Harris Chapter 4: Statistics

Gaussian Distribution & Random Error s Standard Deviation & Confidence Intervals s Comparison of Means s Q-Test s Calibration Curves and Least Squares Regression
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The mean is sometimes called the arithmetic average. For analytical chemistry, we are normally calculating the mean of 3 or more points in a set of data
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Reduced random or indeterminate error

The closer the mean is to the true (sometimes called accepted or known) value, the more accuracy there is

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Standard deviation (s or STDEV) represents how closely data is scattered about the mean. n-1 is called the degrees of freedom A smaller standard deviation means there is less variability in your data, or that your results are more precise.
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You have better precision

 Standard Deviation (s) %RSD = x 100 Mean (x)

What is the mean, standard deviation and percent relative standard deviation (%RSD) for blue M&Ms in little bags of chocolate M&Ms

The Gaussian Curve

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A distribution of events occurring with variations that are due to random errors (indeterminate error) Used to evaluate the distribution of random variation about a mean value Key to the mathematical definitions of mean and standard deviation

Confidence Intervals
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Utilize students t tests. These were originally developed by a brewer for Guinness. Confidence intervals allow on to specify how confident or certain they are that the true value for a set of data lies within a specific range.

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The confidence interval is labeled () s is the standard deviation n is the number of measurements t is a statistical students t value When appropriate, confidence intervals are expressed with units and are sometimes expressed in sentence form.

Confidence Intervals are a statistical tool, and a tool only! They do not supersede an analysts experience or knowledge about the analysis or sample, but can provide complimentary information. What is the 95% confidence interval for the number of M&Ms in a little bag of chocolate M&Ms?

Comparison of Data with ttests.

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Case 1: we can just see if the known or true value falls within the confidence interval.
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A little bag of chocolate M&Ms is supposed to have 24 candies in it? Do our results include the known value at the 90% confidence interval? Problem 4-14 as an example

Case 2: Comparison of 2 data sets.

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Compare 2 sets of data Calculate a standard deviation for each Calculate a t value (tcalculated) Compare tcalc to ttable (from standard table)
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IF tcalc > ttable the values are statistically different at the indicated confidence interval or level IF tcalc < ttable the values are statistically similar at the indicated confidence level

Q-test for Outliers

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A Q-test is used to deal with outliers (suspect or spurious) in data sets

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It is only a statistical test, the chemist must use their experience. For example, if you know you made up 5 solutions for analysis, but you diluted #3 over the mark in the volumetric flask, then you shouldnt consider this in the mean, but perhaps discard that data. You would do this, in this case, even if the Q-test indicated otherwise!

gap Q = range

How to perform a Q-test.

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Write the data out in order (like on a number line) Identify the outlier in question. You can use a Qtest only to remove 1 data point from a set. Identify the gap and the range. Calculate Q (Qcalc) Qtable (table values) include the suspect point If Qcalc > Qtable then you can discard the data point at the indicated confidence level. Lets do problem 4-22.

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Linear Regression
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Used to prepare a best fit straight line to a set of data.

Widely used for calibration curves, where we relate signal (y axis-what you measured) to concentration or amount (x axis) Signal = slope x concentration + intercept R2 is the correlation coefficient squared. The closer it is to 1, the closer the line lies to the points.
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We will largely use the regression functions in EXCEL (most calculators do linear regression too)

Lets do problem 4-29.