Analytical I PDF

ANALYTICAL I
Analytical I
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This text was compiled on 10/11/2020

TABLE OF CONTENTS
1: INTRODUCTION TO ANALYTICAL CHEMISTRY

1.1: WHAT IS ANALYTICAL CHEMISTRY?
1.2: THE ANALYTICAL PERSPECTIVE
1.3: COMMON ANALYTICAL PROBLEMS
1.4: INTRODUCTION TO ANALYTICAL CHEMISTRY (EXERCISES)
1.5: INTRODUCTION TO ANALYTICAL CHEMISTRY (SUMMARY)
2: BASIC TOOLS OF ANALYTICAL CHEMISTRY

In the chapters that follow we will explore many aspects of analytical chemistry. In the process we will consider important questions
such as “How do we treat experimental data?”, “How do we ensure that our results are accurate?”, “How do we obtain a representative
sample?”, and “How do we select an appropriate analytical technique?” Before we look more closely at these and other questions, we
will first review some basic tools of importance to analytical chemists.
2.1: MEASUREMENTS IN ANALYTICAL CHEMISTRY

2.2: CONCENTRATION
2.3: STOICHIOMETRIC CALCULATIONS
2.4: BASIC EQUIPMENT
2.5: PREPARING SOLUTIONS
2.6: SPREADSHEETS AND COMPUTATIONAL SOFTWARE
2.7: THE LABORATORY NOTEBOOK
2.8: BASIC TOOLS OF ANALYTICAL CHEMISTRY (EXERCISES)
2.9: BASIC TOOLS OF ANALYTICAL CHEMISTRY (SUMMARY)
3: THE VOCABULARY OF ANALYTICAL CHEMISTRY

If you leaf through an issue of the journal Analytical Chemistry, you will soon discover that the authors and readers share a common
vocabulary of analytical terms. You are probably familiar with some of these terms, such as accuracy and precision, but other terms,
such as analyte and matrix may be less familiar to you. In order to participate in the community of analytical chemists, you must first
understand its vocabulary.
3.1: ANALYSIS, DETERMINATION, AND MEASUREMENT

3.2: TECHNIQUES, METHODS, PROCEDURES, AND PROTOCOLS
3.3: CLASSIFYING ANALYTICAL TECHNIQUES
3.4: SELECTING AN ANALYTICAL METHOD
3.5: DEVELOPING THE PROCEDURE
3.6: PROTOCOLS
3.7: THE IMPORTANCE OF ANALYTICAL METHODOLOGY
3.8: THE VOCABULARY OF ANALYTICAL CHEMISTRY (EXERCISES)
3.9: THE VOCABULARY OF ANALYTICAL CHEMISTRY (SUMMARY)
4: EVALUATING ANALYTICAL DATA

When using an analytical method we make three separate evaluations of experimental error. First, before beginning an analysis we
evaluate potential sources of errors to ensure that they will not adversely effect our results. Second, during the analysis we monitor our
measurements to ensure that errors remain acceptable. Finally, at the end of the analysis we evaluate the quality of the measurements
and results, comparing them to our original design criteria.
4.1: CHARACTERIZING MEASUREMENTS AND RESULTS

4.2: CHARACTERIZING EXPERIMENTAL ERRORS
4.3: PROPAGATION OF UNCERTAINTY
4.4: THE DISTRIBUTION OF MEASUREMENTS AND RESULTS
4.5: STATISTICAL ANALYSIS OF DATA
4.6: STATISTICAL METHODS FOR NORMAL DISTRIBUTIONS
4.7: DETECTION LIMITS
4.8: USING EXCEL AND R TO ANALYZE DATA
4.9: EVALUATING ANALYTICAL DATA (EXERCISES)
1 10/11/2020
4.10: EVALUATING ANALYTICAL DATA (SUMMARY)
5: STANDARDIZING ANALYTICAL METHODS

Standardization is the process of determining the relationship between the signal and the amount of analyte in a sample. Previously, we
defined this relationship as Stotal=kACA+Sreag where Stotal is the signal, nA is the moles of analyte, CA is the analyte’s
concentration, kA is the method’s sensitivity for the analyte, and Sreag is the contribution to Stotal from sources other than the sample.
To standardize a method we must determine values for kA and Sreag, which is the subject of this chapt
5.1: ANALYTICAL STANDARDS

5.2: CALIBRATING THE SIGNAL
5.3: DETERMINING THE SENSITIVITY
5.4: LINEAR REGRESSION AND CALIBRATION CURVES
5.5: BLANK CORRECTIONS
5.6: USING EXCEL AND R FOR A REGRESSION ANALYSIS
5.7: STANDARDIZING ANALYTICAL METHODS (EXERCISES)
5.8: STANDARDIZING ANALYTICAL METHODS (SUMMARY)
6: EQUILIBRIUM CHEMISTRY
Regardless of the problem on which an analytical chemist is working, its solution requires a knowledge of chemistry and the ability to
apply that knowledge. For example, an analytical chemist studying the effect of pollution on spruce trees needs to know the chemical
differences between p‑hydroxybenzoic acid and p‑hydroxyacetophenone, two phenols found in the needles of spruce trees. Your ability
to “think as a chemist” is a product of your experience in the classroom and in the laboratory.
6.1: REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIA

6.2: THERMODYNAMICS AND EQUILIBRIUM CHEMISTRY
6.3: MANIPULATING EQUILIBRIUM CONSTANTS
6.4: EQUILIBRIUM CONSTANTS FOR CHEMICAL REACTIONS
6.5: LE CHÂTELIER’S PRINCIPLE
6.6: LADDER DIAGRAMS
6.7: SOLVING EQUILIBRIUM PROBLEMS
6.8: BUFFER SOLUTIONS
6.9: ACTIVITY EFFECTS
6.10: USING EXCEL AND R TO SOLVE EQUILIBRIUM PROBLEMS
6.11: SOME FINAL THOUGHTS ON EQUILIBRIUM CALCULATIONS
6.12: EQUILIBRIUM CHEMISTRY (EXERCISES)
6.13: EQUILIBRIUM CHEMISTRY (SUMMARY)
7: GRAVIMETRIC METHODS
Gravimetry includes all analytical methods in which the analytical signal is a measurement of mass or a change in mass. When you step
on a scale after exercising you are making, in a sense, a gravimetric determination of your mass. Mass is the most fundamental of all
analytical measurements, and gravimetry is unquestionably our oldest quantitative analytical technique.
7.1: OVERVIEW OF GRAVIMETRIC METHODS

7.2: PRECIPITATION GRAVIMETRY
7.3: VOLATILIZATION GRAVIMETRY
7.4: PARTICULATE GRAVIMETRY
7.5: GRAVIMETRIC METHODS (EXERCISES)
7.6: GRAVIMETRIC METHODS (SUMMARY)
8: TITRIMETRIC METHODS
Titrimetry, in which volume serves as the analytical signal, made its first appearance as an analytical method in the early eighteenth
century. Titrimetric methods were not well received by the analytical chemists of that era because they could not duplicate the accuracy
and precision of a gravimetric analysis. Not surprisingly, few standard texts from the 1700s and 1800s include titrimetric methods of
analysis.
8.1: OVERVIEW OF TITRIMETRY

8.2: ACID–BASE TITRATIONS
8.3: COMPLEXATION TITRATIONS
8.4: REDOX TITRATIONS
2 10/11/2020
8.5: PRECIPITATION TITRATIONS
8.6: TITRIMETRIC METHODS (EXERCISES)
8.7: TITRIMETRIC METHODS (SUMMARY)
BACK MATTER
INDEX
GLOSSARY
3 10/11/2020
CHAPTER OVERVIEW
1: INTRODUCTION TO ANALYTICAL CHEMISTRY
Chemistry is the study of matter, including its composition and structure, its physical properties, and
its reactivity. There are many ways to study chemistry, but, we traditionally divide it into five fields:
organic chemistry, inorganic chemistry, biochemistry, physical chemistry, and analytical chemistry.
Although this division is historical and, perhaps, arbitrary—as witnessed by current interest in
interdisciplinary areas such as bioanalytical chemistry and organometallic chemistry—these five
fields remain the simplest division spanning the discipline of chemistry.
Topic hierarchy
1.1: WHAT IS ANALYTICAL CHEMISTRY?

Analytical chemistry is too broad and too active a discipline for us to define completely. This
description is misleading. In this chapter we will try to say a little about what analytical chemistry is, as well as a little about what
analytical chemistry is not. Analytical chemistry is often described as the area of chemistry responsible for characterizing the
composition of matter, both qualitatively (Is there any lead in this sample?) and quantitatively (How much lead is in this sample?).
1.2: THE ANALYTICAL PERSPECTIVE

Many analytical chemists describe this perspective as an analytical approach to solving problems. Although there are probably as
many descriptions of the analytical approach as there are analytical chemists, it is convenient for our purpose to define it as the five-
step process.
1.3: COMMON ANALYTICAL PROBLEMS

This is the scope of a qualitative analysis is to identify what is present in a sample. Perhaps the most common analytical problem is a
quantitative analysis.
1.4: INTRODUCTION TO ANALYTICAL CHEMISTRY (EXERCISES)

These are homework exercises to accompany "Chapter 1: Introduction to Analytical Chemistry" from Harvey's "Analytical Chemistry
2.0" Textmap.
1.5: INTRODUCTION TO ANALYTICAL CHEMISTRY (SUMMARY)

This is a summary to accompany "Chapter 1: Introduction to Analytical Chemistry" from Harvey's "Analytical Chemistry 2.0"
Textmap.
1 10/11/2020
1.1: What is Analytical Chemistry?
1.1: What is Analytical Chemistry?
David Harvey 9/13/2020 1.1.1 CC-BY-NC-SA https://chem.libretexts.org/@go/page/167726

1.2: The Analytical Perspective
1.2: The Analytical Perspective

1.3: Common Analytical Problems
1.3: Common Analytical Problems

1.4: Introduction to Analytical Chemistry (Exercises)
1.E: Introduction to Analytical Chemistry (Exercises)

1.5: Introduction to Analytical Chemistry (Summary)
1.S: Introduction to Analytical Chemistry (Summary)

CHAPTER OVERVIEW
2: BASIC TOOLS OF ANALYTICAL CHEMISTRY
In the chapters that follow we will explore many aspects of analytical chemistry. In the process we
will consider important questions such as “How do we treat experimental data?”, “How do we
ensure that our results are accurate?”, “How do we obtain a representative sample?”, and “How do
we select an appropriate analytical technique?” Before we look more closely at these and other
questions, we will first review some basic tools of importance to analytical chemists.
2.1: MEASUREMENTS IN ANALYTICAL CHEMISTRY

Analytical chemistry is a quantitative science. Whether determining the concentration of a species,
evaluating an equilibrium constant, measuring a reaction rate, or drawing a correlation between a
compound’s structure and its reactivity, analytical chemists engage in “measuring important
chemical things.” In this section we briefly review the use of units and significant figures in analytical chemistry.
2.2: CONCENTRATION
Concentration is a general measurement unit stating the amount of solute present in a known amount of solution. Although we
associate the terms “solute” and “solution” with liquid samples, we can extend their use to gas-phase and solid-phase samples as well.
Table 2.4 lists the most common units of concentration.
2.3: STOICHIOMETRIC CALCULATIONS

A balanced reaction, which gives the stoichiometric relationship between the moles of reactants and the moles of products, provides
the basis for many analytical calculations.
2.4: BASIC EQUIPMENT

The array of equipment for making analytical measurements is impressive, ranging from the simple and inexpensive, to the complex
and expensive. With three exceptions—measuring mass, measuring volume, and drying materials—we will postpone the discussion of
equipment to later chapters where its application to specific analytical methods is relevant.
2.5: PREPARING SOLUTIONS

Preparing a solution of known concentration is perhaps the most common activity in any analytical lab. The method for measuring out
the solute and solvent depend on the desired concentration unit and how exact the solution’s concentration needs to be known. Pipets
and volumetric flasks are used when a solution’s concentration must be exact; graduated cylinders, beakers and reagent bottles suffice
when concentrations need only be approximate. Two methods for preparing solutions are described.
2.6: SPREADSHEETS AND COMPUTATIONAL SOFTWARE

Analytical chemistry is an inherently quantitative discipline. Whether you are completing a statistical analysis, trying to optimize
experimental conditions, or exploring how a change in pH affects a compound’s solubility, the ability to work with complex
mathematical equations is essential. Spreadsheets, such as Microsoft Excel can be an important tool for analyzing your data and for
preparing graphs of your results. Scattered throughout the text you will find instructions for using spreadsheet
2.7: THE LABORATORY NOTEBOOK

Your laboratory notebook is your most important tool when working in the lab. If kept properly, you should be able to look back at
your laboratory notebook several years from now and reconstruct the experiments on which you worked. Maintaining a laboratory
notebook may seem like a great deal of effort, but if you do it well you will have a permanent record of your work. Scientists working
in academic, industrial and governmental research labs rely on their notebooks to provide a written record.
2.8: BASIC TOOLS OF ANALYTICAL CHEMISTRY (EXERCISES)

These are homework exercises to accompany "Chapter 2: Basic Tools of Analytical Chemistry" from Harvey's "Analytical Chemistry
2.0" Textmap.
2.9: BASIC TOOLS OF ANALYTICAL CHEMISTRY (SUMMARY)

This is a summary to accompany "Chapter 2: Basic Tools of Analytical Chemistry" from Harvey's "Analytical Chemistry 2.0"
Textmap.
1 10/11/2020
2.1: Measurements in Analytical Chemistry
2.1: Measurements in Analytical Chemistry

2.2: Concentration
2.2: Concentration

2.3: Stoichiometric Calculations
2.3: Stoichiometric Calculations

2.4: Basic Equipment
2.4: Basic Equipment

2.5: Preparing Solutions
2.5: Preparing Solutions

2.6: Spreadsheets and Computational Software
2.6: Spreadsheets and Computational Software

2.7: The Laboratory Notebook
2.7: The Laboratory Notebook

2.8: Basic Tools of Analytical Chemistry (Exercises)
2.E: Basic Tools of Analytical Chemistry (Exercises)

2.9: Basic Tools of Analytical Chemistry (Summary)
2.S: Basic Tools of Analytical Chemistry (Summary)

CHAPTER OVERVIEW
3: THE VOCABULARY OF ANALYTICAL CHEMISTRY
If you leaf through an issue of the journal Analytical Chemistry, you will soon discover that the
authors and readers share a common vocabulary of analytical terms. You are probably familiar with
some of these terms, such as accuracy and precision, but other terms, such as analyte and matrix may
be less familiar to you. In order to participate in the community of analytical chemists, you must first
understand its vocabulary.
3.1: ANALYSIS, DETERMINATION, AND MEASUREMENT

The first important distinction we will make is among the terms analysis, determination, and
measurement. An analysis provides chemical or physical information about a sample. The
component of interest in the sample is called the analyte, and the remainder of the sample is the
matrix. In an analysis we determine the identity, concentration, or properties of an analyte. To make this determination we measure
one or more of the analyte’s chemical or physical properties.
3.2: TECHNIQUES, METHODS, PROCEDURES, AND PROTOCOLS

Suppose you are asked to develop an analytical method to determine the concentration of lead in drinking water. How would you
approach this problem? To provide a structure for answering this question let’s draw a distinction among four levels of analytical
methodology: techniques, methods, procedures, and protocols.
3.3: CLASSIFYING ANALYTICAL TECHNIQUES

Analyzing a sample generates a chemical or physical signal that is proportional to the amount of analyte in the sample. This signal
may be anything we can measure, such as mass or absorbance. It is convenient to divide analytical techniques into two general classes
depending on whether the signal is proportional to the mass or moles of analyte, or to the analyte’s concentration.
3.4: SELECTING AN ANALYTICAL METHOD

A method is the application of a technique to a specific analyte in a specific matrix. We can develop an analytical method for
determining the concentration of lead in drinking water using any of the techniques mentioned in the previous section. The
requirements of the analysis determine the best method and consideration is given the following criteria: accuracy, precision,
sensitivity, selectivity, robustness, ruggedness, scale of operation, analysis time, availability of equipment, and cost.
3.5: DEVELOPING THE PROCEDURE

After selecting a method the next step is to develop a procedure that will accomplish the goals of our analysis. In developing the
procedure attention is given to compensating for interferences, to selecting and calibrating equipment, to acquiring a representative
sample, and to validating the method.
3.6: PROTOCOLS
A protocol is a set of stringent written guidelines specifying an exact procedure that must be followed before an agency will accept
the results of an analysis. A protocol contains explicit instructions regarding internal and external quality assurance and quality
control (QA/QC) procedures. The goal of internal QA/QC is to ensure that a laboratory’s work is both accurate and precise. External
QA/QC is a process in which an external agency certifies a laboratory.
3.7: THE IMPORTANCE OF ANALYTICAL METHODOLOGY

The importance of analytical methodology is evident if we examine environmental monitoring programs. The purpose of a monitoring
program is to determine the present status of an environmental system, and to assess long term trends in the system’s health. These are
broad and poorly defined goals. In many cases, an environmental monitoring program begins before the essential questions are
known. This is not surprising since it is difficult to formulate questions in the absence of any results.
3.8: THE VOCABULARY OF ANALYTICAL CHEMISTRY (EXERCISES)

These are homework exercises to accompany "Chapter 3: The Vocabulary of Analytical Chemistry" from Harvey's "Analytical
Chemistry 2.0" Textmap.
3.9: THE VOCABULARY OF ANALYTICAL CHEMISTRY (SUMMARY)

This is a summary to accompany "Chapter 3: The Vocabulary of Analytical Chemistry" from Harvey's "Analytical Chemistry 2.0"
Textmap.
1 10/11/2020
3.1: Analysis, Determination, and Measurement
3.1: Analysis, Determination, and Measurement

3.2: Techniques, Methods, Procedures, and Protocols
3.2: Techniques, Methods, Procedures, and Protocols

3.3: Classifying Analytical Techniques
3.3: Classifying Analytical Techniques

3.4: Selecting an Analytical Method
3.4: Selecting an Analytical Method

3.5: Developing the Procedure
3.5: Developing the Procedure

3.6: Protocols
3.6: Protocols

3.7: The Importance of Analytical Methodology
3.7: The Importance of Analytical Methodology

3.8: The Vocabulary of Analytical Chemistry (Exercises)
3.E: The Vocabulary of Analytical Chemistry (Exercises)

3.9: The Vocabulary of Analytical Chemistry (Summary)
3.S: The Vocabulary of Analytical Chemistry (Summary)

CHAPTER OVERVIEW
4: EVALUATING ANALYTICAL DATA
When using an analytical method we make three separate evaluations of experimental error. First,
before beginning an analysis we evaluate potential sources of errors to ensure that they will not
adversely effect our results. Second, during the analysis we monitor our measurements to ensure that
errors remain acceptable. Finally, at the end of the analysis we evaluate the quality of the
measurements and results, comparing them to our original design criteria.
4.1: CHARACTERIZING MEASUREMENTS AND RESULTS

One way to characterize data from multiple measurements/runs is to assume that the
measurements are randomly scattered around a central value that provides the best estimate of
expected, or “true” value. There are two common ways to estimate central tendency: the mean and
the median.
4.2: CHARACTERIZING EXPERIMENTAL ERRORS

We call errors affecting the accuracy of an analysis determinate. Although there may be several different sources of determinate error,
each source has a specific magnitude and sign. Some sources of determinate error are positive and others are negative, and some are
larger in magnitude and others are smaller. The cumulative effect of these determinate errors is a net positive or negative error in
accuracy.
4.3: PROPAGATION OF UNCERTAINTY

A propagation of uncertainty allows us to estimate the uncertainty in a result from the uncertainties in the measurements used to
calculate the result.
4.4: THE DISTRIBUTION OF MEASUREMENTS AND RESULTS

A population is the set of all objects in the system we are investigating. For our experiment, the population is all United States pennies
in circulation. This population is so large that we cannot analyze every member of the population. Instead, we select and analyze a
limited subset, or sample of the population.
4.5: STATISTICAL ANALYSIS OF DATA

A confidence interval is a useful way to report the result of an analysis because it sets limits on the expected result. In the absence of
determinate error, a confidence interval indicates the range of values in which we expect to find the population’s expected mean.
When we report a 95% confidence interval for the mass of a penny as 3.117 g ± 0.047 g, for example, we are claiming that there is
only a 5% probability that the expected mass of penny is less than 3.070 g or more than 3.164 g.
4.6: STATISTICAL METHODS FOR NORMAL DISTRIBUTIONS

The normal distribution is the most common distribution used for experimental results. Because the area between any two limits of a
normal distribution is well defined, constructing and evaluating significance tests is straightforward.
4.7: DETECTION LIMITS

A method’s detection limit as the smallest concentration or absolute amount of analyte that has a signal significantly larger than the
signal from a suitable blank. Although our interest is in the amount of analyte, in this section we will define the detection limit in
terms of the analyte’s signal.
4.8: USING EXCEL AND R TO ANALYZE DATA

It can be tedious to work problems using nothing more than a calculator. Both Excel and R include functions for descriptive statistics,
for finding probabilities for different distributions, and for carrying out significance tests. In addition, R provides useful functions for
visualizing your data.
4.9: EVALUATING ANALYTICAL DATA (EXERCISES)

These are homework exercises and select solutions to "Chapter 4: Evaluating Analytical Data" from Harvey's "Analytical Chemistry
2.0" Textmap.
4.10: EVALUATING ANALYTICAL DATA (SUMMARY)

This is the summary to "Chapter 4: Evaluating Analytical Data" from Harvey's "Analytical Chemistry 2.0" Textmap.
1 10/11/2020
4.1: Characterizing Measurements and Results
4.1: Characterizing Measurements and Results

4.2: Characterizing Experimental Errors
4.2: Characterizing Experimental Errors

4.3: Propagation of Uncertainty
4.3: Propagation of Uncertainty

4.4: The Distribution of Measurements and Results
4.4: The Distribution of Measurements and Results

4.5: Statistical Analysis of Data
4.5: Statistical Analysis of Data

4.6: Statistical Methods for Normal Distributions
4.6: Statistical Methods for Normal Distributions

4.7: Detection Limits
4.7: Detection Limits

4.8: Using Excel and R to Analyze Data
4.8: Using Excel and R to Analyze Data

4.9: Evaluating Analytical Data (Exercises)
4.E: Evaluating Analytical Data (Exercises)

4.10: Evaluating Analytical Data (Summary)
4.S: Evaluating Analytical Data (Summary)

CHAPTER OVERVIEW
5: STANDARDIZING ANALYTICAL METHODS
Standardization is the process of determining the relationship between the signal and the amount of
analyte in a sample. Previously, we defined this relationship as Stotal=kACA+Sreag where Stotal is
the signal, nA is the moles of analyte, CA is the analyte’s concentration, kA is the method’s
sensitivity for the analyte, and Sreag is the contribution to Stotal from sources other than the sample.
To standardize a method we must determine values for kA and Sreag, which is the subject of this
chapt
5.1: ANALYTICAL STANDARDS

To standardize an analytical method we use standards containing known amounts of analyte. The
accuracy of a standardization, therefore, depends on the quality of the reagents and glassware used
to prepare these standards. We divide analytical standards into two categories: primary standards and secondary standards.
5.2: CALIBRATING THE SIGNAL

The accuracy of our determination of k and S
A reag depends on how accurately we can measure the signal, S . We measure signals
total
using equipment, such as glassware and balances, and instrumentation, such as spectrophotometers and pH meters. To minimize
determinate errors affecting the signal, we first calibrate our equipment and instrumentation.
5.3: DETERMINING THE SENSITIVITY

To standardize an analytical method we also must determine the value of k . In principle, it should be possible to derive the value of
A
kA for any analytical method by considering the chemical and physical processes generating the signal. Unfortunately, such
calculations are not feasible when we lack a sufficiently developed theoretical model of the physical processes, or are not useful
because of nonideal chemical behavior.
5.4: LINEAR REGRESSION AND CALIBRATION CURVES

In a single-point external standardization we determine the value of k by measuring the signal for a single standard containing a
A
known concentration of analyte. Using this value of k and the signal for our sample, we then calculate the concentration of analyte
A
in our sample. With only a single determination of k , a quantitative analysis using a single-point external standardization is
A
straightforward.
5.5: BLANK CORRECTIONS

Thus far in our discussion of strategies for standardizing analytical methods, we have assumed the use of a suitable reagent blank to
correct for signals arising from sources other than the analyte. We did not, however, ask an important question—“What constitutes an
appropriate reagent blank?” Surprisingly, the answer is not immediately obvious.
5.6: USING EXCEL AND R FOR A REGRESSION ANALYSIS

Although the calculations in this chapter are relatively straightforward—consisting, as they do, mostly of summations—it can be quite
tedious to work through problems using nothing more than a calculator. Both Excel and R include functions for completing a linear
regression analysis and for visually evaluating the resulting model.
5.7: STANDARDIZING ANALYTICAL METHODS (EXERCISES)

This is a summary to accompany "Chapter 5: Standardizing Analytical Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
5.8: STANDARDIZING ANALYTICAL METHODS (SUMMARY)

This is a summary to accompany "Chapter 5: Standardizing Analytical Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
1 10/11/2020
5.1: Analytical Standards
5.1: Analytical Standards

5.2: Calibrating the Signal
5.2: Calibrating the Signal

5.3: Determining the Sensitivity
5.3: Determining the Sensitivity

5.4: Linear Regression and Calibration Curves
5.4: Linear Regression and Calibration Curves

5.5: Blank Corrections
5.5: Blank Corrections

5.6: Using Excel and R for a Regression Analysis
5.6: Using Excel and R for a Regression Analysis

5.7: Standardizing Analytical Methods (Exercises)
5.E: Standardizing Analytical Methods (Exercises)

5.8: Standardizing Analytical Methods (Summary)
5.S: Standardizing Analytical Methods (Summary)

CHAPTER OVERVIEW
6: EQUILIBRIUM CHEMISTRY
Regardless of the problem on which an analytical chemist is working, its solution requires a
knowledge of chemistry and the ability to apply that knowledge. For example, an analytical chemist
studying the effect of pollution on spruce trees needs to know the chemical differences between
p‑hydroxybenzoic acid and p‑hydroxyacetophenone, two phenols found in the needles of spruce
trees. Your ability to “think as a chemist” is a product of your experience in the classroom and in the
laboratory.
6.1: REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIA

Although a system at equilibrium appears static on a macroscopic level, it is important to
remember that the forward and reverse reactions continue to occur. A reaction at equilibrium exists
in a steady-state, in which the rate at which a species forms equals the rate at which it is consumed. Hence, there is no further change
in the amounts of these species.
6.2: THERMODYNAMICS AND EQUILIBRIUM CHEMISTRY

Thermodynamics is the study of thermal, electrical, chemical, and mechanical forms of energy. The study of thermodynamics crosses
many disciplines, including physics, engineering, and chemistry. Of the various branches of thermodynamics, the most important to
chemistry is the study of the change in energy during a chemical reaction.
6.3: MANIPULATING EQUILIBRIUM CONSTANTS

We will take advantage of two useful relationships when working with equilibrium constants. First, if we reverse a reaction’s
direction, the equilibrium constant for the new reaction is simply the inverse of that for the original reaction. Second, if we add
together two reactions to obtain a new reaction, the equilibrium constant for the new reaction is the product of the equilibrium
constants for the original reactions.
6.4: EQUILIBRIUM CONSTANTS FOR CHEMICAL REACTIONS

Several types of chemical reactions are important in analytical chemistry, either in preparing a sample for analysis or during the
analysis. The most significant of these are: precipitation reactions, acid–base reactions, complexation reactions, and oxidation–
reduction (redox) reactions. In this section we review these reactions and their equilibrium constant expressions.
6.5: LE CHÂTELIER’S PRINCIPLE

The observation that a system at equilibrium responds to an external stress by reequilibrating in a manner that diminishes the stress, is
formalized as Le Châtelier’s principle. One of the most common stresses to a system at equilibrium is to change the concentration of a
reactant or product.
6.6: LADDER DIAGRAMS

In this section we introduce the ladder diagram as a simple graphical tool for evaluating the equilibrium chemistry. Using ladder
diagrams we will be able to determine what reactions occur when combining several reagents, estimate the approximate composition
of a system at equilibrium, and evaluate how a change to solution conditions might affect an analytical method.
6.7: SOLVING EQUILIBRIUM PROBLEMS

Ladder diagrams are a useful tool for evaluating chemical reactivity, usually providing a reasonable approximation of a chemical
system’s composition at equilibrium. If we need a more exact quantitative description of the equilibrium condition, then a ladder
diagram is insufficient. In this case we need to find an algebraic solution. In this section we will learn how to set-up and solve
equilibrium problems. We will start with a simple problem and work toward more complex problems.
6.8: BUFFER SOLUTIONS

As outlined below, the Henderson–Hasselbalch approximation provides a simple way to calculate the pH of a buffer, and to determine
the change in pH upon adding a strong acid or strong base.
6.9: ACTIVITY EFFECTS

The activity coefficient for a species corrects for any deviation between its physical and ideal concentration. For a gas, a pure solid, a
pure liquid, or a non-ionic solute, the activity coefficient is approximately one under reasonable experimental conditions. For
reactions involving only these species, the difference between activity and concentration is negligible. The activity coefficient for an
ion, however, depends on the solution’s ionic strength, the ion’s charge, and the ion’s size.
1 10/11/2020
6.10: USING EXCEL AND R TO SOLVE EQUILIBRIUM PROBLEMS
In solving equilibrium problems we typically make one or more assumptions to simplify the algebra. These assumptions are important
because they allow us to reduce the problem to an equation in x that we can solve by simply taking a square-root, a cube-root, or by
using the quadratic equation. Without these assumptions, most equilibrium problems result in a cubic equation (or a higher-order
equation) that is harder to solve. Both Excel and R are useful tools for solving such equations.
6.11: SOME FINAL THOUGHTS ON EQUILIBRIUM CALCULATIONS

Several tools for evaluating the composition of a system at equilibrium were discussed; they differ in both accuracy and ease in
answering questions involving equilibrium chemistry. If you need to know whether a reaction if favorable, or to estimate the pH of a
solution, then a ladder diagram will meet your needs. On the other hand, if you require a more accurate estimate of a compound’s
solubility, then a rigorous calculation that includes activity coefficients is necessary.
6.12: EQUILIBRIUM CHEMISTRY (EXERCISES)

These are homework exercises to accompany "Chapter 6: Equilibrium Chemistry" from Harvey's "Analytical Chemistry 2.0"
Textmap.
6.13: EQUILIBRIUM CHEMISTRY (SUMMARY)

This is a summary to accompany "Chapter 6: Equilibrium Chemistry" from Harvey's "Analytical Chemistry 2.0" Textmap.
2 10/11/2020
6.1: Reversible Reactions and Chemical Equilibria
6.01: Reversible Reactions and Chemical Equilibria

6.2: Thermodynamics and Equilibrium Chemistry
6.02: Thermodynamics and Equilibrium Chemistry

6.3: Manipulating Equilibrium Constants
6.03: Manipulating Equilibrium Constants

6.4: Equilibrium Constants for Chemical Reactions
6.04: Equilibrium Constants for Chemical Reactions

6.5: Le Châtelier’s Principle
6.05: Le Châtelier’s Principle

6.6: Ladder Diagrams
6.06: Ladder Diagrams

6.7: Solving Equilibrium Problems
6.07: Solving Equilibrium Problems

6.8: Buffer Solutions
6.08: Buffer Solutions

6.9: Activity Effects
6.09: Activity Effects

6.10: Using Excel and R to Solve Equilibrium Problems
6.10: Using Excel and R to Solve Equilibrium Problems

6.11: Some Final Thoughts on Equilibrium Calculations
6.11: Some Final Thoughts on Equilibrium Calculations

6.12: Equilibrium Chemistry (Exercises)
6.E: Equilibrium Chemistry (Exercises)

6.13: Equilibrium Chemistry (Summary)
6.S: Equilibrium Chemistry (Summary)

CHAPTER OVERVIEW
7: GRAVIMETRIC METHODS
Gravimetry includes all analytical methods in which the analytical signal is a measurement of mass
or a change in mass. When you step on a scale after exercising you are making, in a sense, a
gravimetric determination of your mass. Mass is the most fundamental of all analytical
measurements, and gravimetry is unquestionably our oldest quantitative analytical technique.
7.1: OVERVIEW OF GRAVIMETRIC METHODS

Before we consider specific gravimetric methods, let’s take a moment to develop a broad survey of
gravimetry. Later, as you read through the descriptions of specific gravimetric methods, this survey
will help you focus on their similarities instead of their differences. You will find that it is easier to
understand a new analytical method when you can see its relationship to other similar methods.
7.2: PRECIPITATION GRAVIMETRY

In precipitation gravimetry an insoluble compound forms when we add a precipitating reagent, or precipitant, to a solution containing
our analyte. In most methods the precipitate is the product of a simple metathesis reaction between the analyte and the precipitant;
however, any reaction generating a precipitate can potentially serve as a gravimetric method.
7.3: VOLATILIZATION GRAVIMETRY

A second approach to gravimetry is to thermally or chemically decompose the sample and measure the resulting change in its mass.
Alternatively, we can trap and weigh a volatile decomposition product. Because the release of a volatile species is an essential part of
these methods, we classify them collectively as volatilization gravimetric methods of analysis.
7.4: PARTICULATE GRAVIMETRY

Precipitation and volatilization gravimetric methods require that the analyte, or some other species in the sample, participate in a
chemical reaction. In a direct precipitation gravimetric analysis, for example, we convert a soluble analyte into an insoluble form that
precipitates from solution. In some situations, however, the analyte is already present as in a particulate form that is easy to separate
from its liquid, gas, or solid matrix.
7.5: GRAVIMETRIC METHODS (EXERCISES)

These are homework exercises to accompany "Chapter 8: Gravimetric Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
7.6: GRAVIMETRIC METHODS (SUMMARY)

This is a summary to accompany "Chapter 8: Gravimetric Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
1 10/11/2020
7.1: Overview of Gravimetric Methods
8.1: Overview of Gravimetric Methods

7.2: Precipitation Gravimetry
8.2: Precipitation Gravimetry

7.3: Volatilization Gravimetry
8.3: Volatilization Gravimetry

7.4: Particulate Gravimetry
8.4: Particulate Gravimetry

7.5: Gravimetric Methods (Exercises)
8.E: Gravimetric Methods (Exercises)

7.6: Gravimetric Methods (Summary)
8.S: Gravimetric Methods (Summary)

CHAPTER OVERVIEW
8: TITRIMETRIC METHODS
Titrimetry, in which volume serves as the analytical signal, made its first appearance as an analytical
method in the early eighteenth century. Titrimetric methods were not well received by the analytical
chemists of that era because they could not duplicate the accuracy and precision of a gravimetric
analysis. Not surprisingly, few standard texts from the 1700s and 1800s include titrimetric methods
of analysis.
8.1: OVERVIEW OF TITRIMETRY

In titrimetry we add a reagent, called the titrant, to a solution containing another reagent, called the
titrand, and allow them to react. The type of reaction provides us with a simple way to divide
titrimetry into the following four categories: (1) acid–base titrations, (2) complexometric titrations,
(3) redox titrations, and (4) precipitation titrations.
8.2: ACID–BASE TITRATIONS

Acid–base titrations, in which an acidic or basic titrant reacts with a titrand that is a base or an acid, is probably the most common
titration used by students in laboratories. To understand the relationship between an acid–base titration’s end point and its equivalence
point we must know how the pH changes during a titration. We will learn how to calculate a titration curve using the equilibrium
calculations from Chapter 6.
8.3: COMPLEXATION TITRATIONS

Complexometric titrations are based on metal–ligand complexation. Practical analytical applications of complexation titrimetry were
slow to develop because many metals and ligands form a series of metal–ligand complexes.
8.4: REDOX TITRATIONS

Redox titration are here the titrant is an oxidizing or reducing agent. In contrast to acid/base titrations, it is convenient for redox
titrations to monitor the titration reaction’s potential instead of the concentration of one species.
8.5: PRECIPITATION TITRATIONS

A reaction in which the analyte and titrant form an insoluble precipitate also can serve as the basis for a titration. We call this type of
titration a precipitation titration.
8.6: TITRIMETRIC METHODS (EXERCISES)

These are homework exercises to accompany "Chapter 9: Titrimetric Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
8.7: TITRIMETRIC METHODS (SUMMARY)

This is a summary to accompany "Chapter 9: Titrimetric Methods" from Harvey's "Analytical Chemistry 2.0" Textmap.
1 10/11/2020
8.1: Overview of Titrimetry
9.1: Overview of Titrimetry

8.2: Acid–Base Titrations
9.2: Acid–Base Titrations

8.3: Complexation Titrations
9.3: Complexation Titrations

8.4: Redox Titrations

8.5: Precipitation Titrations
9.5: Precipitation Titrations

8.6: Titrimetric Methods (Exercises)
9.E: Titrimetric Methods (Exercises)

8.7: Titrimetric Methods (Summary)
9.S: Titrimetric Methods (Summary)

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ANALYTICAL I

This text was compiled on 10/11/2020

1: INTRODUCTION TO ANALYTICAL CHEMISTRY

2: BASIC TOOLS OF ANALYTICAL CHEMISTRY

2.1: MEASUREMENTS IN ANALYTICAL CHEMISTRY

3: THE VOCABULARY OF ANALYTICAL CHEMISTRY

3.1: ANALYSIS, DETERMINATION, AND MEASUREMENT

4: EVALUATING ANALYTICAL DATA

4.1: CHARACTERIZING MEASUREMENTS AND RESULTS

5: STANDARDIZING ANALYTICAL METHODS

5.1: ANALYTICAL STANDARDS

6.1: REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIA

7.1: OVERVIEW OF GRAVIMETRIC METHODS

8.1: OVERVIEW OF TITRIMETRY

1.1: WHAT IS ANALYTICAL CHEMISTRY?

1.2: THE ANALYTICAL PERSPECTIVE

1.3: COMMON ANALYTICAL PROBLEMS

1.4: INTRODUCTION TO ANALYTICAL CHEMISTRY (EXERCISES)

1.5: INTRODUCTION TO ANALYTICAL CHEMISTRY (SUMMARY)

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2.1: MEASUREMENTS IN ANALYTICAL CHEMISTRY

2.3: STOICHIOMETRIC CALCULATIONS

2.4: BASIC EQUIPMENT

2.5: PREPARING SOLUTIONS

2.6: SPREADSHEETS AND COMPUTATIONAL SOFTWARE

2.7: THE LABORATORY NOTEBOOK

2.8: BASIC TOOLS OF ANALYTICAL CHEMISTRY (EXERCISES)

2.9: BASIC TOOLS OF ANALYTICAL CHEMISTRY (SUMMARY)

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3.1: ANALYSIS, DETERMINATION, AND MEASUREMENT

3.2: TECHNIQUES, METHODS, PROCEDURES, AND PROTOCOLS

3.3: CLASSIFYING ANALYTICAL TECHNIQUES

3.4: SELECTING AN ANALYTICAL METHOD

3.5: DEVELOPING THE PROCEDURE

3.7: THE IMPORTANCE OF ANALYTICAL METHODOLOGY

3.8: THE VOCABULARY OF ANALYTICAL CHEMISTRY (EXERCISES)

3.9: THE VOCABULARY OF ANALYTICAL CHEMISTRY (SUMMARY)

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4.1: CHARACTERIZING MEASUREMENTS AND RESULTS