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Chapter 2 - Data Analysis I

This document discusses the importance of statistics in analytical chemistry for communicating the significance of experimental data, describes common types of errors like random, systematic and gross errors, and outlines statistical methods for evaluating data like mean, standard deviation, accuracy and precision to minimize errors and determine the reliability of results. It also covers topics like significant figures and rounding off numbers in calculations.

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Nazratul Najwa
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© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
68 views

Chapter 2 - Data Analysis I

This document discusses the importance of statistics in analytical chemistry for communicating the significance of experimental data, describes common types of errors like random, systematic and gross errors, and outlines statistical methods for evaluating data like mean, standard deviation, accuracy and precision to minimize errors and determine the reliability of results. It also covers topics like significant figures and rounding off numbers in calculations.

Uploaded by

Nazratul Najwa
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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DATA ANALYSIS

Assoc. Prof. Dr. Azli B. Sulaiman


Department of Chemistry
Universiti Teknologi Malaysia
81310 UTM Johor Bahru
Johor Darul Takzim
azli@kimia.fs.utm.my
LECTURE OUTLINES
• Errors in Chemical Analysis
• Descriptive Statistics
• Precision and Accuracy
• Types of Error
• Significant Figures
• Statistics in Data Evaluation
• Calibration Curve
• Method of Validation
Why do we need statistics in
analytical chemistry?

• Scientists need a standard format to communicate


significance of experimental numerical data.
• Objective mathematical data analysis methods
needed to get the most information from finite data
sets.
• To provide a basis for optimal experimental
design.
ERRORS IN CHEMICAL ANALYSIS

• It is impossible to perform a chemical analysis that is


error free or without uncertainty.
• Our goals are to minimize errors and to calculate the
size of the errors.
• Normal phrases in describing results of an analysis:
“pretty sure”
“very sure”
“most likely”
“improbable”
• Replaced by using mathematical statistical tests.
ERRORS IN CHEMICAL ANALYSIS

• Is there such a thing as


“ERROR FREE ANALYSIS”?

- Impossible to eliminate errors.


- Can only be minimized.
- Can only be approximated to an
acceptable precision.
TO OVERCOME ERRORS

• Carry out replicate measurements.


• Analyse accurately known standards (SRM).
• Perform statistical tests on data.

How reliable are our data?


Data of unknown quality are useless.
DESCRIPTIVE STATISTICS

• Mean/Average
• Median
• Range
• Standard Deviation, s or 
• Relative Standard Deviation (RSD)
• Varian, V
MEAN/AVERAGE

• Sum of measurements divided by the number


of measurements
N

 xi
i=1
x =
N
Where xi = individual values of x
N = number of replicate measurements
MEDIAN

• Data in the middle if the number is odd,


arranged in ascending order.
• The average of two data in the middle if the
number is even arranged in ascending order.
RANGE

• The different between the highest and lowest


result.
STANDARD DEVIATION

• Measure of the precision of a population of


data.
• Small Sample Size
 (x  x) 2
i
s i

N 1

• Population
 i
( x  x ) 2

 i

N
RELATIVE STANDARD DEVIATION

• Standard deviation divided by the mean


VARIAN

• The square of standard deviation.


For sample, V = s2
For population, V = 2
EXAMPLE 1

10.08 10.11 10.09 10.10 10.12

Use your calculator to calculate the given data above:


• Mean/Average
• Median
• Range
• Standard Deviation
• Relative Standard Deviation (RSD)
• Varian, V
SCIENTIFIC CALCULATOR
MICROSOFT OFFICE - EXCEL
PRECISION

• Relates to reproducibility or repeatability of a


result.
• How similar are values obtained in exactly the
same way?
• Useful for measuring deviation from the
mean.

di  xi  x
ACCURACY

• Measurement of agreement between


experimental mean and true value
(which may not be known!).
• Measures of accuracy:
- Absolute error: E = xi - 
(where  = true or accepted value)

- Relative error: ER  | xi  μ | 100%


μ
Relative error is more useful in practice.
ACCURACY vs PRECISION
ACCURACY vs PRECISION
ACCURACY and PRECISION

SMART Student A Student B Student C Student D

10.00 10.10 9.65 9.97 9.80


10.00 10.08 9.75 9.98 9.89
DATA 10.00 10.09 9.78 10.02 10.01
10.00 10.07 10.07 10.03 10.13
10.00 10.08 10.24 10.05 10.22

MEAN 10.00 10.10 9.90 10.01 10.01

STD. DEV. 0.00 0.01 0.25 0.03 0.17


TYPES OF ERROR

• Gross Error
• Random Error
• Systematic Error
GROSS ERROR

• Serious but very seldom occur in analysis.


• Usually obvious - give outlier readings.
• Detectable by carrying out sufficient replicate
measurements.
• Experiments must be repeated.
• Examples:
- Instrument faulty
- Contaminate reagent
- Accidentally discarding crucial sample
RANDOM ERROR

• Indeterminate error.
• Data scattered approximately symmetrically
about a mean value.
• Affects precision, can only be controlled.
Dealt with statistically.
• Cannot eliminate but minimise.
• Examples:
- Physical and chemical variables
SYSTEMATIC ERROR

• Determinate error.
• Readings all too high or too low. Can either
be +ve or –ve.
• Affects accuracy.
• Determinable and that presumably can be
either avoided or corrected. Several possible
sources.
• Causing bias in technique.
SOURCES OF SYSTEMATIC ERROR

• Instrument Error
• Method Error
• Personal Error
INSTRUMENT ERROR

• Glassware such as pipets, volumetric flasks, burettes


may hold volume slightly different from those
indicated by their graduation (use at different
temperature from the calibration temp).
• Electronic devices such as spectrometers
(electrical power supply fluctuation, worn out parts).
• Need frequent calibration.
METHOD ERROR

• Due to inadequacies in physical or chemical


behaviour of reagents or reactions (e.g. slow
or incomplete reactions).
• Difficult to detect and the most serious
systematic error.

Example:
• Small excess of reagent required causing an
indicator to undergo colour change that signal
the completion of a reaction.
PERSONAL ERROR

• Sources: Physical handicap, prejudice, not


competence.

Examples:
• Insensitivity to colour changes
• Tendency to estimate scale readings to
improve precision
• Preconceived idea of “true” value.
MINIMIZE SYSTEMATIC ERROR

• Instrument errors by careful recalibration and good


maintenance of equipment.
• Method errors - most difficult. “True” value may not
be known. Three approaches to minimise:
- Analysis of certified standards (SRM)
- Use 2 or more independent methods
- Analysis of blanks
• Personal errors by care and self-discipline.
SIGNIFICANT FIGURES

• Minimum number of digits written in scientific


notation without a loss in accuracy.
• The digits in measured quantity, including all
digits known exactly and one digit (the last)
whose quantity is uncertain.
SIGNIFICANT FIGURES
Rules for the determining the number of significant
figures:
• Disregard all initial zeros.
• Disregard all final zeros unless they follow a decimal
point.
• All remaining digits, including zeros between non-
zero digits, are significant.

Rules for counting significant figures:


• Initial zeros or that set the decimal point are not
significant.
0.00004213 (4 SF) and 470,000 (2 SF)
• Zero is significant only when:

- It occurs in the middle of a number


401 - 3 significant figures
6.0015 - 5 significant figures
- It is the last number to the right of the
decimal point.
3.00 - 3 significant figures
6.00  102 - 3 significant figures
0.0500 - 3 significant figures
SIGNIFICANT FIGURES IN
ARITHMETIC

• Addition-Subtraction

Use the same number of decimal places as


the number with the fewest decimal places.

12.2 + 0.365 + 1.04 = 13.605 = 13.6


(1 dp) (3 dp) (2 dp) (1 dp)
• Multiplication - Division

Use the same number of digits as the number


with the fewest number of digits.
ROUNDING OFF
Rules of rounding off

• Do not retain any digit beyond the first uncertain one.


• If the digit beyond the uncertain one is less than 5,
leave the figure as it is.
• If it is equal or greater than 6, add one to the last
retained digit.
• If the next digit is equal to 5, round up to the nearest
even digit (2,4,6,8,0). This will prevent us from
introducing a bias by always rounding up or down.

Example: Rounding 12.450 to nearest tenth gives 12.4 but


rounding 12.550 to the nearest tenth gives 12.6.

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