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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                                       =
                                                                          
                                                                         =1
                                                                           
                                                                               


           Group
             2




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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   %        Middle value in a data that has been
19.4 ppm                =                                              arranged in a numerical order
                                             6
19.5 ppm                                                               Can be used if data contain some outliers
19.6 ppm                             = 19.8  告                    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.




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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

                       = ヰ                                              ヰ   
                                                                      乞 =             100%
                                                                                ヰ
    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                                   
                                                                               =1(   )2
                                                                       =
                                                                                    1




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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 = =1 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 % Middle value in a data that has been 19.4 ppm = arranged in a numerical order 6 19.5 ppm Can be used if data contain some outliers 19.6 ppm = 19.8 告 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 = ヰ ヰ 乞 = 100% ヰ 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 =1( )2 = 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