STATISTICS IN DATA EVALUATION

Defining confidence limits Estimating the different of two means (t test) Estimating the precision of data from two experiments (F test) Deciding to accept or reject outliers (Q test) Calibration graphs Methods of validation

CONFIDENCE LIMITS AND CONFIDENCE INTERVAL

Confidence - assert a certain probability that the confidence interval does include the true value. The greater the certainty, the greater the interval required.

Confidence Limits (CL) Interval around the mean that probably contains . Extreme value of the range, a < x > b Confidence Interval (CI) Range within which we assume the true value lies. The magnitude of the confidence limits. x Confidence Limits Confidence Level Fixes the level of probability that the mean is within the confidence limits. 99.7%, 99%, 95%, 90%, 80%, 68%, 50%

CONFIDENCE LIMITS (CL) OF MEAN

Since the exact value of population mean, cannot be determined, one must use statistical theory to set limits around the measured mean, x , that probably contain . CL only have meaning with the measured standard deviation, s, is a good approximation of the population standard deviation, , and there is no bias in the measurement.

CONFIDENCE LIMITS (CL)

In the absence of any systematic errors, the limits within which the population mean () is expected to lie with a given degree of probability.

-0.67

+0.67

50%
dN/N dN/N
-1.29

80%
+1.29

95%
dN/N
-1.96

+1.96

-4 -3 -2 -1 0

1 2 3 4

-4 -3 -2 -1 0

1 2 3 4

-4 -3 -2 -1 0

1 2 3 4

CONFIDENCE INTERVAL (CI)

CI when is known (Population)

CI for = x z

N = Number of measurements

VALUES FOR z AT VARIOUS CONFIDENCE LEVELS

Confidence Level, % 50 68 80 90 95 96 99 99.7 99.9 z 0.67 1.0 1.29 1.64 1.96 2.00 2.58 3.00 3.29

CI For Small Data Set (N < 20) Not Known

CI for = x ts

Values of t depend on degree of freedom, (N - 1) and confidence level (from Table t). t also known as students t and will be used in hypothesis test.

Example 2

VALUES OF t AT VARIOUS CONFIDENCE LEVEL

Degrees of Freedom (N-1) 1 2 3 4 5 6 7 8 9 19 59 80% 3.08 1.89 1.64 1.53 1.48 1.44 1.42 1.40 1.38 1.33 1.30 1.29 90% 6.31 2.92 2.35 2.13 2.02 1.94 1.90 1.86 1.83 1.73 1.67 1.64 95% 12.7 4.30 3.18 2.78 2.57 2.45 2.36 2.31 2.26 2.10 2.00 1.96 99% 63.7 9.92 5.84 4.60 4.03 3.71 3.50 3.36 3.25 2.88 2.66 2.58

OTHER USAGE OF CONFIDENCE INTERVAL

To determine number of replicates needed for the mean to be within the confidence interval. To determine systematic error.

TESTING A HYPOTHESIS

Observation

Hypothesis Model NO

Reject

Valid? YES Basis for Further Experiment

SIGNIFICANT TESTS

Approach tests whether the difference between the two results is significant (due to systematic error) or not significant (merely due to random error).

NULL HYPOTHESIS, Ho

The values of two measured quantities do not differ (significantly) UNLESS we can prove it that the two values are significantly different. Innocent until proven guilty

The calculated value of a parameter from the equation is compared to the parameter value from the table. If the calculated value is smaller than the table value, the hypothesis is accepted and vice-versa.

NULL HYPOTHESIS, Ho
Can be used to compare:

and x

x1 and x 2
s and s1 and s2

APPLICATION OF t-TEST
A t-test is used to compare one set of measurement with another to decide whether or not they are significantly different.

t TEST
1. Comparison between experimental mean and true mean ( and x )

To check the presence of systematic error. Steps for t test. Example 4.

t TEST
2. Compare x1 and x 2 from two sets of data

Normally used to determine whether the two samples are identical or not. The difference in the mean of two sets of the same analysis will provide information on the similarity of the sample or the existence of random error. Steps Example 5

F TEST

Comparing the precision of two measurements Is Method A more precise than Method B? Is there any significant difference between both methods?

With the degree of freedom = N 1 Ho : s1 = s2 Then, if Fcalc < Ftable ,Ho is accepted. Since the values of F are always greater than 1, the smaller variance (the more precise) always become the denominator. V1 > V2, so

Example 6 Table F

DIXONS TEST OR Q TEST

A way of detecting outlier, a data which is statistically does not belong to the set.
Data: 10.05, 10.10, 10.15, 10.05, 10.45, 10.10

By inspection, 10.45 seems to be out of the data normal range. Should this data be eliminated? Example 7 Table Q

CALIBRATION GRAPHS

Commonly used in analytical chemistry to find the quantitative relation between two variables (e.g. response and concentration). The calibration curves are normally linear, however not all the points are located on the drawn straight line (random error). Regression analysis can be done on the data to see how good the linearity of the data is. (Method of least squares)

METHOD OF LEAST SQUARES

Linear relationship between analytical signal (y) and concentration (x). Calculate best straight line through data points, each of which is subject to experimental errors.

CALIBRATION CURVES

0.35 0.30

Response (Y)

0.25 0.20 0.15 0.10 0.05 0.00 0.0

y = mx + c

1.0

2.0

3.0 Concentration (X)

4.0

5.0

6.0

m = slope c = intercept

CALIBRATION METHODS

Standard Calibration Method Standard Addition Method

STANDARD CALIBRATION METHOD

1 ppm

2 ppm

3 ppm

4 ppm

5 ppm

Blank

Sample

STANDARD CALIBRATION METHOD

Concentration (ppm) 0.00 1.00 2.00 3.00 4.00 5.00 Sample

Signal 0.00 0.06 0.13 0.21 0.25 0.29 0.22

STANDARD CALIBRATION METHOD

Calibration Plot for Absorbance versus Concentration

0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0.0 1.0 2.0 3.0 Concentration

Absorbance

y = 0.06x + 0.0067

4.0

5.0

6.0

STANDARD ADDITION METHOD

(x + 0) ppm (x + 10) ppm (x + 20) ppm (x + 100) ppm Blank

( x + 50) ppm

STANDARD ADDITION METHOD

Concentration (ppm) (x + 0.00) (x + 10.00) (x + 20.00) (x + 50.00) (x + 100.00)

Signal 5.0 11.0 17.0 28.0 55.0

STANDARD ADDITION METHOD

Abs

60 50 40 30 20 10 0

-20

-10

10

20

30

Concentration

40

50

60

70

80

90

100

110

120

CORRELATION COEFFICIENT

To estimate how good the experimental points fit a linear curve. Calculate the product-moment correlation coefficient, R (or r) or correlation coefficient. Value of R lies in the range of 1 to +1 (1 r +1).

The closer the R value to 1 (or 1), the better the correlation between y and x. R = +1: perfect positive correlation with all points lying on a straight line with positive slope. R = 1: perfect negative correlation. Correlation coefficient, R2 of > 0.999: evidence of acceptable fit of the data to the regression line.

METHOD VALIDATION
DEFINITION

Method validation is the process to confirm that the analytical procedure employed for a specific test is suitable for its intended use.

The process of verifying that a procedure or method yields acceptable results.

PURPOSE OF VALIDATION
To defend validity of the result and demonstrate method is fit for the intended purpose. Responsibility of the laboratories. Based on evaluation of the method performance and the estimated uncertainty on the result.

VALIDATION OF ANALYTICAL METHOD (METHOD VALIDATION)

Analysis of Standard Samples (SRM) Analysis by Other Methods Standard Addition to the Sample