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11/13/2012




                                                Objectives
                                                 Togain an understanding in some
                                                  concepts of statistical analysis
                           Errors in             Apply statistical concepts in analytical
                           Chemical               chemistry
                           Analyses
                           Wilbert Morales




Error in Chemical Analysis                      Basic Statistical Concepts
 Error   can be referred as                     Replicates
     Difference between a measured value and        Samples of about the same size that are
      the “true” or “known” value.                    carried through an analysis in exactly same
                                                      way
     Uncertainty in a measurement or
                                                 Population
      experiment
                                                     Infinite number of results that could be
                                                      collected over an infinite period of time
                                                 Sample
                                                     Subset of a population data




Population vs. Sample                           Basic Statistical Concepts
                                                 Mean
           Group
             1                                       Average value of two or more
                                                      measurements


                          Pop                                       𝑋=
                                                                          𝑁
                                                                         𝑖=1
                                                                           𝑁
                                                                               𝑋𝑖


           Group
             2




                                                                                                            1
11/13/2012




Example                                                           Basic Statistical Concepts
SAMPLE DATA 1                                                      Median
Det. Of Fe(II) conc     Mean:
                           19.4+19.5+19.6+19.8+20.1+20.3   %𝑝𝑝𝑚        Middle value in a data that has been
19.4 ppm                𝑋=                                              arranged in a numerical order
                                             6
19.5 ppm                                                               Can be used if data contain some outliers
19.6 ppm                            𝑋 = 19.8 𝑝𝑝𝑚 𝐹𝑒                    If set contains even no. of measurements,
19.8 ppm                                                                median is the average of central pair
20.1 ppm
20.3 ppm




Basic Statistical Concepts
 Precision
      Describes the reproducibility of
       measurements
      Measures the closeness of results obtained
 Accuracy
      Indicates the closeness of the measurement
       to the true or accepted value




Types of Error in Experimental                                    Three types of Systematic
Data                                                              Errors
 Systematic          Errors                                       Instrumental Errors
      Generally arise from identifiable sources                       Substandard volumetric glassware
       causing measured value to differ from true                      Faulty or worn chemical components
       or accepted value                                               Incorrect electrical signals
      The key feature of this is that the error is
       reproducible.




                                                                                                                            2
11/13/2012




Three types of Systematic                             Three types of Systematic
Errors                                                Errors
 Method    Errors                                     Personal    Errors
    Inadequate method validation                          Carelessness
    Nonideal chemical or physical behavior of             Insufficient training
     analytical system                                     Illness or disability




Accuracy                                              Accuracy
 Absolute   Error                                     Relative    Error

                      𝐸 = 𝑥𝑖 − 𝑥 𝑡                                           𝑥𝑖 − 𝑥 𝑡
                                                                      𝐸𝑟 =            𝑥 100%
                                                                                𝑥𝑡
    Tells whether the value in question is high or
     low




Types of Error in Experimental
Data                                                  Standard Deviation
 Random     Errors                                    shows
                                                            how much dispersion exists from the
    Cause the data to be scattered around the         average.
     mean value
    It affects the precision of measurements                                   𝑛
                                                                               𝑖=1(𝑥 𝑖− 𝑋 )2
                                                                       𝑠=
                                                                                    𝑛−1




                                                                                                          3
11/13/2012




Range or spread                               Example
 It
   is the difference between the largest     Determination of glucose level of diabetic patient
  value and smallest value in the set.       Data 1          Data 2         Data 3         Data 4
                                             Glucose Conc    Glucose Conc   Glucose Conc   Glucose
                                             (mg/L)          (mg/L)         (mg/L)         Conc (mg/L)
                                             1108            992            788            799
                                             1122            975            805            745
                                             1075            1022           779            750
                                             1099            1001           822            774
                                             1115            991            800            777
                                             1083                                          800
                                             1100                                          758




SEATWORK
 Consider
         the following sets of replicate      QUESTION???
  measurements:
                                                Next   meeting
        Set A       Set B         Set C
         3.5        0.812         70.65             Review of Significant Figures
         3.1        0.792         70.63
         3.1        0.794         70.64
         3.3        0.900         70.21
         2.5
 Foreach set, calculate
(a) Mean         (c) range
(b) Median       (d) standard deviation




Assignment
 Perform the following operations and
  observe proper significant figure.
A) 30.5 ml + 16.75 ml - 0.576 ml + 2.0 ml
B) 1.632x105 g + 4.107x103 g + 0.948x106 g
C) (3.26x10-5 L )*(1.78 L)
D) log 339
E) Antilog (-3.42)




                                                                                                                 4

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Errors in chemical analyses

  • 1. 11/13/2012 Objectives  Togain an understanding in some concepts of statistical analysis Errors in  Apply statistical concepts in analytical Chemical chemistry Analyses Wilbert Morales Error in Chemical Analysis Basic Statistical Concepts  Error can be referred as  Replicates  Difference between a measured value and  Samples of about the same size that are the “true” or “known” value. carried through an analysis in exactly same way  Uncertainty in a measurement or  Population experiment  Infinite number of results that could be collected over an infinite period of time  Sample  Subset of a population data Population vs. Sample Basic Statistical Concepts  Mean Group 1  Average value of two or more measurements Pop 𝑋= 𝑁 𝑖=1 𝑁 𝑋𝑖 Group 2 1
  • 2. 11/13/2012 Example Basic Statistical Concepts SAMPLE DATA 1  Median Det. Of Fe(II) conc Mean: 19.4+19.5+19.6+19.8+20.1+20.3 %𝑝𝑝𝑚  Middle value in a data that has been 19.4 ppm 𝑋= arranged in a numerical order 6 19.5 ppm  Can be used if data contain some outliers 19.6 ppm 𝑋 = 19.8 𝑝𝑝𝑚 𝐹𝑒  If set contains even no. of measurements, 19.8 ppm median is the average of central pair 20.1 ppm 20.3 ppm Basic Statistical Concepts  Precision  Describes the reproducibility of measurements  Measures the closeness of results obtained  Accuracy  Indicates the closeness of the measurement to the true or accepted value Types of Error in Experimental Three types of Systematic Data Errors  Systematic Errors  Instrumental Errors  Generally arise from identifiable sources  Substandard volumetric glassware causing measured value to differ from true  Faulty or worn chemical components or accepted value  Incorrect electrical signals  The key feature of this is that the error is reproducible. 2
  • 3. 11/13/2012 Three types of Systematic Three types of Systematic Errors Errors  Method Errors  Personal Errors  Inadequate method validation  Carelessness  Nonideal chemical or physical behavior of  Insufficient training analytical system  Illness or disability Accuracy Accuracy  Absolute Error  Relative Error 𝐸 = 𝑥𝑖 − 𝑥 𝑡 𝑥𝑖 − 𝑥 𝑡 𝐸𝑟 = 𝑥 100% 𝑥𝑡  Tells whether the value in question is high or low Types of Error in Experimental Data Standard Deviation  Random Errors  shows how much dispersion exists from the  Cause the data to be scattered around the average. mean value  It affects the precision of measurements 𝑛 𝑖=1(𝑥 𝑖− 𝑋 )2 𝑠= 𝑛−1 3
  • 4. 11/13/2012 Range or spread Example  It is the difference between the largest Determination of glucose level of diabetic patient value and smallest value in the set. Data 1 Data 2 Data 3 Data 4 Glucose Conc Glucose Conc Glucose Conc Glucose (mg/L) (mg/L) (mg/L) Conc (mg/L) 1108 992 788 799 1122 975 805 745 1075 1022 779 750 1099 1001 822 774 1115 991 800 777 1083 800 1100 758 SEATWORK  Consider the following sets of replicate QUESTION??? measurements:  Next meeting Set A Set B Set C 3.5 0.812 70.65  Review of Significant Figures 3.1 0.792 70.63 3.1 0.794 70.64 3.3 0.900 70.21 2.5  Foreach set, calculate (a) Mean (c) range (b) Median (d) standard deviation Assignment  Perform the following operations and observe proper significant figure. A) 30.5 ml + 16.75 ml - 0.576 ml + 2.0 ml B) 1.632x105 g + 4.107x103 g + 0.948x106 g C) (3.26x10-5 L )*(1.78 L) D) log 339 E) Antilog (-3.42) 4