Paper No: 2 Analytical Chemistry

Module: 2 Errors in analysis and laboratory safety

Development Team
Principal Investigator
Prof. R.K. Kohli
&
Prof. V.K. Garg & Prof. Ashok Dhawan
Co- Principal Investigator
Central University of Punjab, Bathinda
Dr. J. N. Babu,
Paper Coordinator
Central University of Punjab, Bathinda
Dr. Varinder Kaur
Content Writer Department of Chemistry,
Panjab University, Chandigarh
Content Reviewer Prof. Ashok Kumar
Punjabi University, Patiala

Anchor Institute Central University of Punjab

Analytical Chemistry
Environmental
Sciences Errors in Analysis and Laboratory Safety
 Description of Module

Subject Name Environmental Sciences

Paper Name Analytical Chemistry

Module
Errors in Analysis and Laboratory Safety
Name/Title
Module Id EVS/AC-II/02

Pre-requisites

Objectives

Keywords

Analytical Chemistry
Environmental
Sciences Errors in Analysis and Laboratory Safety
Module 2: Errors in Analysis and Laboratory Safety
Objectives: 1. To know about the various types of errors encountered in the analysis and
parameters used to represent these errors
2. To know the following about self generated questions.
1. What types of errors are encountered in analysis?
2. How these errors affect the results?
3. How various errors can be avoided?
4. How analytical data is calculated to minimize the affect of errors?
5. What is accuracy?
6. What is precission?
3. To know about laboratory safety measures and following questions related to
safety.
1. What type of safety procedures can be practiced in a chemical laboratory?
2. What type of precautions can be taken to protect eyes?
3. What are the important measures for personal safety?
4. How the hazardous materials are handled?
5. What is the significance of various signs used on chemical bottles?

Analytical Chemistry
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 ERRORS IN ANALYSIS

1. Description

In the previous module, we discussed about various analytical methods used for the measurement
and/or analysis purposes. These methods involve optimization of several parameters using specific
equipments operated by expert persons. In detail, sample preparation and analytical methods employ
measurement of a particular property with the help of various equipments including glass apparatus
like beaker, pipette, measuring cylinder, measuring flasks; auto-pipettes, weighing machines, weights,
filtration units and instruments with their accessories like pH meter with electrodes, spectrophotometer
with cuvettes, high performance liquid chromatography with columns etc. Secondly, various methods
such as precipitation, washing, drying, filtration, extraction etc are commonly used in sample
preparation procedures. Thirdly, man-power is also involved in the analytical experiments to perform
the experiment and record the data or to operate the instruments involved in the analysis. In addition,
calculative data such as amounts required for the experiment, yields, detection limits etc. is directly
related to the purity of the chemicals and reagents. The involvement of all these parameters directly or
indirectly (equipment, experimentation procedures and operational expertise) may alternate the final
result by adding some errors. For instance, to prepare N/20 NaOH solution, following factors are
responsible for the addition of errors at each step.

Procedure for the preparation Sources of errors involved

of N/20 NaOH solution
The weight of NaOH required
to prepare its N/20 solution is
calculated, weighed and
dissolved in distilled water in a
100 mL measuring flask. The
total volume is made upto the
mark by adding extra distilled
water.
1. Purity of NaOH provided by the manufacturer
2. Accuracy of weighing machine used for weighing NaOH or the
physical balance and the weights used for weighing
3. Accuracy of the graduated apparatus used in the measurement
such as cylinder, measuring flask
4. Purity of the distilled water
5. Environmental parameters such as NaOH is hygroscopic so the
weight may vary.
6. Experimental hand of the person who is performing the
experiment
7. Judgment of the meniscus in the measuring flask to make it
100 mL

Analytical Chemistry
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 It is clear from the example that a single step may add large number of errors and deviate results from
actual value. These deviations go on increasing with each step and may vary the results beyond
acceptable limits. Therefore, it is important to discuss the errors, their origin, effect on the results and
preventive measures to get error free results in detail. Before going into the details of errors,
knowledge of terms ‘accuracy’ and ‘precision’ is very important.

Precision

Precision is the extent to which the results of a multiple repeat experiments agree with one another
e.g. if an experiment is repeated five times and a same result is obtained, it is considered as a precise
result. Therefore, precision can be used to check the reliability of a method. It may be defined as the
“concordance between a series of measurement of the same quantity”. It gives information about the
reproducibility of the measurements and reliability of the method. Precision is the degree to which
several measurements provide results close to each other. It indicates the scatter in the data. Lesser the
scatter higher is the precision. Good precision does not assure good accuracy. A systematic error does
not affect precision of the method. In the analysis of unknown sample, precision is considered to know
the exact value of the analyte in the sample. The poor precision in the result affects estimation of
accuracy in the analysis.
Factors used to express precision

The precision of a method can be expressed in terms of three functions; 1) Standard deviation, 2)
Coefficient of variation, 3) Variance

Standard deviation

The standard deviation () of infinite number of data set can be expressed as the following equation.

Σ(𝑥𝑖 − 𝜇)2
𝜎=√
𝑁

Where xi represents the individual measurement; µ is the mean of the infinite number of measurements
and N is infinite number of measurements (i.e. ).

Analytical Chemistry
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 For N number of measurements, individual deviations for each data set can be calculated by taking a
reference value, which is generally estimated mean (𝑥̅ ) of different data sets. Therefore, estimated
standard deviation (s) of a finite set of experimental data (N<30) can be expressed as follows.

Σ(𝑥𝑖 − 𝑥̅ )2
𝑠=√
𝑁−1

The s value is just estimated  and its value approaches  with the increase in the number of
measurement set. Hence, s is generally used to express precision of a complete data set.

In routine practice, a relative value of standard deviation is given rather than its absolute value. The
relative standard deviation is given by following expression.
𝑠
𝑅𝑆𝐷 = 𝑠𝑟 =
𝑥

Where sr is relative standard deviation, 𝑥̅ is mean of the different values in a data set and s is estimated
standard deviation. It can be expressed in ppt of in percent (coefficient of variation).
𝑠
𝑅𝑆𝐷 𝑖𝑛 𝑝𝑝𝑡 = × 1000 𝑝𝑝𝑡
𝑥

Coefficient of variation

It is the relative standard deviation multiplied by 100% as given below (or RSD in percent).
𝑠
𝐶𝑉 = 𝑅𝑆𝐷 𝑖𝑛 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 = × 100%
𝑥

Variance

It is alternative parameter to express precision. It is the square of estimated standard deviation (s) or
absolute standard deviation (). It can be expressed as given below.

∑𝑁
𝑖=1(𝑥𝑖 − 𝑥)
2 ∑𝑁
𝑖=1(𝑑𝑖 )
2
𝑠2 = =
𝑁−1 𝑁−1

Accuracy

Analytical Chemistry
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 Accuracy is the degree to which the results of an experiment agree with the true or accepted value. e.g.
if the weight of a substance having known standard mass equal to 100 g is measured by a physical
balance and the result shows it 79.5 g it means the result is not accurate. But if the result shows 99.9 g
it means result is accurate.

The accuracy may be defined as the “nearness of a measurement to the standard or true value”.
The highly accurate results are provided by accurate instruments. The accuracy of a result depends
upon the instrument and the ability of an operator. A systematic error affects the accuracy of the
measurement.

Understanding precision and

accuracy by Dart board
The closer the dart hits to the
bulls eye, more accuracy is
obtained (I). If the person misses
the dart board with every throw,
but the shots come very close to
each other, it would be precise
but not accurate (II). If the bulls
are distributed throughout the
board, it is neither precise nor
accurate (III)

Example: The four different refrigerators were tested for accuracy and precision of temperature sensor
by recording temperature at different times. The results are given below along with the accuracy and
precision of temperature sensor. The refrigerator was kept at a constant temperature of 38.0 F.

Read Refrigerator 1 Refrigerator 2 Refrigerator 3 Refrigerator 4

1. 39.4 37.8 39.3 38.0
2. 38.1 38.3 39.2 38.0
3. 39.3 38.1 39.1 37.8
4. 37.5 38.0 39.0 38.1
5. 38.3 37.6 39.1 38.0
6. 39.1 38.2 39.3 37.9
7. 37.7 38.0 39.2 38.2
8. 37.1 38.0 39.1 38.0
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 9. 38.8 37.4 39.2 37.9
10. 39.0 38.3 39.2 38.0
Accuracy BAD GOOD BAD GOOD
Precision BAD BAD GOOD GOOD
Note : It is not necessary that good precision means good accuracy or vice versa.
Expression of accuracy
Accuracy can be expressed in terms of absolute error and relative error.
Absolute error
The absolute error of measurement is the difference between the measured value and the true value. It
can be obtained by the following equation.
𝐸 = 𝑥∘ − 𝑥𝑡
E = xo - xt
Where E is absolute error, xo is the measured value and xt is the true value
If the measurement value is more than the true value, the sign for absolute error is positive.
If the measurement value is less than the true value, sign for absolute error is negative.
Relative error
It is the absolute error divided by the true value. It may be expressed in percent or parts per million or
parts per thousand depending upon the magnitude of the result. It can be obtained using following
equation.
𝑥∘ − 𝑥𝑡
𝐸= × 100%
𝑥𝑡

Er = (xi – xt) x 100%

xt

2. Classification of errors

The errors may be divided into categories; systematic and random errors. The main features of two
types of errors are given below.

Analytical Chemistry
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 Systematic (Determinate) errors Random (Indeterminate) errors
 These errors can be measured or determined,  These are the errors encountered by an
and can be avoided. Although, their value observer during the repeated measurements
may be constant or variable, but preventive of same sample. These errors are added even
measures may eliminate the problems if the observer is very much expert and
associated with errors. perform the experiment carefully.
 These errors are generally introduced either  These errors follow normal distribution or
due to the negligence of operator, or Gaussian curve of probability.
improper functioning of instrument, or
selection of inappropriate method or presence
of impurities etc. These are mainly divided
into following categories on the basis of their
origin.
1. Operational and personal errors
2. Instrumental and reagent errors
3. Errors of method
These errors can be additive or
multiplicative depending upon the nature
and source of error.
 Personal or instrumental errors may be  These errors are difficult to eliminate
avoided by calibrating the instrument and because they may be very small or
errors related to method can be avoided by undetectable. Sometimes, they may be
using standard reference materials, avoided by applying the laws of probability
independent analysis or blank to achieve most probable result.
determinations.

1. Operational and personal errors:

These errors are associated with the expertise of the analyst and are added during experimentation.
These errors depend upon the knowledge, experimental hand and experience of the person who is
doing the experiment and interpreting the data. Examples:

1. Weighing of a compound slightly more or less than the actual quantity.

2. Prediction of the end point one drop after or before the appearance of accurate color.

3. Weighing of hygroscopic materials on filter paper

Analytical Chemistry
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 3. Overheating or insufficient cooling of contents

4. Measurement of small volumes of reagents with inappropriate apparatus

5. Inappropriate use of pipette

6. Improper setting of baseline for recording data of a sample

2. Instrumental and reagent errors

These errors are associated with the equipments and the quality of the reagents employed during the
analytical procedure. In this type errors, instruments such as physical balance, electrodes for recording
pH, conductance, potential etc., add errors to the measurement or analysis due to negligence in their
operation such their cleanliness, calibration, improper washing procedures of electrodes, improper
connections etc. Secondly, the quality of reagents used is equally important and use of low quality
reagent and chemicals deviate the amounts and related data from the actual value. In addition, use of
low quality apparatus adds impurities during experiment and act as additional source of errors. For
instance, use of low quality glassware adds impurities such as metal ions due to the attack of reagents
(acids or solvents) and dissolution of labels in solvents etc. These errors can be avoided by analyzing
reference samples.

3. Errors of method

These errors are concerned with procedures followed during sampling and analysis due to incomplete
reaction, loss of sample during washing, incomplete precipitation, volatility of the reactant or products
involved etc. Like instrumental and reagent errors, use of reference samples help in the removal of
errors related to method. Some of the examples related to errors of methods involved in a particular
procedure are elaborated below.

1. Precipitation: Incomplete precipitation, co-precipitation of impurities, loss of precipitates during

washing, volatilization of precipitates during drying and transference from the filter paper for
weighing etc.

2. Titration: Incompleteness of reaction or equilibrium set up which prevents the completion of

reaction, inappropriate reaction conditions such as pH, temperature etc which may also vary during the

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 course of reaction, involvement of impurities with similar chemical properties in the reaction,
interpretation of end point and improper shaking of the solution for maximum interaction between
titrant and titrand .

3. Liquid-liquid extraction: Choice of inappropriate solvent like partially miscible solvents, incomplete
partitioning of analyte in the two phases, loss of analyte during repeated operations and separation etc.

Effect of systematic errors on analytical results

The effect of systematic errors on the final result varies on the basis of its nature. These may be either
constant or proportional. The details of the errors are discussed below.

Constant errors Proportional errors

Magnitude of the error remains constant Magnitude of proportional errors always shows
with the variation in size, so, it is termed as variation with the variation in the size of the
constant error. sample.

In such cases, the absolute error is constant In such cases absolute errors vary with the
but relative error varies with the change in sample size while relative error is always
the size of the sample. constant with the variation in the size of sample.

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 LAB SAFETY

In this part, various safety measures are covered to prevent the accidents and mishaps usually
encountered due to lack of knowledge for handling chemicals. The main purpose is to understand
proper laboratory safety, to aware the student about possible risks or hazards involved with laboratory
work so that a safe place can be created by following the proper safety guideline. The overall safety
includes personal safety, chemical safety, radiation safety, gas safety, fire safety and steps to be
followed in case of any accident.

Personal Safety

The individual working in a lab is responsible for his/her own safety as well as the safety of co-
workers, lab staff, and maintenance of lab. It is the personal responsibility of worker to use personal
protection equipment and follow the safety rules and regulations. Some of the general precautions
which should be followed by a research personal while working in a chemical lab are given below.

S.No. List of do’s and don’ts while working in a chemical lab

1 Eatables in the lab are strictly prohibited, so don’t eat or drink anything in the working
area.

2 Don’t apply cosmetics in the lab.

3 Don’t wear contact lenses while working in the lab because the vapors or gases may
cause eye damage.

4 Don’t store food/drinks in the refrigerators/freezers or cabinets used for the storage of
chemicals.

5 Don’t put pens or pencils in the mouth while working in the lab.

6 Don’t wear very tight, extremely loose and short clothing in lab.

7 Don’t wear long necklaces, scarves and ties etc in the lab.

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 8 Always tie the long hair at the back to avoid their contact with chemicals and other
toxic substances.

9 Don’t wear rings or other jewelery while working in the lab.

10 Don’t wash utensils in the sinks and drain boards of the lab.

11 Don’t consume ice made in the ice machine of lab.

Personal protective equipments

The personal protective equipments must be used for personal safety. These are described below.

Item Description

1. Lab coat or It is very important to wear a long lab coat to cover the dress. It protects
apron clothing of a person from contamination as well as exposure of skin to
hazardous or toxic materials. The lab coats should not be worn outside the
laboratory.

2. Lab Lab footwear should be closed/completely covered shoes which can prevent
footwear the feet from sharp objects, corrosive reagents and infectious materials.

3. Gloves Gloves should be worn while working with chemicals, biological samples like
blood samples, body fluids, mucous membranes etc. The washing of
apparatus and experimentation must be done by wearing gloves of good
quality.

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 4. Eyewear The eyes should be protected by wearing eye glasses to prevent contact with
any type of gas or contamination in the lab. It is very important while
working with caustic reagents, solvents, concentrated acids/bases, body
fluids, under high pressure and in the vicinity of UV and other radiations.

5. Masks To prevent the face from the acidic fumes and corrosive gases, masks are very
important.

Chemical safety

All the chemicals should be treated as per their nature, so special care must be taken during handling
the reagents and chemicals. The materials safety data sheets (MSDS) concerned with the handling of
each material should be available to each personnel. Therefore, a proper record and MSDS should be
maintained in the lab. To work in a lab, research personnel must wear personal protective equipments
like lab coat, gloves, lab shoes etc. After the completion of activity, gloves should be removed and
hands must be washed properly. The personnel should remove protective equipment before leaving the
lab. The personnel should be aware about the chemical hazard symbols given on the bottles.

Pictogram Meaning Hazards

Explosive Risk of explosion by heat or shock

Highly Flammable Risk of inflammation by contact with

heat or spark

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 Oxidizing Risk to contribute to inflammation of
other substances

Corrosive Risk of metal corrosion or irreversible

damage to skin or eye

Poisonous Acute intoxication by exposure and may

lead to death

Dermal sensitizer, irritant, specific Toxicity with low hazardous properties

target organ toxicity and acute
toxicity (category 3 and 4)

Carcinogenic, mutagenic, Risk of allergy through inhalation,

reproductive toxicity, Dermal carcinogen
sensitizer, specific target organ
toxicity (category 1 and 2)

Hazardous to aquatic life Risk of contamination of water

Gas under pressure Risk of explosion when heated

Radiation

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 Biohazard

Radiation safety

A radioactive material is an unstable substance which continuously produces radiations. These

radiations are harmful and cause adverse effects to the living beings and environment. Therefore, the
radioactive materials must be labeled and stored properly as per the guidelines. The materials must be
handled carefully and their spillage or leakage should be prevented. In case of spillage, recommended
adsorbents should be used and the area should be cleaned with soap and water.

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 Bibliography
 D.A. Skoog; F. J. Holler, T.A. Nieman (1998). Principles of Instrumental Analysis, 5th edition.
Orlando, FL: Harcourt Brace College Publishers.
 J. Tyson, Analysis. What Analytical Chemists Do. London: Royal Society of Chemistry, 1988.
A brief book that succinately discusses what analytical chemists do and how they do it.
 R.W. Murray, Analytical Chemistry is what analytical chemists do, Editorial, Anal. Chem., 66
(1994) 682A.
 D.C. Harris, Quantitative chemical analysis, 6th Ed
 Douglas A. Skoog, James Holler, Stanley R. Crounch, “Principles of Instrumental Analysis”
 Willard H.W Merritt, L.L Dean J A Settie FA, Instrumental Methods of Analysis
 Douglas A Skoog, Donald M, West Holler Thomson, Fundamentals of Analytical Chemistry,
8th Ed
 Galen W. Ewing, Instrumental Methods of Chemical Analysis
 D. C. Harris, Exploring Chemical Analysis, 3rd Ed
 J. Mendham, R.C. Denney, J.D. Barnes, M.J.K. Thomas, Vogel's Quantitative Chemical
Analysis (6th Edition) 6th Edition
 Robert H. Hill, Jr., David C. Finster, Lab Safety for Chemistry students, 2nd Edition, 2016
 Anthony A. Fuscaldo, Barry J. Erlick, Barbara Hindman, Laboratory Safety: Theory and
Practice, Academic Press

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