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BASICS OF ANALYTICAL
CHEMISTRY AND
CHEMICAL EQUILIBRIA
BASICS OF ANALYTICAL
CHEMISTRY AND
CHEMICAL EQUILIBRIA: A
QUANTITATIVE APPROACH
By
BRIAN M. TISSUE
Virginia Tech
Department of Chemistry
Blacksburg, VA
Second Edition
Copyright © 2023 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form
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Paperback ISBN: 9781119707356; ePub ISBN: 9781119707387; ePDF ISBN: 9781119707349
Cover Images: Background: © kundoy/Getty Images; Figure: Courtesy of Brian M. Tissue

Cover Design: Wiley
Set in 11/13pt TimesNewRomanPSMT by Integra Software Services Pvt. Ltd, Pondicherry, India
CONTENTS
PREFACE ix
ABOUT THE COMPANION WEBSITE xiii
I QUANTITATIVE ANALYSIS USING REACTIONS

THAT GO TO “COMPLETION” 1
1 MAKING MEASUREMENTS 3
1.1 Introduction / 3
1.2 Glp and a Few Other Important Acronyms / 10
1.3 Precision and Random Error / 14
1.4 Discarding a Suspected Outlier / 25
1.5 Calibration / 28
1.6 Maintaining Accurate Results / 44
Practice Exercises / 49
2 SAMPLE PREPARATION, EXTRACTIONS, AND
CHROMATOGRAPHY 53
2.1 Sampling and Control Samples / 53
2.2 Sample Preparation / 59
2.3 Solvents and Solutions / 65
2.4 Introduction to Solubility / 69
2.5 Extraction and Partitioning Theory / 72
v
vi contents
2.6 Introduction to Stationary Phases / 84

2.7 Solid-Phase Extraction (SPE) / 88
2.8 Column Chromatography / 94
3 CLASSICAL METHODS 103
3.2 Review of Chemical Reactions / 105
3.3 Reactions in Aqueous Solution / 112
3.4 Gravimetry / 121
3.5 Titration / 125
3.6 Titration Curves / 133
3.7 Coulometry / 135
4 MOLECULAR SPECTROSCOPY 143
4.2 Properties of EM Radiation / 144
4.3 Electromagnetic Spectrum / 148
4.4 Spectroscopic Transitions / 150
4.5 UV/Vis Absorption Spectroscopy / 155
4.6 UV/Vis Instrumentation / 158
4.7 Beer–Lambert Law / 161
4.8 Molecular Fluorescence / 170
II REACTIONS THAT DO NOT GO TO “COMPLETION.”

EQUILIBRIA IN AQUEOUS SOLUTIONS 183
5 ACID–BASE EQUILIBRIA AND ACTIVITY 185

5.1 Acids and Bases / 185
5.2 Weak Acids and Weak Bases / 192
5.3 Water and Kw / 197
5.4 Acid Strength / 202
5.5 The Concept of Activity / 207
5.6 Acid–Base Equilibrium Calculations / 219
6 BUFFER SOLUTIONS AND POLYPROTIC ACIDS 229
6.1 Buffer Solutions / 229
6.2 Alpha Fraction Plots / 234
contents vii
6.3 Weak Acid Titration Curve / 238

6.4 Polyprotic Acids / 241
7 METAL–LIGAND COMPLEXATION 253
7.1 Complex Terminology / 254
7.2 Complex Equilibria / 258
7.3 Competing Equilibria / 264
7.4 Stepwise Complexation / 271
7.5 Immunoassays / 276
8 PRECIPITATION EQUILIBRIA 283
8.1 Precipitate Equilibrium / 284
8.2 Molar Solubility / 291
8.3 Common-Ion Effect / 297
8.4 Precipitation and Competing Equilibria / 299
8.5 Drinking Water / 304
III INSTRUMENTAL METHODS AND ANALYTICAL

SEPARATIONS 311
9 ELECTROANALYTICAL CHEMISTRY 313

9.2 Standard Reduction Potentials / 316
9.3 Using Half Reactions / 321
9.4 Background on Spontaneous Reactions and Equilibrium / 327
9.5 Reaction Energies, Voltages, and the Nernst Equation / 331
9.6 Electrochemical Cells / 334
9.7 Potentiometry / 340
9.8 Ion-Selective Electrodes (ISE) / 342
9.9 Voltammetry / 350
10 ATOMIC SPECTROMETRY 361
10.1 Atomization / 363
10.2 Atomic Absorption Spectrometry (AAS) / 368
10.3 Atomic Emission Spectrometry (AES) / 378
10.4 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) / 381
viii contents
10.5 Other Mass Spectrometer Designs / 390

11 MOLECULAR STRUCTURE DETERMINATION 399
11.2 Molecular Mass Spectrometry / 402
11.3 Fourier-Transform Infrared Spectroscopy / 407
11.4 FTIR Instrumentation / 412
11.5 Nuclear Magnetic Resonance Spectroscopy / 416
11.6 NMR Instrumentation / 421
12 ANALYTICAL SEPARATIONS 425
12.1 Thin-Layer Chromatography / 426
12.2 Chromatogram Terminology / 431
12.3 Separation Efficiency / 435
12.4 Gas Chromatography (GC) / 439
12.5 Gas Chromatography Mass Spectrometry (GC-MS) / 444
12.6 High Performance Liquid Chromatography / 447
12.7 Electrophoresis / 460
INDEX 469
PREFACE
This text will introduce you to analytical chemistry: the science of making
quantitative measurements. Quantifying the individual components in a com-
plex sample is an exercise in problem solving. An effective and efficient analyst
will have expertise in
● sampling, sample processing, and method validation;

● the chemistry that can occur in a sample before and during analysis;
● selecting an appropriate analytical method; and
● proper record keeping, data analysis, and reporting of results.
I do not attempt to be comprehensive in this text. Samples that require anal-

ysis are so diverse that it is not possible to describe every sample preparation
protocol, separation method, and measurement technique. These details are
contained in handbooks and method compilations, many of which are now
accessible from online sources. This text emphasizes the fundamental chemical
and physical concepts that underlie the analytical methods. With an under-
standing of the fundamental concepts, a scientist faced with a difficult anal-
ysis can apply the most appropriate techniques, identify when a particular
problem cannot be solved with existing methods, and develop new analytical
methods. The proficient analyst will also be alert to interferences and prob-
lems in analytical measurements and recognize when an “answer” might not
be correct.
ix
x preface
I organize the discussion of the core principles of analytical chemistry into

three parts:
● Part I: Analytical concepts such as calibration and uncertainty, sample

preparation, classical (wet-chemical) methods, and molecular UV/Vis
spectroscopy
● Part II: Chemical equilibria involving acids, bases, complexes, and insol-
uble precipitates
● Part III: Electroanalytical methods, atomic spectrometry, molecular struc-
ture determination, and chromatographic separations
The analytical methods in Part I rely on reactions that go to completion.

Part II is a detailed treatment of chemical equilibria—reactions in which reac-
tants and products coexist. Chemical equilibria are critical to many aspects of
chemical, biochemical, and environmental systems. Part III describes the most
common instrumental methods of analysis, illustrating many of the tools of
the trade for making quantitative measurements. Even if your future career
veers away from science, you will find the problem-solving and graphical data
analysis skills developed in this text to be useful.
Many of the topics in this text follow directly from first-year college chem-
istry. You will want access to a general chemistry text or online resource to
refresh your memory of the underlying principles of physical processes and
chemical species. The level of this text presumes that you know
Basic math Algebra

Exponential functions
Calculating and plotting in a
spreadsheet
Basic chemistry Predicting properties based on the
periodic table
The nature of chemical compounds
Stoichiometry and balancing reactions
Reaction types Acid–base
Complexation
Precipitation
Reduction and oxidation (redox)
The beginning of each chapter lists learning outcomes that serve as a brief
outline to help categorize new material. After completing a chapter, make a
concept map to help yourself see the big picture and underlying concepts.
You will often encounter a repeat of concepts in the text. Making connec-
tions with prior material makes learning analytical concepts much easier.
Treating every topic as something new becomes overwhelming. Each chapter
preface xi
contains sample calculations and practice exercises. I assume that your goal
is success. Achieving success requires skills, and acquiring skills takes
practice.
Variables and constants are italicized to not be confused with other text. As
much as possible, I use the conventions and terminology in the IUPAC Gold
Book.1 You will find other symbols in other books and resources, so use the
context to decipher the differences. This second edition adds substantial
information on instrumental methods and manufacturers will often use differ-
ent terms for similar instruments. Relevant spreadsheets and links to useful
resources are available at https://www.achem.org.
Blacksburg, VA Brian M. Tissue

August 2022
1
See IUPAC Compendium of Chemical Terminology, “The Gold Book,” https://goldbook.iupac.
org; Accessed August 2022.
ABOUT THE COMPANION WEBSITE
This book is accompanied by a companion website:
www.wiley.com/go/tissue/analyticalchemistry2e
This website includes:

● Solutions to the end-of-chapter practice exercises.
● Spreadsheet templates and solution guides for the “You-Try-It” exercises.
● A glossary of analytical chemistry terms.
● General spreadsheets for common analytical calculations.
xiii
PART I
QUANTITATIVE ANALYSIS USING

REACTIONS THAT GO TO “COMPLETION”
CHAPTER 1
MAKING MEASUREMENTS
Learning Outcomes
● Describe aspects of good laboratory practice (GLP).

● Use correct terms to describe analytical measurements and data.
● Calculate analyte concentration from measurement results.
● Use statistical formulas to express the precision of analytical measurements.
● Use calibration methods to obtain accurate results.
1.1 INTRODUCTION
There are few areas in our modern life in which the quantity of substances is
not important. Industries and government agencies spend substantial
resources to determine and monitor the safe levels of chemicals in foods, phar-
maceuticals, and the environment. Setting permissible levels of contaminants
is based on quantitative results from toxicological studies and raising or low-
ering a level has significant costs and consequences. Similarly, companies
compete for sales by providing high-quality goods at the lowest price.
Optimizing industrial processes depends on making decisions based on ana-
lytical measurements. Poor measurements or incorrect data interpretation will
lead to poor decisions.
Basics of Analytical Chemistry and Chemical Equilibria: A Quantitative Approach, Second Edition. Brian M. Tissue.
© 2023 John Wiley & Sons, Inc. Published 2023 by John Wiley & Sons, Inc.
Companion Website: www.wiley.com/go/tissue/analyticalchemistry2e
3
4 making measurements
You might not make many measurements yourself, but you probably rely on
data and quantitative results to make decisions. You’ve probably read the
ingredients or nutritional information on a product label to choose one prod-
uct over another. I certainly want manufacturers to perform quality checks on
the contents of the products that I buy. I’m also expecting an independent
agency, say the FDA or USDA,1 to check that there is not too much of a min-
eral, or contaminants such as Pb or rat poison, that could make the food
unhealthy. Think about the last time that you had a medical checkup. Did the
doctor determine your health by just looking at you? At the least you had a
quantitative measure of pulse rate and blood pressure. Modern medicine relies
on a variety of technological tools and clinical analyses. At some time, you
might need to make a significant decision such as beginning daily doses of a
cholesterol-lowering drug. We all hope that doctors and clinical technicians
analyzing our samples were paying attention when they took an analytical
chemistry course!
When you make a measurement, or you need to make a decision based on
someone else’s measurement, do you trust the value? This chapter introduces
the terminology and statistical tools to describe and assess quantitative results.
Some of the details will be new to you, but they all fit into a framework for
collecting and reporting quantitative measurements. Table 1.1 begins building
our vocabulary of measurement science and data-handling concepts by
defining general terms. Many of these terms are used rather loosely in the
scientific and manufacturer literature. You might need to dig into the details to
know exactly what is meant when a procedure refers to the sample, the signal,
etc. It is also common that a given term will have a different definition for dif-
ferent instruments or techniques. Resolving power is a measure of selectivity
in mass spectrometry. However, resolving power and the related term resolu-
tion have different meanings when discussing a spectrum, a microscope image,
or the separation of components in a mixture.
In quantitative analysis, we want a measurement or detector signal that we
can relate to an analyte concentration. Doing so can be quite involved, and
Chapter 2 discusses various sample preparation methods to isolate an analyte
from interferences so that it can be measured. What mechanisms are available
to detect an analyte? I can think of only three general strategies to detect and
quantitate an analyte:
● measuring a physical property,

● using electromagnetic radiation, called spectroscopy, and
● measuring an electric charge or current.
1
US Food and Drug Administration and US Department of Agriculture. See “FDA
Fundamentals,” https://www.fda.gov/about-fda/fda-basics/fda-fundamentals; accessed August
2022. Other countries and trade blocs have similar agencies.
introduction 5
TABLE 1.1 Measurement Terms

Term Definition
Sample v. To collect one or more samples.
Sample n. Substance of interest. Assumed to be representative of remaining
substance that is not collected. May refer to an unprocessed field sample or
to a laboratory sample that has undergone one or more sample preparation
steps. Test portion is the preferred term for laboratory samples.
Unknown n. A sample, the source of which is usually known. Calling a sample an
“unknown” indicates that the identity of the substance or the analyte
concentration in the sample is unknown and to be determined.
Test portion n. A portion of a collected sample that is processed and measured.
Test solution n. Analogous to test portion but specific for a liquid solution.
Analyte n. The chemical species to be identified or quantitated. It might exist as a
pure substance or as one constituent of a multicomponent sample.
Qualitative n. Making measurements to determine the identity, structure, or physical
analysis properties of a substance.
Quantitative n. Making measurements to determine the amount of an analyte in a sample.
analysis
Detector n. Device that responds to the presence of analyte, usually generating an
electrical output.
Signal n. The detector output that is displayed or recorded.
Sensitivity n. The change in detector signal versus change in analyte concentration.
Selectivity n. The discrimination of an analyte versus other components in the sample.
TABLE 1.2 Measurement Strategies

Physical Property Spectroscopy Electric Charge or Current
Mass or volume Absorption Electrical conductivity
Density Emission Electrical potential, for example, pH meter
Refractive index Scattering Voltammetry (reduction and oxidation current)
Freezing point depression Mass spectrometry (ion current)
Thermal conductivity
Table 1.2 lists some examples in each of these categories. We will discuss
most of these methods, so do not worry if they are unfamiliar. Chapter 3 dis-
cusses classical methods that rely on physical measurements and Part III of
the text introduces instrumental methods based on electrochemistry, spectros-
copy, and mass spectrometry.
Although I list only three general detection strategies, each of these general
categories encompass a multitude of specific analytical techniques. For example,
spectroscopic methods have been developed to use most of the electromagnetic
spectrum, including X-ray, ultraviolet (UV), visible (Vis), infrared, and radio
waves. The different regions of the electromagnetic spectrum interact with
matter differently and provide different types of information. This text concen-
trates on quantitative methods for analytes in aqueous solution. There are
numerous other spectroscopic techniques to make quantitative measurements

of solids and to determine physical properties of materials.
These general categories vary in sensitivity and selectivity. Measurements
based on a physical property are usually less sensitive than spectroscopic or
charge-based instrumental methods. The methods based on physical methods
are useful when analyte concentrations are relatively high and when preparing
standards to calibrate instrumental methods. When coupled with a separation
column, detectors based on physical methods are the most universal and
capable of detecting all analytes in the sample. Spectroscopic and electroana-
lytical methods can be extremely sensitive and selective for specific analytes.
Selecting from one of these three general strategies for a given analytical
problem depends on the nature of the analyte, the expected concentration, and
the sample matrix.
New analytical methods and instruments are developed continuously. The
breadth of research and development in analytical chemistry is too extensive
to convey through just a few examples. For an overview of current research
topics in analytical sciences, browse the Technical or Preliminary Programs of
upcoming analytical chemistry conferences.2
1.1.1 Concentration Units

Most of the quantitative methods that we will discuss are aimed toward deter-
mining the concentration of an analyte in a sample. Concentration is the quantity
of one substance, the analyte, divided by the total quantity of all substances in
the sample. Concentration is different from an amount, in moles, mass, or
volume, and we often interconvert between the two. Table 1.3 lists the SI base
units that are used to derive other units.3 In addition to these units, we drop or
add the prefixes listed in Table 1.4 to indicate numerical factors. Common units
that we work with in addition to the mole and kg are mmol (millimole),
TABLE 1.3 SI Base Units

Unit of Name Symbol
Length Meter m
Mass Kilogram kg
Time Second s
Electric current Ampere A
Thermodynamic temperature Kelvin K
Amount of substance Mole mol
Luminous intensity Candela cd
2
EAS (Eastern Analytical Symposium), https://eas.org; FACSS (Federation of Analytical
Chemistry and Spectroscopy Societies), https://facss.org; or Pittcon (Pittsburgh Conference on
Analytical Chemistry and Applied Spectroscopy), https://pittcon.org; URLs accessed August 2022.
3
SI is the abbreviation for “The International System of Units.” For more information see
https://physics.nist.gov/cuu/Units/index.html; accessed August 2022.
introduction 7
mg (milligram), and g (gram). The purpose of the prefixes is to simply express

results in convenient values rather than using scientific notation. From the SI
base units, we derive other useful units, and some are listed in Table 1.5.
The SI unit for an amount of a substance is the mole. A mole is a fixed
number of something. If you have one mole of fish, you have 6.022 × 1023 fish
(that’s a lot of fish). The mole is a large number because atoms and molecules
are incredibly small. The mole is determined from the number of atoms in 12 g
of carbon-12 (12C). We cannot count individual atoms or molecules easily, so
the physical means of measuring an amount is to determine a mass and convert
it to moles. The unified atomic mass unit or atomic mass constant is 1/12 of the
mass of a carbon-12 atom and has units of u (amu is common in older litera-
ture). For large biomolecules, the equivalent unit of Dalton (Da) is common.
The atomic weight or standard atomic weight of an element is the relative mass
to the unified atomic mass unit. Atomic weights are therefore relative, unitless
quantities. Since most elements have multiple isotopes, the atomic weight is the
weighted average based on the abundance of the different isotopes.
We will neglect cases where the atomic weight of a specific sample varies from
published values, but it can be significant for some light elements and radioac-
tive materials that are enriched in one isotope. We will also not show conversion
of unitless atomic weights to proportionality factors when converting between
amount and mass. For our calculations, we will use atomic or molecular formula
weights with units of gram per mole (g/mol). As a final practical note, mass and
weight are not the same thing. Mass is an intrinsic property of a substance, but
weight is a force that is dependent on mass and gravity. Modern analytical bal-
ances can be calibrated to read mass accurately, so we will follow common usage
and assume that any weights that we measure are equal to mass.
TABLE 1.4 Common Numerical Prefixes

Prefix Name Factor Prefix Name Factor
−12
p Pico 10 k Kilo 103
n Nano 10−9 M Mega 106
μ Micro 10−6 G Giga 109
m Milli 10−3 T Tera 1012
TABLE 1.5 SI Derived Units

Unit of Name Symbol
2
Area Square meter m
Volume Cubic meter m3
Volume Liter (=0.001 m3) l
Concentration Kilogram per cubic meter kg/m3
Concentration Moles per liter M (mol/l)
Density Mass per volume ρ (g/ml)
Relative density (specific gravity) Ratio of a density to a reference d (unitless)
Different types of analytical methods will measure concentration, volume,

or mass. Similarly, different types of detectors respond to analytes in different
ways, that is, respond to either the analyte concentration or the analyte amount.
Part of the common language that we need are conventions for describing
amounts and concentration in different orders of magnitudes. Table 1.6 lists
common units for describing analytical results.4
The reason to use different concentration units and numerical prefixes is
convenience (see Example 1.1). We could quote every concentration as a
percentage. For example, the EPA5 lead limit in drinking water of 15 ppb
would be written as 0.0000015%. This expression is not only awkward, it is
susceptible to typographical errors in calculations. Some units will be accom-
panied by explanatory text, for example a percentage might be listed as a
“weight percentage” or “percentage v/v” (volume per volume). For ppm, ppb,
and ppt units, the “per l” definitions are equivalent to “per kg” only for dilute
aqueous solution, that is, at a solution density of 1.0 kg/l.
There are many other units for specialized measurements. Water hardness is
usually quoted as the equivalent amount of calcium carbonate in mg/l or grains/
gallon (1 grain/gallon = 17.1 mg/l). The salinity of salt water is expressed in
parts per thousand or as a ratio to a reference solution. When measured versus
a reference, units are expressed as a practical salinity scale, PSS, where 1 PSS
unit is equal to approximately 1 g sea salt per kg of seawater. There are numerous
other cases where some standard protocol is adopted so that measurements
made by different analysts in different locations can be compared directly.
Air sampling can require different approaches. The EPA limits for particulate
matter in indoor air, PM2.5, are 15.0 μg/m3 for the annual average limit and 35
μg/m3 for the 24-h limit.6 As this example illustrates, quoting a single quantity
might not be sufficient to describe the concentration or criteria for an analyte
in a real sample or situation.
TABLE 1.6 Common Concentration Units

Name Symbol Description
Molality m Moles solute/kilogram solvent (mol/kg)
Molarity M Moles solute/liter solution (mol/l)
Mole fraction X Moles solute/moles total (unitless)
Percentage % Parts per hundred, often as weight percent
Parts per thousand ‰
Parts per million ppm (mg/kg or mg/l)
Parts per billion ppb (μg/kg or μg/l)
Parts per trillion ppt (ng/kg or ng/l)
4
Note that parts per thousand is sometimes abbreviated as ppt in older literature. It should not
be confused with parts per trillion.
5
US Environmental Protection Agency, https://www.epa.gov; accessed August 2022.
6
Solid and liquid particles less than 2.5 μm in diameter suspended in air. US Envi
ronmental Protection Agency, National Ambient Air Quality Standards, https://www.epa.gov/
environmental-topics/air-topics; accessed August 2022.
introduction 9
Example 1.1 Unit Conversion. The EPA maximum contaminant limit (MCL)
for benzene, C6H6, in drinking water is 0.005 mg/l. What is this limit written in
units of ppm, ppb, M, and wt%?
The question does not specify the density of the water. Given that drinking
water is purified, we will take it to be 1.0 g/ml or 1.0 kg/l. As we have only one
significant figure in 0.005 mg/l, this assumption does not affect this calcula-
tion.7 Given a density of 1.0 kg/l, the units mg/l and ppm are the same:
0.005 mg C 6 H6  1.0 l 
  = 0.005 ppm C 6 H6
1.0 l water 1.0 kg 
Converting ppm to ppb is accomplished by multiplying by 1000:
1000 ppb 
0.005 ppm C 6H6   = 5 ppbC 6H6
 1ppm 
To convert to molarity, M, we use the formula weight of benzene, which is

78.11 g/mol. Converting 0.005 mg to mol is
5 ×10−6 g C 6 H6
= 6.4 ×10−8 molC 6 H6
78.11g/mol
Now dividing by 1.0 l to obtain concentration, c, gives
6.4 ×10−8 mol

cC6H6 = = 6.4 ×10−8 M
1.01
To find the weight percent, wt%, we need grams of benzene per 100 g of solu-
tion. The MCL of 0.005 mg/l for a water density of 1.0 g/ml is 0.005 mg/1000 g.
I multiply both numerator and denominator by 0.1 to get the units that I want
in the denominator:
5×10−6 g C 6H6  0.1 5×10−7 g C 6H6

 =
1000 g water  0.1 100 g water
5×10−7 g C 6H6
×100% = 5×10−7 % C 6H6
100 g water
As you can see, 0.005 mg/l or 5 ppb is simply more convenient for describing
this limit than other concentration units.
The following spreadsheet calculation is the first You-Try-It exercise in the

text. An Excel spreadsheet file containing this exercise and a step-by-step guide
are available at: https://www.achem.org.
7
Pure water at 25°C has a density of 0.997 g/ml.
I place these exercises at appropriate locations in each chapter, and I recommend

that you practice the just-completed topics before moving to new material. If
you are new to or want more practice using spreadsheets, work through the
spreadsheet-help.pdf document that is also available on the achem.org
website.
You-Try-It 1.A
The conversions worksheet in you-try-it-01.xlsx contains two tables
of measurement results. Convert these results to other common units.
1.2 GLP AND A FEW OTHER IMPORTANT ACRONYMS
1.2.1 Good Laboratory Practice (GLP)

GLP (Good Laboratory Practice) refers to specific regulations by which labo-
ratories must conduct, verify, and maintain their procedures, results, and
records. These regulations, effective in the United States in 1979, were a
response to the unreliability of data that were submitted to government
agencies to certify that agricultural chemicals, food additives, drugs, and cos-
metics were safe and effective. The current GLP regulations are found in the
Code of Federal Regulations as8
● Title 21, Part 58: US Food and Drug Administration,

● Title 40, Part 160: US Environmental Protection Agency pertaining to the
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA),
● Title 40, Part 792: US Environmental Protection Agency pertaining to the
Toxic Substances Control Act (TSCA).
The different regulations are similar in their overall structure and purpose,
but they are tailored to specific types of chemicals and laboratories. The details
of the Code of Federal Regulations are not important to us, but they are use-
ful to recognize the origin of regulations that we will discuss. Reference to
sections of the federal code use an abbreviation based on title, part, and sec-
tion number. The following paragraph illustrates the coding with a small
excerpt of the Code of Federal Regulations, 21CFR58.83, where the .83 in the
title refers to this specific section.
[Code of Federal Regulations]

[Title 21, Volume 1]
[Revised as of April 1, 2006]
From the U.S. Government Printing Office via GPO Access
[CITE: 21CFR58]
[Page 308]
8
Available from US Government Printing Office: https://www.ecfr.gov; accessed August 2022.
glp and a few other important acronyms 11
TITLE 21--FOOD AND DRUGS
CHAPTER I--FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF

HEALTH AND HUMAN SERVICES
PART 58_GOOD LABORATORY PRACTICE FOR NONCLINICAL LABORATORY
STUDIES
--Table of Contents
Subpart E_Testing Facilities Operation
Sec. 58.83 Reagents and solutions.

All reagents and solutions in laboratory areas shall be
labeled to indicate identity, titer or concentration,
storage requirements, and expiration date. Deteriorated or
outdated reagents and solutions shall not be used.
Besides codifying good science and common sense as federal law, the GLP
regulations stipulate a framework for personnel responsibilities, analytical
methods, and record keeping. These tasks include
1. Personnel and management responsibilities for individual laboratory

workers, Study Director, and a Quality Assurance unit (QAU).
2. Written protocols, study plans, and standard operating procedures (SOP)
for individual steps or instruments.
3. Record keeping, final written reports, and retention of records.
With the formalized GLP regulations, quality assurance (QA) now indicates
an auditing role, while quality control (QC) refers to instrument calibration and
method validation (discussed in Section 1.5). My point in this discussion is not
that we must memorize government regulations but that all workers in an analyt-
ical laboratory have certain roles. Laboratory workers must follow documented
and reproducible procedures and create an audit trail of all work. Following
GLP ensures the reliability of analytical measurements and maintains the
credibility of reported results. An analyst should develop “GLP” habits-of-mind
to become adept at measurement science and to work safely in the laboratory.
1.2.2 Standard Operating Procedure (SOP)

An SOP is a document containing the instructions for a specific analytical
procedure or instrument. SOPs can serve as a user’s guide, reference source,
and safety manual. As per GLP regulations, they are reviewed and approved
by other members of the laboratory management team. The following example
shows a simple SOP. Other SOPs might be the size of a novella, depending on
the complexity of a task, an instrument, or a hazard.
Standard Operating Procedure

Title: Use of Ocean Optics FL-400 Flame-Resistant Fiber Probe
SOP No: AC-21 Author: B. Tissue Version: 05/27/06
1. Purpose
To ensure correct and safe usage of the FL-400 Flame-Resistant
Fiber Probe when recording flame emission spectra.
2. Scope
This SOP provides operating procedures for the Ocean Optics FL-400
Flame-Resistant Fiber Probe for recording flame emission spectra.
Consult other SOPs or your instructor for sample handling and use
of the flame source and spectrometer.
3. Precautions
● Do not touch the tip when hot.
● Handle the probe with care. It contains a glass fiber and should
not be dropped or bent.
● Let tip cool for at least 10 seconds before placing in sample or
cleaning solutions. Do not place a hot probe tip in a cool solution
as the glass fiber could crack.
4. Specific Procedures
4.A. Set-up: The flame-resistant fiber probe should be connected to a
1-m optical patch cable using the stainless steel SMA splice bushing
stored with the probe. Do not attempt to use the probe connected
directly to the USB2000® spectrometer.
4.B. Use: To load a test portion onto the flame loop (1) dip into a
solution and allow to dry or (2) wet the loop with dilute HCl and dip
into solid sample. Insert only the loop into a flame and not the whole
tip. A separate sample loop or splint may also be used.
4.C. Cleaning: The flame loop and fiber tip should be cleaned with
distilled water. A mild detergent and ultrasound is acceptable if
necessary.
5. Related SOPs and References

a. SOP No. AC-20 Use of Ocean Optics USB2000® spectrometer.
b. Ocean Optics web site: http://www.oceanoptics.com.
Reviewed: J.R. Morris 5/29/06 Approved: M. Anderson 6/7/06

glp and a few other important acronyms 13
SOPs provide a handy reference to ensure proper use of a procedure or

instrument, which is necessary to obtain reproducible results. SOPs, and other
procedural documentation, can serve as traceable legal documents in patent
and criminal legal proceedings. As an example, try searching the internet for
a forensic procedures manual.9 Failure of an analyst to follow the approved
procedures can result in measurements being inadmissible in court cases.
1.2.3 Still More Acronyms

There are numerous other regulatory practices that are similar to GLP. Some
examples are
Good Clinical Practice (GCP). Regulations governing clinical trials.

Good Manufacturing Practice (GMP). Regulations governing the pharma-
ceutical industry. Also cGMP denotes current Good Manufacturing
Practice.10
Organisation for Economic Co-operation and Development (OECD). An
international organization concerned chiefly with economic and social
issues. They also publish guidelines on science and technology including
chemical safety, chemical testing, and GLP.11
International Union of Pure and Applied Chemistry (IUPAC). A nongov-
ernmental agency that recommends standardization of chemical nomen-
clature, terminology, and chemical and physical data.
The point of this list is not that you should memorize acronyms. The
purpose is that you can recognize the purpose and origin of regulations when
you see them in the context of your work or study. Many of these regulatory
structures are available online, and a search will often find all that you need to
know about the details of the regulations. The chances are high that you will
deal with scientific regulations sometime during your work life, possibly in
more than one laboratory role as analyst, supervisor, or auditor.
1.2.4 Safety Data Sheet

I finish this section with a reference document that is very important for anyone
working with laboratory chemicals. A safety data sheet (SDS) provides
chemical and toxicological information for a specific chemical. A laboratory
worker can use this information to select proper equipment, personal protective
9
See for example the Toxicology Procedures Manual available at: https://www.dfs.virginia.gov/
documentation-publications/manuals; accessed August 2022.
10
GCP and GMP are both administered by the Food and Drug Administration in the United
States.
11
“OECD Principles on Good Laboratory Practice” and “Guidelines for Testing of Chemicals”
can be found by searching at https://www.oecd.org; accessed August 2022.
equipment (PPE), and work practices to work with a chemical safely. A lab
worker should read the SDS information before using a substance, that is,
before spilling, inhaling, or igniting anything. It is very difficult to read an
SDS when you are dizzy, burned, or unconscious. Some of the more useful
sections of an SDS include
● Section 2, Hazard(s) identification

● Section 4, First-aid measures
● Section 8, Exposure controls/personal protection
● Section 10, Stability and reactivity (including incompatible materials)
SDS sheets must be readily available to lab workers. Medical personnel can
refuse to treat a case of chemical exposure without an SDS for the substance
involved. If you do not have an SDS, most chemical suppliers provide them
online. The following excerpt illustrates the type of information that is avail-
able for hydrochloric acid.
Section 4: First-aid measures
General advice: First responders need to protect themselves.

Show this safety data sheet to responders or medical per-
sonnel.
After inhalation: Move to fresh air. Seek medical attention
if irritation persists.
After skin contact: Take off contaminated clothing. Rinse
skin with water/shower for 15 min. Seek medical attention.
After eye contact: Rinse with plenty of water. Remove contact
lenses. Seek medical attention.
After swallowing: Have victim rinse mouth and drink water.
Do not induce vomiting. Do not try to neutralize. Seek med-
ical attention.
1.3 PRECISION AND RANDOM ERROR
A good lab practice to improve the credibility of any type of measurement is to

simply repeat it more than once. We call measurements of multiple test portions
from the same sample replicate measurements. Placing a test portion in an instru-
ment and recording the signal multiple times is signal averaging, which is useful
if the signal fluctuates. Signal averaging is not the same as making replicate mea-
surements. Signal averaging will not identify the bias if a test portion was diluted
by a factor of 10 when the experimental procedure called for a dilution by 5.
After dividing a sample into several test portions, each test portion is treated
and measured using the identical procedure. If an analytical procedure
requires 10 steps, the 10 steps are done on each test portion. Doing replicate
precision and random error 15
measurements can identify gross errors such as omitting one step in a procedure,
one-time instrument glitches, or writing a value incorrectly. Even when making
individual measurements, an analytical method will specify remeasuring a stan-
dard or sample at some frequency. The frequency could be twice daily, one
duplicate measurement for each batch of samples, or once every 10 measure-
ments. The frequency depends on the stability that is expected for a given method
or instrument. Making duplicate measurements is especially useful to identify
drift. Drift is the gradual change in instrument response over time. It introduces
a bias in measurements that gets worse with time. Observing drift in a duplicate
measurement can indicate that a method or instrument requires recalibration.
The repeatability in making replicate measurements is called precision.12 We
use the term repeatability when we are talking about replicate measurements
made on the same sample and performed under identical conditions. When we
compare measurements of the same sample by different analysts or different
methods, we use the term reproducibility. The calculation of precision is the
same for repeatability and reproducibility, the difference is the source of the
measurements and the purpose of the result. Quantitative measures of preci-
sion include standard deviation, standard error, and confidence limits (CL).
These measures quantitate the variation or spread in the individual measure-
ments due to random fluctuations, which we call random errors. The distribu-
tion of random fluctuations follows a Gaussian-shape “bell curve,” and
precision is a measure of the width of this distribution. Graphically, we display
the precision by placing error bars about a data point.
The accuracy of a measurement is how close an experimental result comes
to the true value. The difference between a measurement and the true value is
called the systematic error or bias. We determine the bias in a measurement by
measuring samples of known composition, which we call standards. We will
discuss accuracy and systematic errors fully in Section 1.5 on calibration,
which is the process of measuring standards to be able to obtain accurate
results for unknowns.
We can never know with 100% certainty if we have determined the true
concentration of an analyte in a real sample. The accuracy of a measurement
depends on the care in validating sample processing procedures, calibrating
the measurement, and making sure that standards match the samples. The best
that we can do, by following GLP, is to
● use reproducible methods;

● maintain equipment, reagents, and instruments in good working
condition;
● verify the accuracy of our analytical abilities with standards of known
concentrations;
● use a calibration procedure that is appropriate for the unknown sample.
12
Imprecision, or the lack of precision, is probably a better term to describe the repeatability of
measurements, but precision is the more common term.
As an example, the chemical treatment of a municipal water supply is based

on the measurement of a pollutant being less than the EPA action level.
Analysis of randomly collected water samples shows that it contains 14 ppb
Pb, below the EPA action level of 15 ppb.13 If you drink water from this system,
you will probably have a few questions about the result. First, you might ask
the analyst how confident she is of the accuracy of the result. Did the analyst
follow GLP and check the accuracy of the analytical methods by measuring a
known standard? Next, what is the spread in the measurement, that is, what is
the precision of the reported result? Is the range of measured values 14.0 ± 0.1
ppb or is it 14 ± 5 ppb? You might be more concerned if the upper value of the
error bars exceeds the EPA action level.
The terms accuracy and precision are often used interchangeably, but they
are not the same. Precision does not tell us anything about the accuracy of a
result due to systematic errors in the measurement procedure. Figure 1.1 illus-
trates the difference between accuracy and precision using the results of arrows
shot at targets by three different archers. The archer on the left was very steady.
She was precise, but she hit high on the target with every shot. She possibly
aligned her sight incorrectly, estimated the distance to the target incorrectly, or
made some other systematic error. Unfortunately, it is not always possible to
identify the source of a systematic error without performing more experiments.
The center archer hit the middle of the target repeatedly. We describe her
shooting as being accurate and precise. The archer on the right was rather shaky
and tended to hit far from the center of the target. However, if you average the
positions of the four arrows on the right target, you will find that it falls on the
bull’s-eye. We describe his shooting as accurate but with poor precision.
Now let us think about what these archers might do when they try again.
The center archer did very well, and she will not want to make any changes.
The archer on the left might adjust her sight to try to be more accurate. If she
was shooting from 20 m on her first try, should she now adjust her sight and
shoot from 25 m? No, she wants to make one change and keep everything else
Precise but Accurate Accurate but

not accurate and precise not precise
Figure 1.1 The results from three archers.
13
The EPA action level is the concentration of a contaminant that requires a response such as
public notification, exposure monitoring, or remediation.
the same. The same goes for analytical measurements. If you want repeatable
results, keep all conditions the same. The archer on the right just needs more
practice to get steadier. As in any human endeavor, achieving high accuracy
and precision requires practice and care.
1.3.1 Standard Deviation

As you can see from the archery example, shooting only one arrow might not
provide a reliable measure of how well an archer can shoot. Based on only one
shot, the archers on the left and right might appear very close in proficiency.
The four shots show us that the archer on the left is much steadier than the
archer on the right, but with some systematic error.
On making a series of repetitive measurements, we report the result as the
mean or average, plus-or-minus, ±, some measure of precision. We can quan-
tify the repeatability of replicate measurements using the difference of each
individual measurement from the mean. We call this difference for each
measurement the deviation or residual, di:
d i = xi − x (1.1)
where the mean, x , is
n
∑xi
i =1
x= (1.2)
n
n
The summation symbol, ∑ i =1, indicates that we are to add up all n numbers
in the data set, where the i is an index to refer to each individual measurement.
I will often drop the i = 1 and n notation for clarity. Unless noted otherwise,
take a summation in the statistical formulas for all data points, i.e., from i = 1
to i = n.
As the mean value is an average of all measurements, the deviations will be
both positive and negative. Averaging the deviations produces zero, which is
not a realistic measure of repeatability. A common measure of precision is the
standard deviation or more specifically the sample standard deviation, s:
s=
∑( xi − x )2 (1.3)
n −1
where n is the number of data points and n − 1 is called the degrees of free-
dom.14 By squaring each deviation before summing them, we eliminate the
14
The degrees of freedom is the number of measurements minus the number of results obtained
from the measurements. When calculating the mean of a data set, it is n − 1. On obtaining the
slope and y-intercept of a line, it is n − 2. Taylor, J. R. An Introduction to Error Analysis: The
Study of Uncertainties in Physical Measurements, 2nd ed.; University Science Books: Sausalito,
CA, 1996.
problem of an average deviation going to zero. Taking the square root of the
summed squares gets the standard deviation back to the scale of the mean.
The standard deviation provides a “typical” deviation for a series of measure-
ments. We will see later that this typical deviation encompasses approximately
68% of all measurements in a set of data.
The equation for s is used to describe the precision of a relatively small number
of replicate measurements. For a large number of measurements, say 20 or more
for a reliable procedure, we can use the true or population standard deviation, σ:
σ=
∑( xi − µ )2 (1.4)
n
where μ is taken to be the true value. For a large number of measurements

reporting s or σ will not be very different. Given that there are numerous mea-
sures of precision, you should specify the measure that you use when reporting
the repeatability in a result.
The calculation of the mean and standard deviation can be accomplished
using the built-in functions of a calculator or spreadsheet. These tools will
often calculate both sample standard deviation, s, and population standard
deviation, σ, so be sure you know what your calculator or program returns.
The population standard deviation, σ, is only valid for a large number of mea-
surements. Even though the numerical difference between s and σ might be
small, you will almost always want the sample standard deviation, s, when
working with analytical results.
Table 1.7 lists the results of four replicate titrations to determine the acetic
acid concentration in a vinegar sample. These results are plotted graphically in
Figure 1.2. The filled diamonds are the individual measurements for each stu-
dent and the open squares, shifted to the right for clarity, are the mean of each
data set. The vertical lines with horizontal caps are error bars showing the
sample standard deviation, s, of each data set. The dotted line shows the true
value, which was known for this sample.
These titration results are similar to the archery results in Figure 1.1.
Student A was precise, but a systematic error made his mean result lower than
TABLE 1.7 Titration Results

Concentration, M
Student A Student B Student C
0.824 0.848 0.817
0.849 0.861 0.869
0.834 0.872 0.860
0.839 0.865 0.901
Mean 0.837 0.862 0.862
Std dev 0.010 0.010 0.035
Student A Student B Student C

0.90
Concentration (M)
0.88
0.86
0.84
0.82
Figure 1.2 Results of four replicate titrations.
the true value. Students B and C were both accurate, their means were very
close to the true value. Compared to Student B, Student C’s measurements
were less precise. The error bars on her results were larger than for the other
two students, leading to greater uncertainty in her reported result. Given a
choice, I will take a large error bar on an accurate result in place of a very
repeatable wrong answer.
1.3.2 Relative Standard Deviation

The relative standard deviation (RSD), sr, is a unitless fraction that is calculated
by dividing the standard deviation, s, by the mean of the measurement15:
s
sr = (1.5)
x
The RSD normalizes the standard deviation to the magnitude of the mean
value, making it easier to compare the relative precision in different sets of
measurements. We often express it as a percentage for convenience. IUPAC
recommends the symbol sr(%) for percentage relative standard deviation, but
we will use the more common abbreviation of %-RSD. The expression for
%-RSD is
s
%-RSD =  ×100% (1.6)
x 
If your measurements are also expressed as a percentage, be sure to specify if

you are reporting the RSD or %-RSD to avoid confusion.
Example 1.2 illustrates the usefulness of using the %-RSD to compare the
precision in different data sets when the means vary in magnitude. The table in
the calculation shows measurement results obtained from four students for
four different samples. Each student reports an equivalent standard deviation.
Because the samples are different, quoting equivalent standard deviations does
15
The relative standard deviation is also called the “coefficient of variation” in some disciplines.
not provide a true representation of each student’s repeatability. Recalculating

the precision as a relative percentage provides values that are easier to
compare.
Example 1.2 Percentage Relative Standard Deviation. The table lists the
results from four students who each measured a different sample using the
identical analytical procedure. Let us see which measurement result was most
precise.
Student Mean, ppm Std Dev, ppm
A 1.03 0.01
B 10.03 0.01
C 3.58 0.01
D 0.11 0.01
Each measurement has the same standard deviation, but each measurement
was not made with equal precision. Calculating the standard deviation as
%-RSD for Student A gives
 0.01 ppm 
%-RSD A =  ×100% = 1%
1.03 ppm 
Repeating this calculation for the other students and adding the results to the
table shows clearly which measurements are most and which are least precise.
The result from Student B was measured to 0.1%, much better than the ones
the other students achieved. We cannot say anything about the accuracy of the
results based only on this data, but Student B certainly had a more repeatable
technique in performing the measurement.
Student Mean, ppm Std Dev, ppm %-RSD, %

A 1.03 0.01 1
B 10.03 0.01 0.1
C 3.58 0.01 0.3
D 0.11 0.01 9
1.3.3 Other Measures of Precision

The quantitative measures of precision described above, s and %-RSD, are the
ones that we will use most often to describe analytical results. The %-RSD is
most useful to compare the precision of different measurements that vary in
magnitude or that use different units. The practical significance of s (or σ) is
that 68% of the measurements will fall between ±1s. The 68% range assumes
that the deviations from the mean are due only to random variations in the
measurement. The 68% range of the standard deviation is not always the best
measure to state the degree of confidence that we have in the repeatability of a
measurement or in the spread in results from multiple samples. Several other
quantities—variance, standard error, and CL—are described here for com-
pleteness. Each of these measures of precision derive from the standard
deviation and are useful for different purposes.
1.3.3.1 Variance The variance is simply the square of the standard deviation:
n
∑( xi − x )2
v = s2 = i =1
(1.7)
n −1
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. The topic of the propagation of uncertainty is beyond the needs
of this text, but it is treated in several other sources on practical statistics.16
1.3.3.2 Standard Error The standard error, sm, also called the standard
deviation of the mean (SDOM), is the standard deviation divided by the square
root of n:
s
sm = (1.8)
n
By dividing by n, the sm provides a better reflection of the amount of data
collected than other measures of precision. Taylor considers it the “best” mea-
sure of the uncertainty in a set of multiple measurements.17 A significant
difference between the standard error and the standard deviation is that the
standard error will decrease with increasing number of measurements,
although slowly for large n.
1.3.3.3 Confidence Limits For a set of measurements in which the

deviations of the individual measurements vary only due to random fluctuations,
we expect a normal or “bell curve” distribution. The mean ± standard deviation
of a normal distribution will encompass approximately 68% of the individual
measurements. Two standard deviations, ±2s, will encompass approximately
95% of the individual measurements. These values are the ideal case for a very
16
Taylor, J. R. An Introduction to Error Analysis: The Study of Uncertainties in Physical
Measurements, 2nd ed.; University Science Books: Sausalito, CA, 1996; also useful are Bevington
P.; Keith Robinson, D. K. Data Reduction and Error Analysis for the Physical Sciences, 3rd ed.;
McGraw-Hill: New York, 2002 and Garland, C. W.; Nibler, J. W.; Shoemaker, D. P. Experiments
in Physical Chemistry, 7th ed.; McGraw-Hill: New York, 2003.
17
Taylor, J. R. An Introduction to Error Analysis: The Study of Uncertainties in Physical
Measurements, 2nd ed.; University Science Books: Sausalito, CA, 1996.
Figure 1.3 Histogram and normal distribution.
large number of measurements. Figure 1.3 shows a histogram of one hundred

data points (n = 100) that have a mean of 10.0 and a sample standard deviation
of 2.0. “Frequency” on the y-axis is the number of data points within a span of
0.5; for example, the bar at 11 shows that 12 data points fall between 10.75 and
11.25. The solid line is a normal distribution for this same mean and standard
deviation.18 You can see that there are noticeable differences between the
histogram and the normal distribution even for n = 100. The normal distribution
curve does match the overall shape of the scatter in the data points. In this
example data, 68 values fall between 8 and 12 (±1 s) and 97 values fall between
6 and 14 (±2 s), as expected for a normal distribution.
There are frequent occasions when we must compare analytical results to
other values. This type of task is known as hypothesis testing, and several
common cases in chemical analysis are based on the following.
● Is an experimental procedure operating correctly, that is, is a measured

result statistically equivalent to a known value?
● Is a measured result above or below some specified level?
● Is the difference between two sets of experimental measurements statisti-
cally significant?
To answer these questions, we use a more definitive description for the impre-
cision of repetitive measurements.
Consider again our example of lead in drinking water, for which the EPA
has set an action level of 15 ppb Pb. Suppose that measurements from a
random sampling of water in homes show a mean and standard deviation of
14 ± 1 ppb. For this municipal water supply, 68% of the measurements fall bet-
ween 13 and 15 ppb. 16% of the water samples contain less than 13 ppb Pb,
which is not an issue for the quality and safety of the drinking water. However,
16% of the water samples contain Pb greater than the 15 ppb EPA action level.
In this case, reporting the standard deviation might not be the best measure of
precision on which to base water treatment decisions. If I lived in this locality,
18
The histogram data was generated in Excel using Random Number Generation in the Data
Analysis Toolpak and the curve was generated with the NORMDIST function.
I might not want to take the risk that my tap water is in the 16% of cases with
high Pb levels. So the question is: To what level should the average lead level be
reduced?
In such cases, we introduce the “level of confidence” to specify the proba-
bility of a value being within or outside of a given distribution of measure-
ments. CL is a statistical measure of the precision for replicate measurements
that can be calculated for different levels of confidence. It is calculated from
the standard deviation, s, using
t×s
CL = (1.9)
n
where n is the number of measurements and t is a critical t-value taken from

Table 1.8. These values are for a two-tailed test, meaning that the true value
could be larger or smaller than the predicted distribution. For a 95%
confidence level, you are allowing for a 2.5% probability of the true value
being greater than your CI or a 2.5% probability of the true value being less
than your CI.19
CI = (x − CL)to (x + CL) (1.10)
TABLE 1.8 Table of Critical t-Values

t-Values for Different Levels of Confidence
80.0% 90.0% 95.0% 99.0% 99.9%
n−1 (0.20) (0.10) (0.05) (0.01) (0.001)
1 3.078 6.314 12.706 63.657 636.600
2 1.886 2.920 4.303 9.925 31.590
3 1.638 2.353 3.182 5.841 12.920
4 1.533 2.132 2.776 4.604 8.610
5 1.476 2.015 2.571 4.032 6.869
6 1.440 1.943 2.447 3.707 5.959
7 1.415 1.895 2.365 3.500 5.408
8 1.397 1.860 2.306 3.355 5.041
9 1.383 1.833 2.262 3.250 4.781
10 1.372 1.812 2.228 3.169 4.587
15 1.341 1.753 2.131 2.947 4.073
20 1.325 1.725 2.086 2.845 3.850
25 1.316 1.708 2.068 2.787 3.725
30 1.310 1.697 2.068 2.750 3.646
50 1.299 1.676 2.068 2.678 3.496
100 1.290 1.660 2.068 2.626 3.391
∞ 1.310 1.645 2.068 2.576 3.300
19
NIST/SEMATECH e-Handbook of Statistical Methods; https://www.itl.nist.gov/div898/
handbook/eda/section3/eda3672.htm; accessed August 2022.
where CI, confidence interval, is the span of values that encompasses the true
value with the stated level of confidence (see Example 1.3).
Table 1.8 also introduces the α notation, the values in parentheses, which is
called the significance level. Referring to a significance of α = 0.05 or a
confidence level of 0.95 (or 95%) is the same for our purposes, and the symbol
for confidence level is 1 − α.
Returning to the lead in the drinking water example, if the 14.0 ppb mean
was the result of six measurements, the 99% CL is
2.78×1.0 ppb
CL = = 1.2 ppb (1.11)
5
If the mean was the result of 21 measurements, the 99% CL is
2.09×1.0 ppb
CL = = 0.5 ppb (1.12)
20
In these two cases, the number of measurements affects our level of confidence.
With only six water samples the range of 14.0 ± 1.2 ppb encompasses the EPA
action level, but for 21 measurements the result of 14.0 ± 0.5 ppb is safely
below the action level.
Example 1.3 CI Calculation. What is the 95-% CI for the following four tri-
als of an iron analysis of a soil?
Weight Percent of Fe in Soil
Test Portion Result
1 3.44% Fe
2 3.11% Fe
3 2.98% Fe
4 3.27% Fe
The sum of the four data points is 12.80, the mean is 3.20, and the standard
deviation is 0.20 (determined from a spreadsheet).
Using the expression for CL and a t value from Table 1.8 for n − 1 of 3:
(3.182)(0.20)
CL = = 0.32
4
The CI at 95% confidence is (3.2 ± 0.3)%.
You-Try-It 1.B
Replicate measurement data is in the precision worksheet in you-try-
it-01.xlsx. Open this worksheet and type formulas to find the mean,
discarding a suspected outlier 25
standard deviation, and %-RSD of the experimental data. Change col-

umn widths and formatting to create a worksheet that will be suitable
to cut and paste into a report.
The data shown in the example above is in the confidence-interval
worksheet in you-try-it-01.xlsx. Open this worksheet and repeat the
calculation for the 90% and 99% level of confidence. As a check, run
the Descriptive Statistics in the Data Analysis Toolpak.
1.4 DISCARDING A SUSPECTED OUTLIER
If one value in a set of data appears very different from the rest, it might be
possible to discard that value. The basis to discard a value is that some unrec-
ognized error causes that value to not be representative of the sample. There
are a number of criteria for removing an apparent outlier from a set of mea-
surements. This section will illustrate Dixon’s Q test and Peirce’s Criterion.
Note that performing a test is not necessary to discard data that you know is
erroneous. For example, if you were making a UV/Vis absorption measurement
and one solution was turbid due to a precipitate being disturbed from the bot-
tom of a reaction tube, you may make a note of your observation in your note-
book and discard the data value for that one experimental trial. Similarly, it is
not necessary to discard a suspected outlier, and the conservative approach is
to report all data with the larger standard deviation. If you do remove a point
from a set of data, you must acknowledge the change to your data and specify
your criterion for discarding the data.
1.4.1 Dixon’s Q Test

To use Dixon’s Q test as the criterion to discard a suspected outlier, calculate
Q using the following formula:
suspected outlier − closest value
Q= (1.13)
highest value − lowest valuee
If Q is larger than the critical value, Qc, for n repetitive measurements (see
Table 1.9), then the outlier may be discarded. This expression and the table of
Qc is only valid for discarding one data point from a series of measurements
(see Example 1.4). A more complete list at different levels of confidence can be
found in the literature.20
20
Adapted with permission from Rorabacher, D. B. “Statistical treatment for rejection of deviant
values: critical values of Dixon’s ‘Q’ parameter and related subrange ratios at the 95% confidence
level,” Anal. Chem. 1991, 63, 139–146. Copyright 1991 American Chemical Society.
TABLE 1.9 Critical Values of Dixon’s

Q Parameter (Qc)
95% 99%
n (α = 0.05) (α = 0.01)
3 0.970 0.994
4 0.829 0.926
5 0.710 0.821
6 0.625 0.740
7 0.568 0.680
8 0.526 0.634
9 0.493 0.598
10 0.466 0.568
15 0.384 0.475
20 0.342 0.425
25 0.317 0.393
30 0.298 0.372
Example 1.4 Q-Test Calculation. Consider the following five potentiometric

measurements of Mg2+ in five test portions of water from a fish aquarium.
Ca2+ must be precipitated before measurement, leading to a source of error.
Potentiometric measurements for Mg
Test Portion Measurement, mV
1 39.8
2 36.5
3 39.9
4 39.2
5 39.6
The value of 36.5 mV appears lower than the rest of the values in the set.
Can this value be discarded?
To answer this question, we find Q and compare it to Qc:
36.5 − 39.2
Q= = 0.794
39.9 − 36.5
At the 95% confidence level, which is usually suitable for working with analyti-
cal data sets, Qc = 0.710 for five data points. Our calculated Q is larger than Qc,
so the suspected outlier may be discarded. Recalculating the mean after dis-
carding the outlier gives a much smaller standard deviation 39.6 ± 0.3 mV,
compared to an original value of 39.0 ± 1.4 mV.
1.4.2 Peirce’s Criterion

Another approach to determine if data points are outliers and may be removed
from a data set is to ask the question:
What is the probability of a suspected outlier occurring in a normal distri-
bution given the number of measured values, n?
discarding a suspected outlier 27
TABLE 1.10 Values of R for Peirce’s Criterion

Number of Suspected Outliers
n 1 2 3 4
3 1.196
4 1.383 1.078
5 1.509 1.200
6 1.610 1.299 1.099
7 1.693 1.382 1.187 1.022
8 1.763 1.453 1.261 1.109
9 1.824 1.515 1.324 1.178
10 1.878 1.570 1.380 1.237
11 1.925 1.619 1.430 1.289
12 1.969 1.663 1.475 1.336
13 2.007 1.704 1.516 1.379
14 2.043 1.741 1.554 1.417
15 2.076 1.775 1.589 1.453
20 2.209 1.914 1.732 1.599
25 2.307 2.019 1.840 1.709
50 2.592 2.326 2.158 2.035
If the probability is very low, then the suspected outlier(s) may be discarded.
Using the data in the previous example, the mean and standard deviation of
the data are 39.0 ± 1.4 mV. The suspected outlier, 36.5 mV, is nearly two stan-
dard deviations from the mean. A value this distance from the mean should
arise in approximately 5% of measurements. We would expect a value such as
36.5 mV to appear in a set of more than 20 measurements, but not when we
have only 5 measurements.
Two similar methods that use this approach are Chauvenet’s criterion and
Peirce’s criterion. I will describe Peirce’s criterion because it is easier to imple-
ment using a published table of critical values (Table 1.10).21 This method
compares the deviation of the suspected outlier, that is, the difference from the
mean value, to the probability of a data point being that different from the
mean assuming a normal distribution of n measurements. Peirce’s criterion
can test multiple outliers, but we will use it here to test only one suspect value.
The procedure to use Peirce’s criterion is to first calculate the absolute value
of the deviation from the mean for a suspected outlier:
d i = xi − x
where xi is the suspected outlier and x is the mean. This deviation is then com-
pared to the maximum deviation, dmax, that is expected for a random distribu-
tion given the number of data values. dmax is found from
d max = sR
21
Adapted with permission from Ross, S. M. “Peirce’s criterion for the elimination of suspect
experimental data,” J. Eng. Technol. Fall 2003.
where s is the sample standard deviation and R is taken from a table of values.
If the deviation of the suspected outlier is larger than dmax, it is improbable
that the outlier occurred owing to a random fluctuation. The suspected outlier
may be discarded if this condition is met:
| d i| > d max
You-Try-It 1.C
The above data is replicated in the outlier worksheet in you-try-it-01.
xlsx. Use this worksheet to test for the suspected outlier using Dixon’s
Q test at the 99% CL and using Peirce’s criterion. Use the = MIN(range)
and = MAX(range) functions to find the potential outliers in the data
set. Check that you get the same result as the Q-test calculation above.
1.5 CALIBRATION
The preceding section described the statistical tools to describe the repeat-
ability of replicate measurements. Calibration is the process of measuring a
known quantity to determine the relationship between the measurement signal
and the analyte amount or concentration. Calibration allows the analyst to
estimate the accuracy of a measurement, procedure, or instrument.
Calibration is critical to GLP and method development and validation.
Method development is the process to determine the experimental conditions
for sample collection, preparation, and measurement that produce accurate
and repeatable results. Very often this work has been done by someone else
and you are using one or more standard methods. When a standard method is
not available, analysts usually start with a method for an analyte in a similar
type of sample and modify it to obtain good results. Method validation is the
process to ensure that you are obtaining accurate and repeatable results. To
quote 21 CFR 211.165 (e) 22:
The accuracy, sensitivity, specificity, and reproducibility of test methods

employed by the firm shall be established and documented. Such validation and
documentation may be accomplished in accordance with Section 211.194(a)(2).
where section 211.194(a)(2) refers to proper record keeping of analytical

methods or citation to standard methods.
Periodic calibration is necessary to maintain methods and instruments
in proper working order and to identify and eliminate systematic errors. The
22
Part 211—Current Good Manufacturing Practice for Finished Pharmaceuticals.
calibration 29
frequency and extent of calibration procedures will be method dependent and

should be specified in SOPs for a given procedure or instrument. Systematic
errors might result from a bias due to unidentified components in a sample, an
uncontrolled instrument factor, or a persistent human error. An example of an
instrumental bias is an incorrectly calibrated pH meter that always reads a pH
value that is 0.5 units lower than the true value. An example of a method error
is the partial loss of a volatile metal analyte during an ashing step to remove
organic material. An example of human bias is a student who records titration
endpoints beyond the correct endpoint owing to color blindness. Systematic
errors can be identified and corrected by analyzing standards that closely
match the real sample. As Figure 1.4 illustrates, if something seems odd, it
probably is odd, and it might introduce a bias.
There are several common calibration procedures for analytical measurements:
● a simple proportionality (one-point calibration),
● using a calibration or working curve,
● using an internal standard,
● using the standard-addition method.
All of these calibration methods require one or more standards of known

composition to calibrate the measurement. We will look at the key aspects of
these different calibration approaches and then discuss the proper use and
preparation of standards in the next section.
1.5.1 Linear Proportionality
Most of the analytical methods that we will discuss assume that the measured
signal is directly proportional to an analyte amount or concentration. The
generic expression of a direct or linear proportionality is
y = a1x (1.14)
where y is the measured signal, a1 is the proportionality factor, and x is the

analyte amount or concentration. I will continue discussing these topics in
100 g
50 g
5g
5g
Calibration weights
Figure 1.4 Source of a systematic error.

terms of concentration, but these concepts apply equally to detection systems

that are sensitive to analyte amount. The proportionality factor, a1, is called
the sensitivity of the measurement. The larger the sensitivity, the larger the
signal for a given analyte concentration. The basic concept of calibration is to
measure the signal produced by a standard of known composition to deter-
mine the sensitivity, a1. Knowing a1, we can determine the analyte concentration
in a test portion by measuring the signal from the test portion.
Given a linear proportionality, we expect a signal of zero in the absence of
analyte, that is, y = 0 when x = 0.23 It is good practice to always measure the
signal produced by a standard that contains no analyte, which we call the
blank or 0.0 concentration standard. It is not uncommon for the blank to
have a nonzero signal, which can arise from an offset of the recording device
or a substance in the blank that produces a signal. The calculation in Example
1.5 illustrates the use of a nonzero blank measurement in an analytical
measurement.
Example 1.5 Calibration Calculation. Total dissolved solids (TDS) in water
and soils can be estimated from the electrical conductivity of solution. Solution
conductivity is proportional to the number and types of ions in solution. It is
expressed as siemens per unit distance (S/cm), where the unit S, siemens, is the
measure of conductance. You add 50 ml of tap water to 10 g of dried and
crushed soil from an irrigated field and shake for 5 min. After filtering you
measure the conductivity of the water. For a standard you use 5.00 g of high
purity KCl (f.w. 74.551 g/mol) in 1.00 l of tap water. Performing the measure-
ment on solutions of a blank (water only), standard, and soil sample gives the
following solution conductivities. What is the TDS in the soil sample?
Solution Concentration, Measured Conductivity,

g/l mS/cm
Blank 0.00 0.05

Standard 5.00 9.26
Soil sample ? 5.50
This calculation is a one-point calibration. You expect 0.0 mS/cm for the
blank, but there is some residual salt in the tap water. To correct the stan-
dard and unknown measurements, subtract the nonzero blank from each
value. The corrected measurements are 9.21 mS/cm for the standard and
5.45 mS/cm for the soil sample. There are two approaches to work with a
proportionality: determine the sensitivity, a1, or set up a simple ratio. The
two calculations are equivalent, so use whichever one is most intuitive for
you. I will show the calculation first by finding the sensitivity and then using
23
The potentiometric methods discussed in Chapter 8 are one notable exception.
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XIII
Then, at the drooping of the twilight hour,
We wander in the ancient plaza where
We breathe the attar of the jasmine flower
Like incense on the altar of the air;
And list, as music swells
Down drifting from the old cathedral tower,
The arpeggio of the bells.
XIV
We linger by the sea-wall while the tide
Below us murmurs like a sad refrain,
Bearing from outer ocean reaches wide
The lore and legend of the Spanish main,
Nor leave that spot serene
Till Sleep, as with the mantle of the bride,
Wraps fair Saint Augustine.
XV
Days dedicate to rapturous things were these;
It was as though Youth came again, and brought
Past aims, past ardors and past ecstasies,
And toward the shrine of Beauty turned our thought.
And there were after times
Of exultation, prismic harmonies,
When hours ran by in rhymes.
XVI
Once, ’mid cathedral Carolinian pines,
We saw the Springtide, at its radiant birth,
Kindle to fragrant gold the coiling vines,
And make a garden of the wakened earth;
And every morning heard
Within the treetops, melody linked with mirth,
The hidden mocking-bird.
XVII
And while the cardinal through the waving bredes
Of pendulous moss swift flitted like a flame,
Back flooded to our minds the illustrious deeds,
Emblazoned on the honor-scroll of Fame,
When Liberty was won,
Hearkening the Ashley whisper to its reeds
The name of Marion.
XVIII
From Gloucester cliffs and brown Nantucket dunes
The mountains lured you, and the mountain star;
For us the Woodland sang its lyric runes
Where’er we followed it, or near or far,
In sun or shadow cool,
Or loitered through long languorous afternoons
By Dian’s darkling pool.
XIX
Far up the valley Wittenberg’s vast form,
Its summit beckoning, with you I view,
And above sweeping slopes where wild bees swarm
Glimpse timid deer at dawn and fall of dew;
Through Panther Kill we roam,
And mark the purple streamers of the storm
Ascend behind the Dome.
XX
And, too, in bookmen’s mines of dusty ore
Ever shall I remember how we delved,
Plucking from out the musty treasure-store
Rich rarities within the darkness shelved,
Elated if we found
Leaves that some name we long had honored bore
In frayed morocco bound.
XXI
Thus, step by step, we trod adown the years,
Thus, side by side, with ne’er a break between;
We shared our laughter and we shared our tears,
Nor deemed inexorable Fate might intervene
To sever the strong cord
That bound us, Fate with its “abhorrèd shears,”
That is man’s over-lord.
XXII
You that in Autumn came, in Autumn went;
How vain to say the mourning word! how vain
To beat the bars of that arbitrament
That metes to mortals pleasurement or pain!
How vain!—how vain!—and yet
We beat upon them, and we only gain
The poignance of regret!
XXIII
Autumn again with all its loveliness;
Autumn again that brought an end to joy,
Despite the sight of earth in amber dress,
And airs that bear the blitheness of a boy!
Autumn, and leaves that toss
In bright brief triumphing, while they express
The brooding sense of loss.
XXIV
Autumn again down every winding way
That, in the days gone by, our footsteps pressed!—
Instead of woven amaranth would I lay
Above your dust—you gone by paths unguessed—
Love’s deathless asphodel;
Until some happier hour,—when, who shall say?—
Brother in song, farewell!
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Basics of Analytical Chemistry and

Chemical Equilibria A Quantitative

Chemistry in Quantitative Language: Fundamentals of

Archaeology The Basics 4th Edition Brian M. Fagan

World Prehistory The Basics 1st Edition Brian M. Fagan

Practical Soft Tissue Pathology. A Diagnostic Approach

The Thermodynamics of Phase and Reaction Equilibria 2nd

Atlas of Wound Healing: A Tissue Regeneration Approach

Chemical Reaction Engineering: A Computer-Aided

Quantitative Chemical Analysis Tenth Edition Daniel C

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

Paperback ISBN: 9781119707356; ePub ISBN: 9781119707387; ePDF ISBN: 9781119707349

Cover Images: Background: © kundoy/Getty Images; Figure: Courtesy of Brian M. Tissue

ABOUT THE COMPANION WEBSITE xiii

I QUANTITATIVE ANALYSIS USING REACTIONS

2.6 Introduction to Stationary Phases / 84

II REACTIONS THAT DO NOT GO TO “COMPLETION.”

5 ACID–BASE EQUILIBRIA AND ACTIVITY 185

6.3 Weak Acid Titration Curve / 238

III INSTRUMENTAL METHODS AND ANALYTICAL

9 ELECTROANALYTICAL CHEMISTRY 313

10.5 Other Mass Spectrometer Designs / 390

● sampling, sample processing, and method validation;

I do not attempt to be comprehensive in this text. Samples that require anal-

I organize the discussion of the core principles of analytical chemistry into

● Part I: Analytical concepts such as calibration and uncertainty, sample

The analytical methods in Part I rely on reactions that go to completion.

Basic math Algebra

Blacksburg, VA Brian M. Tissue

This book is accompanied by a companion website:

This website includes:

QUANTITATIVE ANALYSIS USING

● Describe aspects of good laboratory practice (GLP).

● measuring a physical property,

TABLE 1.1 Measurement Terms

TABLE 1.2 Measurement Strategies

numerous other spectroscopic techniques to make quantitative measurements

1.1.1 Concentration Units

TABLE 1.3 SI Base Units

mg (milligram), and g (gram). The purpose of the prefixes is to simply express

TABLE 1.4 Common Numerical Prefixes

TABLE 1.5 SI Derived Units

Different types of analytical methods will measure concentration, volume,

TABLE 1.6 Common Concentration Units

Converting ppm to ppb is accomplished by multiplying by 1000:

To convert to molarity, M, we use the formula weight of benzene, which is

Now dividing by 1.0 l to obtain concentration, c, gives

6.4 ×10−8 mol

5×10−6 g C 6H6  0.1 5×10−7 g C 6H6

The following spreadsheet calculation is the first You-Try-It exercise in the

I place these exercises at appropriate locations in each chapter, and I ­recommend

1.2 GLP AND A FEW OTHER IMPORTANT ACRONYMS

1.2.1 Good Laboratory Practice (GLP)

● Title 21, Part 58: US Food and Drug Administration,

[Code of Federal Regulations]

TITLE 21--FOOD AND DRUGS

CHAPTER I--FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF

Subpart E_Testing Facilities Operation

ABOUT THE COMPANION WEBSITE xiii

I QUANTITATIVE ANALYSIS USING REACTIONS

II REACTIONS THAT DO NOT GO TO “COMPLETION.”

5 ACID–BASE EQUILIBRIA AND ACTIVITY 185

III INSTRUMENTAL METHODS AND ANALYTICAL

9 ELECTROANALYTICAL CHEMISTRY 313

Blacksburg, VA Brian M. Tissue

I place these exercises at appropriate locations in each chapter, and I recommend