jason Zamora Fruto

Institute of Chemistry, University of the Philippines, Diliman, Quezon City 1101 Philippines Institute of Biology, College of Science, University of the Philippines, Diliman, Quezon City 1101 Philippines

ABSTRACT The objective of the experiment is the application of statistical concepts in analytical chemistry. The use of statistical methods in the variations in weight of the 25-centavo coin samples gives significance to the analysis. Two different determinations of this experiment is completed and presented for analysis of the comparative data. After the application of statistical methods to the data, the results enable the experimenters to attain results that are generally precise and accurate. The small values of the calculated results are good signs of an accurate and precise data. A high precision analytical balance was used to weigh the samples, for a better understanding of how it works and how to use it properly.

Introduction A quantitative science that aims to provide scientists with reliable and notable results is known as Analytical chemistry. It depends on reliable measurements to provide useful data for problem solving. These data are evaluated for their figures of merit such as accuracy and precision, and the optimum technique to achieve these performance parameters is to carry out replicate measurements. In making observations, many problems can arise, due to either systematic or random errors, or simply due to gross or human error. Inaccuracy is usually evident in some degree in analytical chemistry due to these different kinds of errors. Nevertheless, it must be noted that these errors that occur in such studies are important. [1] The accurate value for the concentration of some particular constituent in the analysis material cannot be determined exactly because such a determination requires that an infinite number of measurements be made. It is rational to assume that the accurate value exists and this

allows the scientists to estimate the limits between which the value lies. It is therefore a prerequisite for a scientist to be familiar with the fundamentals of statistical methods in order to achieve consistency in the presentation of analytical results and derivation of reliable estimates from the observational data. It would be hard to judge the significance of the results since the statistical method, like other mathematical procedures, cannot reveal anything that is not already implicit in the data. Here are some formulas used in the calculations: Mean:

[1]

Standard deviation:

[2]

Relative Standard Deviation:

[3]

Range: [4]

The samples are placed on a watch glass, and then each coin was weighed by weighing by difference. Forceps are used to transfer the samples from the watch glass to the small beaker to make sure that there will be no fingerprints on the sample. Even a fingerprint can cause a variation in the weight of the samples and can lead to gross errors in the analysis of the samples. Results and Discussion

Relative Range:

Table 1. Reported Values [5]

X

Confidence Limits:

[6]

s RSD R RR

Data Set 1 3.632217 0.053822 14.81807 0.2338 64.36841

Data Set 2 3.626094 0.052581 18.79099 0.2947 81.27201

Table 2. Confidence Limits at 95% Q-test:

| |

[7]

Data Set A B

The experiment also aims to familiarize students with the proper usage of the analytical balance, and also for a more in depth understanding of how it works. It also aims to introduce the use of statistical concepts and how to apply these in analytical chemistry.

CL at 95% 3.68 3.60 3.65 3.6

Table 3. Q-test Data Set A B Suspect Values H: 3.6683 L: 3.5587 H: 3.6683 L: 3.5587 Q tab 0.625 0.625 0.466 0.466 Q exp Conclusion 0.0958 Accepted 0.6387 Rejected 0.0958 Accepted 0.1332 Accepted

Experimental Detail The experiment was done by weighing ten 25-centavo coins using an analytical balance, through weighing by difference. Weighing by difference is a technique especially useful when a series of samples of about similar size are to be weighed. In weighing by difference, the container with all the samples is tared onto the analytical balance, and for every sample removed, the balance is tared again. [2]

In the values above, the two kinds of data sets should be noted. The Q-test and T-test was applied to the values acquired by each group (Appendix A), while the reported values refer to the values acquired by all the groups altogether (Appendix B). This was done to replicate measurements in order to reveal the 2

presence of random errors. These errors can be numerous, and with variable magnitudes. However, measurement errors can be minimized and can be eliminated altogether by careful experimental design and control. Quantitative data, organized or unorganized, show a common characteristic to concentrate at certain values usually somewhere in the center of the distribution. Thus, various measures are employed to measure this tendency, and these measures of tendency are also called Averages. The mean is the best known and most widely used measure of central tendency. [3] The mean, X, is the average value of the data. This average summarizes a mass of individual observations and provides a common denominator for making comparison. . It is of statistical certainty that the mean is more correct than any single, randomly chosen data in a series of measurement. Hence, the mean is reported in the results of the measurement. However, though it is an admitted fact that an average is very useful, the use of a single value to represent the whole distribution conceals many important facts. The use of a single value to represent the whole series gives misleading results because variability is as much characteristic of statistical data as similarity. Thus to have the proper knowledge of the formations of the series, we need some measurement that summarizes the dispersion of a frequency distribution. A good measure of dispersion should be based upon all observations, simple to understand, easy to compute, not be affected by sampling fluctuations, amenable to algebraical treatment, and should be rigidly defined. [3] Range and standard deviation are two examples of a category of dispersion known as absolute measures of dispersion. The range is the simplest of all measures of dispersion, and defined as the difference between extreme values i.e., maximum and minimum as shown in table 1, both data sets have low values for the range, wherein the range of data set 2 is higher. The standard deviation is the most important, the

most reliable and the most widely used measure of dispersion. It is the most useful parameter for illustrating measures of precision. It is regarded to be the most reliable measure of dispersion because it is amenable to algebraic treatment, it is a good estimate of the percentages of observations included between mean and various standard deviations, independent of the origin of measurement, and it is always computed from the mean, wherein the sum of squared deviations from mean is always minimum as compared to sum of squared deviations from any other value. Though it is based upon the deviations of the values from mean, it involves a different method of averaging the deviations. Here deviations are squared to make them positive. It is the square root of the quotient obtained by dividing the sum of the squares of deviations of items from the arithmetic mean by the number of observations. The fact that the process of square root is employed in standard deviation neutralizes the squared deviations because the square root is the anti-process of squares. [3] Thus, standard deviation is an average of deviations. As shown in table 1, the standard deviations of both data sets are low, with data set 1 being lower than data set 2. The confidence limits are the interval estimates of the mean. These intervals generate the upper and lower limits of the mean. It indicates the value of uncertainty for the estimated value of the true mean. [4] A narrow interval is an indication that our estimate for the true mean is more precise. As shown in table 2, the true mean of the data set A lies within 3.60 and 3.68 with 95% chance and probability whereas, the confidence limits for data set B lies between 3.60 and 3.65 with the same confidence level. It is implied with the confidence interval value that both data sets have great precision. It has a narrow interval value. A 95% level of probability does not necessarily mean that there is a 95% probability that the interval contains the true mean. This is because the interval computed from a given sample can contain the true mean or not. It is merely the proportion of the samples of a given size that contain the true mean. Thus, a 95% confidence level indicates that 95% of the value within the interval would contain the true mean. 3

There are times when a set of data contains an outlying result that appears to be outside the range of what random errors in the procedure would give. It is generally considered inappropriate to discard data without a reason. [3] However, the outlier could be the result of an undetected gross error. Hence, the Q-test was created to reject or accept a suspected result. Qtest is used when dealing with a small number of observations to determine whether to reject or retain a suspected data. In order for a value to be accepted, the value of its Q exp must be smaller than the Q tab. [2] For this experiment, the highest and the lowest values for each data set are established to be the suspected values to be tested for acceptance. The data that failed to pass the Qtest will be eliminated and will not be included in the statistical calculations. The data for the weights of the six samples from data set A passed the Q-test at 95% confidence level whereas one of the weight results from the data set B failed to pass the Q-test. This means that the results of data set 2 are less accurate compared to the data set. However, due to the fact that the Q-test was performed only on data sets A and B, the outlier cannot be removed from the statistical calculations, which involve data sets 1 and 2, which have a greater number of samples per data set. Conclusion The analytical balance is a high precision weighing instrument. It can measure masses to within 0.0001 g. In weighing using an analytical balance, the experimenters should be careful because a single fingerprint on a sample can cause a gross error on the values. The proper usage of the analytical balance is important to get reliable values, and also to maintain the high quality performance of the balance. Statistical methods are very essential in comparative and quantitative studies. As the complexity of the data increases, it is harder to come up with a consistent result by unaided judgment. The application of statistical methods

serves as an objective test for conclusion to avoid bias in the part of the experimenter. If a suspected value fails to pass the Qtest, it is rejected. This value could have been be a result of a human error, or it may also be due to the natural differences in the weights of the samples. These natural differences can be due to the dirt accumulated on the surface of the coins. These possibilities only show why there are times wherein a set of data containing an outlying result appears to be outside the range of what random errors in the procedure would give. It is generally considered inappropriate to discard data without a reason. Hence, the Q-test was created to reject or accept a suspected result.

The values for the range, standard deviation and relative standard deviation were generally small. These small values are good signs that the results from the experiment were generally accurate and precise. Certain treatments can be done to minimize the errors that can contribute to the inconsistency of the result. Instrument errors can be minimized by careful recalibration and good maintenance of the equipment. Personal errors can be minimized by care and self-discipline. It is also recommended that all of the 25-centavo coin samples be clean and dry to avoid outlying results. References [1] Skoog, D. A., et al. (2004). Fundamentals of Analytical Chemistry: Eighth Edition. Belmont, CA: Brooks/Cole, Thomson Learning, Inc. [2] Analytical Chemistry Laboratory Manual (2009) edition [3] Grewal, P. S. (1987). Numerical Methods of Statistical Analysis. New Delhi, India: Sterling Publishers PVT LTD [4] Whitmore, G. A., Neter, J., & Wasserman, W. (1993). Applied Statistics: Fourth

Edition. Englewood Prentice-Hall, Inc.

Cliffs,

New

Jersey: 9 3.587 4 3.655 1 3.577 1 3.762 9 3.613 4 3.572 1 3.623 9 3.772 1 3.659 4 3.633 3.634 8 3.747 3 3.633 3 3.622 2 3.554 9 3.613 7 3.648 4 3.624 8 3.614 7 3.569 6

Appendices

10

Appendix A 3.5587 3.6287 3.6683 3.6314 3.6555 3.6578 3.6341 3.6172 3.6448 3.5733

11 12

13

Data set A

14

15 Data set B 16 17

Appendix B 18 A. 19 Data Set 1 Sampl e# 20 X 3.558 7 3.628 7 3.668 3 3.631 4 3.655 5 3.657 8 3.645 3 3.686 5 0.07351666 7 0.00351666 7 0.03608333 3 0.00081666 7 0.02328333 3 0.02558333 3 0.01308333 3 0.05428333 3 21

0.0054047

22

2 3

1.23669E-05 0.00130200 7

23

24 6.66944E-07 0.00054211 4 0.00065450 7 0.00017117 4 0.00294668 25

4 5 6 7 8

26

27 28

0.04481666 7 0.02288333 3 0.05511666 7 0.13068333 3 0.01881666 7 0.06011666 7 0.00831666 7 0.13988333 3 0.02718333 3 0.00078333 3 0.00258333 3 0.11508333 3 0.00108333 3 0.01001666 7 0.07731666 7 0.01851666 7 0.01618333 3 0.00741666 7 0.01751666 7 0.06261666

0.00200853 4 0.00052364 7 0.00303784 7 0.01707813 4 0.00035406 7 0.00361401 4

6.91669E-05 0.01956734 7 0.00073893 4 6.13611E-07 6.67361E-06 0.01324417 4 1.17361E-06 0.00010033 4 0.00597786 7 0.00034286 7 0.0002619

5.50069E-05 0.00030683 4 0.00392084 7 5

29 30

3.576 5 3.672 6 3.630 7

31

32 33 34 35

3.595 3.764 9 3.648 7 3.659 8

36

3.593 3.630 4 3.770 1 3.581 3 3.538 3 3.597 6

37 38

39

40

41

42 43

3.59 3.658 4 3.582 1 3.608 3 3.608 3 3.592

44

45

46 47

7 0.05571666 7 0.04038333 3 0.00151666 7 0.03721666 7 0.13268333 3 0.01648333 3 0.02758333 3 0.03921666 7 0.00181666 7 0.13788333 3 0.05091666 7 0.09391666 7 0.03461666 7 0.04221666 7 0.02618333 3 0.05011666 7 0.02391666 7 0.02391666 7 -

1 0.00310434 7 0.00163081 4 3.641 8 3.655 4 3.669 4 3.622 5 3.588 1 3.595 8 3.616 3

48 49 50

2.30028E-06 51 0.00138508 0.01760486 7 0.0002717 53 0.00076084 0.00153794 7 B. 3.30028E-06 0.01901181 4 0.00259250 7 Data Set 2 Sample # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 54

52

0.04011666 7 0.00958333 3 0.02318333 3 0.03718333 3 0.00971666 7 0.04411666 7 0.03641666 7 0.01591666 7

9.18403E-05 0.00053746 7 0.0013826

9.44136E-05

0.00194628 0.00132617 4

0.00025334

X 3.5587 3.6287 3.6683 3.6314 3.6555 3.6578 3.6341 3.6172 3.6448 3.5733 3.6453 3.6865 3.5874 3.6551 3.5771

0.00882034 0.00119831 4 0.00178224 7 0.00068556 7

0.00251168 0.00057200 7 0.00057200 7 0.00160934

0.067394444 0.002605556 0.042205556 0.005305556 0.029405556 0.031705556 0.008005556 0.008894444 0.018705556 0.052794444 0.019205556 0.060405556 0.038694444 0.029005556 0.048994444

0.004542011 6.78892E-06 0.001781309 2.81489E-05 0.000864687 0.001005242 6.40889E-05 7.91111E-05 0.000349898 0.002787253 0.000368853 0.003648831 0.00149726 0.000841322 0.002400456 6

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

3.7629 3.6414 3.6287 3.604 3.6168 3.6134 3.5721 3.6239 3.7721 3.6594 3.633 3.6307 3.6081 3.5588 3.5587 3.6348 3.7473 3.6333 3.6222 3.5549 3.6137 3.5717 3.5773 3.6174 3.5589 3.6484 3.6248 3.6147 3.5696

0.136805556 0.015305556 0.002605556 0.022094444 0.009294444 0.012694444 0.053994444 0.002194444 0.146005556 0.033305556 0.006905556 0.004605556 0.017994444 0.067294444 0.067394444 0.008705556 0.121205556 0.007205556 0.003894444 0.071194444 0.012394444 0.054394444 0.048794444 0.008694444 0.067194444 0.022305556 0.001294444 0.011394444 0.056494444

0.01871576 0.00023426 6.78892E-06 0.000488164 8.63867E-05 0.000161149 0.0029154 4.81559E-06 0.021317622 0.00110926 4.76867E-05 2.12111E-05 0.0003238 0.004528542 0.004542011 7.57867E-05 0.014690787 5.192E-05 1.51667E-05 0.005068649 0.000153622 0.002958756

45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68

3.5765 3.6726 3.6514 3.6309 3.5706 3.6279 3.6307 3.595 3.7649 3.6487 3.6598 3.593 3.6013 3.6604 3.6117 3.6498 3.6304 3.7701 3.5813 3.5383 3.5976 3.59 3.656 3.5607 3.5338 3.8285 3.6584 3.5821 3.6083 3.6083 3.5921

0.002380898 7.55934E-05 0.004515093 0.000497538 1.67559E-06 0.000129833 0.003191622 69 70 71 72 73 74 75

0.049594444 0.046505556 0.025305556 0.004805556 0.055494444 0.001805556 0.004605556 0.031094444 0.138805556 0.022605556 0.033705556 0.033094444 0.024794444 0.034305556 0.014394444 0.023705556 0.004305556 0.144005556 0.044794444 0.087794444 0.028494444 0.036094444 0.029905556 0.065394444 0.092294444 0.202405556 0.032305556 0.043994444 0.017794444 0.017794444 0.033994444

0.002459609 0.002162767 0.000640371 2.30934E-05 0.003079633 3.26003E-06 2.12111E-05 0.000966864 0.019266982 0.000511011 0.001136064 0.001095242 0.000614764 0.001176871 0.0002072 0.000561953 1.85378E-05 0.0207376 0.002006542 0.007707864 0.000811933 0.001302809 0.000894342 0.004276433 0.008518264 0.040968009 0.001043649 0.001935511 0.000316642 0.000316642 0.001155622 7

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

3.6418 3.6399 3.6396 3.6618 3.5878 3.6554 3.6694 3.6225 3.5881 3.5958 3.6163 3.6341 3.6414 3.5938 3.5855

0.015705556 0.013805556 0.013505556 0.035705556 0.038294444 0.029305556 0.043305556 0.003594444 0.037994444 0.030294444 0.009794444 0.008005556 0.015305556 0.032294444 0.040594444

0.000246664 0.000190593 0.0001824 0.001274887 0.001466464 0.000858816 0.001875371 1.292E-05 0.001443578 0.000917753 9.59311E-05 6.40889E-05 0.00023426 0.001042931 0.001647909