Practical Statistics for the Analytical Scientist Table of Contents
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1 Practical Statistics for the Analytical Scientist Table of Contents Chapter 1 Introduction - Choosing the Correct Statistics 1.1 Introduction 1.2 Choosing the Right Statistical Procedures Planning Experiments Representative Test Portions for Large Samples Reviewing and Checking Data Reporting Results - Summarising and Describing Data Decisions about Differences and Limits Comparing Results with Limits Differences Between Sets of Data Calibrating Instruments Describing Analytical Method Performance Analytical Method Validation Analytical Quality Control Testing Laboratory Performance Proficiency Testing Measurement Uncertainty Chapter 2 Graphical Methods 2.1 Some Example Data 2.2 Dot Plots 2.3 Stem-and-Leaf Plots 2.4 Tally Charts 2.5 Histograms 2.6 Frequency Polygon 2.7 Cumulative Distribution 2.8 Box Plots 2.9 Scatter Plots 2.10 Normal Probability Plots Chapter 3 Distributions and Types of Data 3.1 Introduction 3.2 Describing Distributions 3.3 Distributions of Analytical Data The Normal Distribution The Lognormal Distribution Page 1 of 10
2 3.3.3 Poisson and Binomial Distributions 3.4 Distributions Derived from the Normal Distribution Distribution of Student s t The Chi-Squared Distribution The F Distribution 3.5 Other Distributions Rectangular Distribution (or Uniform Distribution) Triangular Distribution 3.6 Populations and Samples 3.7 Checking Normality 3.8 Types of Data Chapter 4 Basic Statistical Techniques 4.1 Summarising Data: Descriptive Statistics Introduction Counts, Frequencies and Degrees of Freedom Measures of Location Arithmetic Mean Median Mode Measures of Dispersion Variance Standard Deviation Standard Deviation of the Mean Relative Standard Deviation and Coefficient of Variation Range Quartiles and the Inter-Quartile Range Skewness Kurtosis 4.2 Significance Testing Introduction A Procedure for Significance Testing Steps in Significance Testing Stating the Hypotheses Checking the Distribution Selecting the Appropriate Test Choosing the Level of Significance Choosing the Number of Tails Page 2 of 10
3 Calculating the Test Statistic Obtaining the Critical Value Compare the Test Statistic with the Critical Value Using P-Values Tests on One or Two Mean Values - The Student t-test Comparing the Mean with a Stated Value (One-Sample Test) Comparing the Means of Two Independent Sets of Data (Two-Sample Test) Paired Comparisons Comparing Two Observed Standard Deviations or Variances - The F-test Comparing Observed Standard Deviation or Variance with an Expected or Required Standard Deviation Using Tables for the F Distribution 4.3 Confidence Intervals for Mean Values Chapter 5 Outliers in Analytical Data 5.1 Introduction 5.2 Outlier Tests The Purpose of Outlier Tests Action on Detecting Outliers The Dixon Tests The Dixon Q Test Extended Tests The Grubbs Tests The Cochran test 5.3 Robust Statistics Introduction Robust Estimators for Population Means Median and Trimmed Mean The A15 Estimate Huber s Proposal Robust Estimates of Standard Deviation Median Absolute Deviation MAD E Mean Absolute Deviation and smad Huber s Proposal When to use Robust Estimators Chapter 6 Analysis of Variance 6.1 Introduction Page 3 of 10
4 6.2 Interpretation of ANOVA Tables Anatomy of an ANOVA Table Rows in the ANOVA Table Columns in the ANOVA Table Interpretation of ANOVA Results 6.3 One-Way ANOVA Data for One-Way ANOVA Calculations for One-Way ANOVA Calculating the ANOVA Table Calculating Variance Components for One-Way ANOVA 6.4 Two-Factor ANOVA Applications of Two-Factor ANOVA 6.5 Two-Factor ANOVA: Cross-classification Two-Factor ANOVA for Cross-classification without Replication Data for Two-Factor ANOVA without Replication Results Table for Two-Factor ANOVA without Replication F-Tests in Two-Factor ANOVA without Replication Two-Factor ANOVA for Cross-classification with Replication Data for Two-Factor ANOVA with Replication The Concept of Interaction Results Table for Two-Factor ANOVA with Replication F-Tests in Two-Factor ANOVA with Replication Creating and Interpreting Interaction Plots Random Effects and Two-Factor ANOVA with Replication 6.6 Two-Factor ANOVA for Nested Designs (Hierarchical Classification) Data for Two-Factor ANOVA for Nested Designs Results Table for Two-Factor ANOVA for Nested Designs Variance Components F-Tests for Two-Factor ANOVA on Nested Designs 6.7 Checking Assumptions for ANOVA Checking Normality Checking Homogeneity of Variance Levene s Test 6.8 Missing Data in ANOVA Appendix: Manual Calculations for ANOVA Chapter 7 Regression 7.1 Linear Regression Introduction to Linear Regression Assumptions in Linear Regression Page 4 of 10
5 7.1.3 Visual Examination of Regression Data Calculating the Gradient and Intercept Inspecting the Residuals The Correlation Coefficient Calculating the Correlation Coefficient Interpretation of the Correlation Coefficient Uncertainty in Predicted Values of x Interpreting Regression Statistics from Software Statistics Describing Gradient and Intercept Estimates ANOVA Tables for Linear Regression Testing for Non-Linearity Inspection of the Residuals F-Test of Residual Standard Deviation Against Repeatability Standard Deviation ANOVA Applied to Residuals Testing for Significant Higher-Order Terms Designing Linear Calibration Experiments Minimising Prediction Uncertainty Replication in Calibration Summary of Linear Calibration Design Recommendations Planning Linearity Checks Two Common Mistakes 7.2 Polynomial Regression Polynomial Curves and Non-Linearity Fitting a Quadratic (Second Order Polynomial) Using Polynomial Regression for Checking Linearity Appendix: Calculations for Polynomial Regression Chapter 8 Designing Effective Experiments 8.1 Some New Terminology 8.2 Planning for Statistical Analysis Measuring the Right Effect Single-Versus Multi-Factor Experiments 8.3 General Principles 8.4 Basic Experimental Designs for Analytical Science Simple Replication Linear Calibration Designs Nested Designs Factorial Designs Page 5 of 10
6 8.5 Number of samples Number of Samples for a Desired Standard Deviation of the Mean Number of Samples for a Given Confidence Interval Width about a Mean Value Number of Samples for a Desired t-test Power Number of Observations for Other Applications and Tests 8.6 Controlling Nuisance Effects Randomisation The Advantage of Randomisation Implementing Randomisation Limitations of Randomisation Pairing Blocked Designs Introduction to Blocking Analysing Blocked Experiments Latin Square and Related Designs Validating Experimental Designs 8.7 Advanced Experimental Designs Fractional Factorial Designs Optimisation Designs Optimisation and Response Surface Modelling Star Design Central Composite Designs Box-Behnken Design Data Processing for Response Surface Designs Mixture Designs D-Optimal Designs Advanced Blocking Strategies Simple Blocking Extended to Multi-Factor Experiments Confounding with High Order Interaction Incomplete Block Designs Appendix: Calculations for a Simple Blocked Experiment and Further Reading Chapter 9 Validation and Method Performance 9.1 Introduction 9.2 Assessing Precision Types of Precision Estimate Repeatability Intermediate Precision Page 6 of 10
7 Reproducibility Experimental Designs for Evaluating Precision Simple Replication Studies Nested Design Precision Limits Statistical Evaluation of Precision Estimates Comparison with the Precision of an Existing Method Comparison with a Specified Precision Value 9.3 Assessing Bias Statistical Evaluation of Bias Data Comparison with a Reference Value Comparison with an Existing Method 9.4 Accuracy 9.5 Capability of Detection Limit of Detection Limit of Quantitation 9.6 Linearity and Working Range 9.7 Ruggedness Planning a Ruggedness Study Evaluating Data from a Ruggedness Study Chapter 10 Measurement Uncertainty 10.1 Definitions and Terminology 10.2 Principles of the ISO Guide to the Expression of Uncertainty in Measurement Steps in Uncertainty Assessment Specifying the Measurand Identifying Sources of Uncertainty The Measurement Equation Obtain Standard Uncertainties for Each Source of Uncertainty Convert Uncertainties in Influence Quantities to Uncertainties in the Analytical Result Combining Standard Uncertainties and Propagation of Uncertainty Reporting Measurement Uncertainty 10.3 Practical Implementation Using a Spreadsheet to Calculate Combined Uncertainty Alternative Approaches to Uncertainty Evaluation - Using Reproducibility Data 10.4 A Basic Methodology for Uncertainty Estimation in Analytical Science Page 7 of 10
8 Chapter 11 Analytical Quality Control 11.1 Introduction 11.2 Shewhart Charts Constructing a Shewhart chart Shewhart Decision Rules 11.3 CuSum Charts Constructing a CuSum Chart CuSum Decision Rules Chapter 12 Proficiency Testing 12.1 Introduction 12.2 Calculation of Common Proficiency Testing Scores Setting the Assigned Value and the Standard Deviation for Proficiency Assessment Assigned Value Standard Deviation for Proficiency Assessment z-score and Q-Score 12.3 Interpreting and Acting on Proficiency Test Results 12.4 Monitoring Laboratory Performance Cumulative Scores 12.5 Ranking Laboratories in Proficiency Tests Chapter 13 Simple Sampling Strategies 13.1 Introduction 13.2 Nomenclature 13.3 Principles of Sampling Randomisation Representative Samples Composite Samples 13.4 Sampling Strategies Simple Random Sampling Description Advantages and Disadvantages Statistical Treatment Stratified Random Sampling Description Advantages and Disadvantages Page 8 of 10
9 Statistical Treatment Systematic Sampling Description Advantages and Disadvantages Statistical Treatment Cluster and Multi-Stage Sampling Description Advantages and Disadvantages Statistical Treatment Quota Sampling Description Advantages and Disadvantages Statistical Treatment Sequential Sampling Description Advantages and Statistical Treatment Judgement Sampling Description Advantages and Disadvantages Statistical Treatment Convenience Sampling Description Advantages and Disadvantages Statistical Treatment Sampling in Two Dimensions Description Statistical Treatment 13.5 Uncertainties Associated with Sampling 13.6 Conclusions and Further Reading Appendix A Statistical Tables Table 1a Critical values for the Dixon test (95% confidence, two-tailed) Table 1b Critical values for the Dixon test (99% confidence, two-tailed) Table 2 Critical values for the Grubbs tests Table 3a Critical values for the Cochran test (95% confidence) Table 3b Critical values for the Cochran test (99% confidence) Table 4 Critical values for the Student t-test Table 5a Critical values for the F-test (95% confidence) Page 9 of 10
10 Table 5b Critical values for the F-test (97.5% confidence) Table 5c Critical values for the F-test (99% confidence) Table 5d Critical values for the F-test (99.5% confidence) Appendix B Symbols, Abbreviations and Notation Appendix C Questions and Solutions Page 10 of 10
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