Chapter 3:

Experimental Errors

Chapter 4:

Statistics

Steps in a Typical Quantitative Analysis

Data of unknown quality are useless! All laboratory measurements contain experimental error.
It is necessary to determine the magnitude of the accuracy and reliability in your measurements. Then you can make a judgment about their usefulness.

Terms & Definitions

Replicates - two or more determinations on the same sample Example 3-1: One student measures Fe (III) concentrations six times. The results are listed below: 19.4, 19.5, 19. 6, 19.8, 20.1, 20.3 ppm (parts per million) 6 replicates = 6 measurements The "middle" or "central" value for a group of results: Mean: average or arithmetic mean

x=

x
i =1

Median: the middle value of replicate data If an odd number of replicates, the middle value of replicate data If an even number of replicates, the middle two values are averaged to obtain the median

Calculation: Mean and Median

Example 3-2: measurements of Fe (III) concentrations: 19.4, 19.5, 19. 6, 19.8, 20.1, 20.3 ppm (parts per million) What are the mean and median of these measurements Mean = 19.4 + 19.5 + 19.6 + 19.8 + 20.1 + 20.3

6
= 19.78 ppm = 19.8 ppm

6 replicates
An even number of replicates !!! Median =

19.6 + 19.8 2

= 19.7 ppm

Calculation: Mean and Median

Example 3-3: measurements of Fe (III) concentrations: 19.4, 19.5, 19. 6, 19.8, 20.1 ppm (parts per million) What are the mean and median of these measurements Mean =

19.4 + 19.5 + 19.6 + 19.8 + 20.1 5

= 19.68 ppm = 19.7 ppm

5 replicates
An odd number of replicates !!!

Median = 19.6 ppm

Any Questions???

Terms & Definitions

Precision - describes the reproducibility of measurements. How close are results which have been obtained in exactly the same way? The reproducibility is derived from the deviation from the mean:
Deviation from the mean = di = |xi - X |

Standard deviation Variance Coefficient of variation

Terms & Definitions

Accuracy - the closeness of the measurement to the true or accepted value. This "closeness" called as the error: absolute or relative error of a result to its true value.

absolute error relative error

Terms & Definitions

Outlier - Occasional error that obviously differs significantly from the rest of the results.

Precision & Accuracy

Mean & True Value

Mean :

Xt = true value

Absolute and Relative Errors

Absolute Error (E) - the difference between the experimental value and the true value. Has a sign and experimental units:

E = xi xt
Experimental value true (acceptable) value Relative Error (Er) - the absolute error corrected for the size of the measurement or expressed as the fraction, %, or parts-per-thousand (ppt) of the true value. Er has a sign, but no units.

xi xt Er = xt x 100%

parts per hundred (pph) = Er x100 parts per thousand (ppt) = Er x1000

Calculation: Absolute and Relative Errors

Example 3-4: measurements of Fe concentrations: 19.4, 19.5, 19. 6, 19.8, 20.1, 20.3 ppm
Assumed we already knew the true value of Fe (III) concentration at 20.0ppm. What are absolute and relative errors of each

measurement?

E = 19.4 - 20.0 = -0.6 ppm E = 19.5 - 20.0 = -0.5 ppm E = 19.6 - 20.0 = -0.4 ppm E = 19.8 - 20.0 = -0.2 ppm E = 20.1 - 20.0 = 0.1 ppm E = 20.3 - 20.0 = 0.3 ppm

Er =(-0.6/20)x100% = - 3% Er =(-0.5/20) x100%= -2.5% ~ -3% Er =(-0.4/20) x100% = -2% Er =(-0.2/20) x100% = -1% Er=(0.1/20)x100% = 0.5% Er = (0.3/20)x100% =1.5% ~ 2%

Example 3-5
A method of analysis yields weights for gold that are low by 0.3 mg. Calculate the percent relative error caused by this uncertainty if the weight of gold in the sample is (a) 800 mg; (b) 500 mg; (c) 100 mg; (d) 25 mg

E = xi xt
xi xt Er = xt x 100%
E = -0.3 mg Er = (-0.3 mg/500 mg) x100% = -0.06% = -0.06 pph = -0.6 ppt

Any Questions???

Types of Errors
Systematic or determinate errors affect accuracy! Random or indeterminate errors affect precision! Gross errors or blunders Lead to outliers and require statistical techniques to be rejected.

Systematic or Determinate Errors

1. Instrument errors - failure to calibrate, degradation of parts
in the instrument, power fluctuations, etc.

2. Method errors - errors due to no ideal physical or chemical behavior - completeness and speed of reaction, interfering side reactions, sampling problems

3. Personal errors - occur where measurements require judgment, result from prejudice, color acuity problems

Systematic or determinate errors Potential Instrument Errors Variation in temperature Contamination of the equipment Power fluctuations Component failure
All of these can be corrected by calibration or proper instrumentation maintenance.

Systematic or determinate errors Method Errors Slow or incomplete reactions Unstable species Nonspecific reagents Side reactions These can be corrected with proper method development.

Systematic or determinate errors Personal Errors Misreading of data Improper calibration Poor technique/sample preparation Personal bias Improper calculation of results
These are blunders that can be minimized or eliminated with proper training and experience.

The Effect of Systematic Error - normally "biased" and often very "reproducible". 1. Constant errors - Es is of the same magnitude, regardless of
the size of the measurement. This error can be minimized when larger samples are used. In other words, the relative error decreases with increasing amount of analyte. Er = (Es/Xt )x100%

Constant eg. Solubility loss in gravimetric analysis eg. Reading a buret 2. Proportional errors - Es increases or decreases with
increasing or decreasing sample size, respectively. In other words, the relative error remains constant.

Proportional Typically a contaminant or interference in the sample

Detection of Systematic Method Errors

1. Analysis of standard samples 2. Independent Analysis: Analysis using a "Reference Method" or "Reference Lab" 3. Blank determinations 4. Variation in sample size: detects constant error only

Gross Error
Gross errors cause an experimental value to be discarded. Lead to outliers and require statistical techniques to be rejected. Examples of gross error are an obviously "overrun end point" (titration), instrument breakdown, loss of a crucial sample, and discovery that a "pure" reagent was actually contaminated. We do NOT use data obtained when gross error has occurred during collection.

Random Errors
caused by uncontrollable variables which normally cannot be defined The accumulated effect causes replicate measurements to fluctuate randomly around the mean. Random errors give rise to a normal or gaussian curve. Results can be evaluated using statistics Usually statistical analysis assumes a normal distribution

Term & Definition

The Nature of Random Errors also called "indeterminate" and follow a predictable pattern. Error is the deviation from the "true value" Random error results in values that are higher or lower than the "true value".

The Statistical Treatment of Random Error A. The Population and the Sample Data The population data is an infinite number of observations (all the possible results in the universe!). The sample data is a finite number of observations that are, hopefully, representative of the population.

A Normal or Gaussian Curve

Frequency

X-

The Statistical Treatment of Random Error

B. Properties of a Gaussian Curve - has a population mean, , and a population standard deviation. 1. Population mean. In the absence of systematic error, , is the true value for the measurement. The sample mean, x, approaches when the number of observations approach infinity. 2. Population standard deviation.

Standard Deviation
The Population of Standard Deviation ()

( x )
i =1 i

N ( x x)
i =1 i N

Sample of Standard Deviation (s)

2

Standard Deviation = s =

N -1

Sample Standard Deviation as a measure of precision

Reliability of the sample standard deviation (s) increases with the number of replicates (N). For N greater than 20, s Measuring 20 replicates is usually not practical!

Standard Deviation

Standard Deviation = s =

( x x)
i =1 i

N -1

Other measures of precision

Standard deviation Variance (s2) Relative standard deviation Coefficient of variation Spread or range

Other measures of precision

Variance (s2) The advantage of working with variance is that variances from independent sources of variation may be summed to obtain a total variance for a measurement

Other measures of precision

Relative standard deviation (RSD)

100 pph Coefficient of variation (CV)

Spread or Range (w)

The difference between the largest and the smallest values in the set of data.

Another term that is occasionally used to described the precision of a set of replicate data.

Calculation: S, Variance, RSD, CV, Range

Example 3-6: measurements of Fe (III) concentrations: 19.5, 19. 6, 19.4, 19.8, 20.1, 20.3 ppm (parts per million) What are the standard deviation, variance, RSD, coefficient of variation (CV) and range (w) of the data set?

N -1 19.5 + 19.6 + 19.4 + 19.8 + 20.1 + 20.3 Mean = = 19.78 ppm 6

Standard Deviation = s =

( x x)
i =1 i

N = replicates = 6
N-1 = 6-1 = 5 (number of degrees of freedom)
(19.5 19.78) + (19.6 19.78) + (19.4 19.78) + (19.8 19.78) + (20.1 19.78) + (20.3 19.78) s= 6 -1
2 2 2 2 2 2

= 0.396 = 0.40 ppm

Standard Error of a Mean or Standard Deviation of a Mean (sm)

The standard deviation of each mean is known as the standard error of the mean or Standard Deviation of a Mean

s Standard Deviation of a mean = s = N

m

It shows that the standard error of the mean is inversely proportional to the square root of the number of data (replicates), N.

Calculation: S, Sm, Variance, RSD, CV, Range

Example 3-7: measurements of Fe (III) concentrations: 19.5, 19. 6, 19.4, 19.8, 20.1, 20.3 ppm (parts per million) What are the standard deviation, Sm, variance, RSD, coefficient of variation (CV) and range (w) of the data set?
(19.5 19.78) + (19.6 19.78) + (19.4 19.78) + (19.8 19.78) + (20.1 19.78) + (20.3 19.78) s= 6 -1
2 2 2 2 2 2

= 0.396 = 0.40 ppm

s Standard Deviation of a mean = s = N 0.40 = = 0.16 ppm 6

m

Calculation of Sm (the standard error of the mean)

a) For 50 trails

0.0056 = = 0.00080 50 = 8.0x10 4 mL

b) For 1-25 trails S1-25 =0.0058 mL S26-50 =0.0054 mL

s s = N
m

0.0058 = = 0.0012 25 =1.2x10 3 mL

Pooled standard deviation

Combine standard deviation from different experiments to obtain a reliable estimate of the precision of a method

Example 3-8

Example 3-8

Pooled standard deviation

Combine standard deviation from different experiments to obtain a reliable estimate of the precision of a method

Quiz 3-1: Multiple choices: please circle the best answer. 1. Systematic errors affect _______ (a) accuracy (b) precision (c) none of these (a) accuracy 2. Random errors affect _________ (a) accuracy (b) precision (c) none of these (b) precision

Quiz 3-2: Multiple choices: please circle the best answer. 1. What is used to describe precision of measurements? (a) relative error (b) standard deviation (c) mean (d) medium (e) none of these (b) standard deviation 2. What is used to describe accuracy of measurements? (a) relative error (b) standard deviation (c) mean (d) medium (e) none of these (a) relative error

Error (Uncertainty) Propagation

Error (Uncertainty) Propagation

Error Propagation:Addition and Subtraction

Example 3-7: The volume delivered by a buret is the difference between the final and the initial reading. If the uncertainty in each reading is 0.02 mL, what is the uncertainty in the volume delivered? Supposed that the initial reading is 0.05 ( 0.02) mL and the final reading is 17.88 ( 0.02) mL 17.88 ( 0.02) 0.05 ( 0.02) 17.83 ( S) mL

S Volume delivered =

S + S = S + S = (0.02) + (0.02)
2 2 b 2 2 2 a i f

= 0.028 0.03 mL Volume delivered = 17.83 ( 0.03) mL

Example 3-9:
y = ax

S S =x y a
y

Example 3-10:
Y = a + b -c Sy =

S +S +S
2 2 b a

ab y= c S S S S = ( ) +( ) +( ) y a b c
y a 2 b 2 c

Any Questions???

Significant Figures
The number of digits reported in a measurement reflect the accuracy of the measurement and the precision of the measuring device. All the figures known with certainty plus one extra figure are called significant figures. In any calculation, the results are reported to the fewest significant figures (for multiplication and division) or fewest decimal places (addition and subtraction).

Significant Figures

30.2? mL 30.24 mL 30.25 mL 30.26 mL

Significant Figures
1. Determining the number of significant figures in a number.

Rule 1. Significant figures are: all the certain figures and the first uncertain figure!

Significant Figures
Type of balance Macrobalance
SemimicroAnalytical balance Analytical balance Analytical balance

Precision (s) (mg) 0.1 mg 0.01 mg 0.001 mg 0.0003 mg

Price ($) ~$3,000 ~ $7,000 ~ $13,000 ~ $16,000

a) 1.23 g

b) 1.230 g c) 1.2300 g

Methods for Reporting Data: Significant Figures

Disregard all initial zeros All remaining digits including zeros between nonzero integers are significant. Addition and Subtraction the smallest number of digits to the right of the decimal sets the significance Products and Quotients - the smallest number of significant digits determines significance Logarithms - for logs, keep as many digits to the right of the decimal as there are significant figures in the original number Antilogarithms - keep as many digits as there are digits to the right of the decimal point in the original number

Methods for Reporting Data: Significant Figures Disregard all initial zeros All remaining digits including zeros between nonzero integers are significant.
Example 3-11: (A) 0.002 has _______ significant figure. (B) 0.0202 has _______ significant figure. (C) 0.0020 has _______ significant figure (D) 24.00 has _______ significant figure. Answers (A) 1 (B) 3 (C) 2 (D) 4

Methods for Reporting Data: Significant Figures Addition and Subtraction the smallest number of digits to the right of the decimal sets the significance

Products and Quotients - the smallest number of significant digits determines significance

Calculation: Sum and Mean

Example 3-12: measurements of sample weight using different types of balances: 9.54, 9.542, 9.5, 9.5421, 9.5423 g. What are the sum and mean of these measurements? Sum = 9.54 + 9.542 + 9.5 + 9.5421 + 9.5423 = 47.6664 g = 47.7 g 9.54 9.542 9.5 9.5421 9.5423

9.54 + 9.542 + 9.5 + 9.5421 + 9.5423 47.67 47.7 = = 5 5 5 Mean =

= 9.53 g

Rounding Data
Round up for digits > or = 5, and round down for digits <5 Use common sense when rounding. Remember that even though 3 significant figures may be permissible for a S value, S is term so that, 2.10 0.0111 becomes 2.10 .011. Remember not to round off calculations until the final result is obtained!

Example 3-13:

Any Questions???

Summary
Mean: Median: Accuracy: Precision:

Errors:
Absolute and Relative Errors Systematic or determinate errors Random or indeterminate errors Gross errors or blunders

Summary
Absolute standard deviation or standard deviation Relative standard deviation

Standard deviation of the mean (sm)

Pooled standard deviation Coefficient of variation Variance (s2) Spread or range Significant Figures

Homework

Chapter-3: 3-1, 2, 5, 10, 12, 13, 15, 16, 22

Before working on Homework,

Practice with all examples that we discussed in the class and related examples in textbook !!

The End!