Errors in Chemical Analysis Assessing Quality of Results

CHM202 Dr. S. Korfali

The following items will be discussed Uncertainty and Significant Figures (Chap.6) Errors in chemical Analysis (Chap. 5) a) Mean, Median b) Accuracy , Precision c) Absolute Error, Relative Error d) Systematic Error Random Error (Chap.6) a) Statistical Treatment of Random Errors b) Measure of Precision : Standard deviation, Relative standard deviation, Coefficient of variation Spread Sheet and Statistics
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Introduction and Uncertainty

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It is impossible to perform a chemical analysis is such a way that results are free of errors or uncertainties This imply that for a set of observations containing numbers and mainly for any experimental result involved with the numbers. The following should be discussed: a) uncertainty and significant figures b) errors; so that the final analysis of results be scientifically clarified and accepted.

Uncertainty in Measurement
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Results should be reported in such a way that the last digit (to right) is uncertain (estimated). For example you are given two different volume measurement devices (Graduated cylinder and burette) calibrated as:
1.3 (uncertain, estimated), exact reading 1 and 2 Absolute uncertainty 0.1 1.25 (uncertain, estimated), exact reading 1.2 and 1.3 Absolute uncertainty 0.01 In order to relate uncertainty to error What is needed is Relative Uncertainty = Absolute Uncertainty/ Magnitude of measured quantity e.g. an error of 0.1 cm to length a classroom means no error; while an absolute uncertainty of 0.1 cm to an object of 1 cm length is an error

2 1 0

Absolute uncertainty has same unit of measurement

Significant Figures
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The digits required to express a measurement or calculated result to correct uncertainty is referred to as Significant Figures The significant figures in a number are all known digits with certainty plus the first uncertain digit Example 1.3 ( 2SF); 1.31 (3SF) Zero may or may not be significant depending on its location in a number A zero that is surrounded by other digits is always significant, such as 30.24 Position zeros are not counted Zeros that document points are not counted (zeros to left are not counted, zeros to right are counted) Powers are not counted Example: 0.001457 (4SF) 1.00145 (6SF) 1000 (4SF) 100x102 (3 SF)

Rounding Rules of Numbers

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In order to record a measurement to correct significant figure, rounding rules of numbers should be reviewed Round off numbers means discard the unwanted digits. How ? Retain digits as required to correct SF, Check the last digit to be discarded. If: a) > 5, increase the preceding digit by one (or add 1 to preceding digit). b) < 5, retain the preceding digit as it is c) = 5 , always round so as result end with even number (preceding odd, add 1; preceding even retain) Example : Round the following to 3SF : 25.48 (8 > 5 ; add 1 to 4) number : 25.5 25.42 ( 2 < 5; retain preceding) number : 25.4 25.35 (= 5; preceding odd, add 1 to 3) number : 25.4 25.25 (=5; preceding even, retain) number: 25.2

Significant Figures in Numerical Computation

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How to report final result to correct SF Sum and Differences (addition and subtraction) : Absolute value of the reported result is important. The Answer can be expressed with no more certainty than the value with greatest absolute uncertainty. That is final result should contain decimal places as the one with least decimal place Example : 2.4 + 0.020 + 7.31 = 10.73 (least decimal is one) answer is : 10.7. Product and Quotient (multiplication and division): results should have relative uncertainty of comparable magnitude as the one with worst relative uncertainty. That is it should contain SF as one with least Example : 24x4.52/100.0 = 1.0848 (LEAST 2 SF) answer is : 1.1

Logarithm (Log): keep as many digits to right of decimal place as there are SF in original number Example log (4.000x10-5) = -4.3979400
4SF -4.3979

Antilogarithm : Keep as many digits as there to right of decimal point in original number Example : Antilogarithm (12.5) = 3.162277x1012

One decimal point

One digit : 3x1012

Errors in Chemical Analysis

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Every experimental result contain to an extent an error. The magnitude of the error determines the validity of experimental results In order to discuss the reliability of measurement (how to express errors), sources of errors, types and treatment. The mean and median should be first defined: N Mean :arithmetic mean (average) : Xi
x =
i =1

xi represents the individual values of x making up the set of N replicate measurements

Median : It is the middle result when replicate data are arranged in order of size. n For an odd number of data points, the median can be evaluated directly. n For an even number, the number of the middle pair is used n Example : Find Median of the following set: 19.4, 19.5, 19.6, 19.8, 20.1, 20.3; Median : (19.6 + 19.8)/2 = 19.7 Ideally the mean and median are identical Frequently, they are not, particularly when the number of measurements in a set is small The median is used advantageously when a set of data contains an outlier An outlier can have a significant effect on the mean of the set without affecting median.
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How to give or affirm reliability of measurement or report error ?

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Errors are generally reported as precision or accuracy: Precision: It describes the reproducibility of measurement, the closeness of results that have been obtained in exactly same way Thus precision is agreement among various results of same experiment Three terms are widely used to describe the precision of a set of replicate data : standard deviation, variance, and coefficient of variation In all of these there is how much individual results xi differs from the mean, which is called deviation from the mean di di = |xi - x | The relation to precision will be discussed later

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Accuracy: It indicates the closeness of measurement to its true or accepted value. That is it is the agreement between the mean of result of experimentally measured values and actual or true value. Accuracy is expressed in terms of either absolute error or relative error . The term absolute has a different meaning than mathematics absolute. Absolute error E = xi xt xi is the experimental mean , xt is the true value E can be Negative : show that experimental mean of results are smaller than true Positive : show that experimental mean of results are higher than true Relative Error is more useful quantity than the absolute error : Relative Error = (xi- xt)/ xt * 100 ( or it can be expressed as ppt)

Systematic Errors (Determinate Errors)

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Systematic errors have a definite value and an assignable cause They can be corrected for and affect repeated measurement (replicate) in same direction. Sources of systematic errors are: a) Instrumental, b) Personal, c) Methodical Instrumental: are caused by : Imperfection of measuring devices and instabilities in their components. All measuring devices have sources of systematic errors. For example pipettes, burettes and volumetric flasks may deliver volumes slightly different from those indicated by their graduation Due to temperature difference from calibration temperature Due to or from distortion in containers walls. Electronic instruments: subjected to instrumental systematic errors For example change in voltage of a battery-operated power supply that decrease with use. To minimize these errors one resorts to such techniques as calibration of equipment. and running blanks.

Personal Errors : result from carelessness or personal limitation of experimental techniques For example: Misreading of burette, adding 10 mL of reagent rather than 1 mL, adding NH3 rather than HNO3, overshooting end point in titration q These errors would be eliminated by a careful re-run of determination q Method Error : they arise from the non-ideal chemical or physical behavior of the reagents and reactions Examples of non-ideality include : slowness of reaction incompleteness of reaction instabilities of some species possible occurrence of side reactions that interfere with measurement process q These errors can be discovered and corrected for by calculation or procedure change
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Systematic error may be either constant or proportional That is the error might exist as constant or proportional Constant Error: The magnitude of a constant error stays essentially the same as the size of the quantity measured is varied. The absolute error is constant with sample size; but relative error varies with sample size The effect of constant error becomes more serious as the size of the quantity measured decreases. For example suppose 0.5 mg of precipitate is lost as a result of washing with 200 mL of a liquid. If : Precipitate weighs 500 mg relative error = (-0.50 mg/500 mg) * 100 = -0.1 % Precipitate weighs 50 mg relative error = (-0.50 mg/50 mg) * 100 = -1 %

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Proportional error: it increases or decreases with sample size Absolute error varies with sample size, but relative error stays constant with sample size A common cause of proportional error is the presence of interfering contaminants in the sample For example a widely used method for determining Cu is based on reaction of Cu (II) with I- : Cu2+ + I- I2 (measured and proportional to amount of Cu) If Fe3+ is present then it also reacts to give I2 Unless steps are not taken to prevent this interference, high results are observed for % of Cu, because I2 is due to Cu2+ an Fe3+. If sample size is doubled then amount of I2 liberated by both Cu and Fe is also doubled. The absolute error will be doubled, but relative error does not change. The magnitude of reported Cu is independent of sample size

Random Errors Indeterminate Errors

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Random Errors causes data to be scattered more or less symmetrically around a mean Errors arise from unknown causes and affect each determination in a different way Essentially non of errors can be discovered or corrected for Random error in measurement is reflected by its precision Indeterminate errors cause poor precision

Indeterminate errors scatter around the mean in a curve called Gaussian curve

a) Errors of small magnitude occur frequently, but large errors seldom occur b) Both positive and negative errors are probable

Describing the distribution of Experimental data

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The distribution of replicate data for most quantitative experiments approach that of Gaussian curve. Example consider data in Table (6-2, p 108) for calibration of 10 mL pipette This information is easier to visualize when data are arranged into frequency distribution (Table 6-3), Tabulate the number of data points falling in a series of adjacent 0.003 mL cells and calculate the % of measurement falling in each cell The 26 % of data reside in cell containing mean and median

The frequency distribution data in Table 6-3 are plotted as a bar graph or Histogram (A) As the number of measurement increases, the histogram approaches the shape of continuous or normal curve (B) that shows symmetrical distribution of data around the mean of an infinite set of data.

Sources of Random Error

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Personal : such as misestimating level of water with respect to the marking on pipette and mercury level in the thermometer Instrumental Variation in line voltage Variation of external conditions, where the observer has no control such as: Variation and drafts that cause small variations in balance Variation of temperature Variation of humidity

Treating Random Errors with Statistics

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In statistics, a finite number of experimental observation is called a sample data The sample is treated as a tiny of an infinite number of observations Statisticians call the theoretical number of data a population of data Statistical laws have been derived assuming a population data, often they must be modified substantially when applied to small sample because a few data points may not be representative of population Our concern is in sample data Data and plot follow a normal Gaussian curve, most concentrated around sample mean (x ). The population standard deviation (s ) The population standard deviation is a measure of the precision or scatter of population data.

The sample standard deviation is given by (s)

s=

(x
i =1

-m)

s=

( xi -x)
i= 1

N-1

(di)2
i= 1

N-1

q Chemists ordinary employ standard deviation (s) in reporting

precision of their data qOther terms are also employed for precision

Variance standard deviation of variation

Relative

Coefficient

Range

Variance (s2) : the variance is the square of standard deviation

2 s =

i =1

(d i )

N -1

i =1

(d i ) 2

N -1

q Relative standard deviation : Chemists frequently quote standard deviation in relative rather than absolute terms q The relative standard deviation is RSD and expressed in parts per thousand (ppt) s RSD = _ x 1000 x q Coefficient of Variation (CV) is RSD expressed as percentage

CV

s
_

x 100

Relative standard deviation often gives a clearer picture of data quality than absolute standard deviation n For example suppose a sample contains about 50 mg of copper and standard deviation (s) is 2 mg CV = (2/50) *100 = 4 % For sample containing only 10 mg CV = (2/10) *100 = 40 % Spread or Range: it is another term that sometimes used to describe the precision of a set of replicate results. It is the difference between largest and smallest.
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