Course Overview

Course : Maj Sci 303

Number
Course Code
Descriptive Analytical Chemistry
Title
Credit Units 3
School/Term First Sem./ AY: 202-2021
Mode of Deliver Online/ Offline Learning
Name of Instructor MARILOU B. SIEGA
The course involves a study of the principles and theories important to the
practice of analytical chemistry. It involves a discussion of the techniques,
methods and instrumentation involved in determining the amount of
Course Description constituents in samples. Particular attention is given to stoichiometric
problems.

It is expected that at the end of the course, the students must have:

1. Explained and discussed the fundamental principles relating to

Course Outcomes analytical techniques: the analytical process, chemical reactions
used in quantitative analysis, stoichiometry, gravimetric and
volumetric analysis, titrations, and instrumental methods through
desired learning opportunities in various media;
2. Applied and demonstrated the principles and theories of analytical
chemistry through various learning opportunities (such as problem
solving, laboratory exercises and others) in order to boost their
higher thinking skills;
3. Developed the scientific attitude such as critical and analytical
thinking, curiosity, objectiveness, open-minded and others; and
4. Relate the scientific concepts to real life situations.

SLSU Vision A high quality corporate University of Science, Technology and Innovation.

SLSU will develop science, technology and innovation leaders and

SLSU professionals; produce high-impact technologies from research and
Mission innovations; contribute to sustainable development through responsive
community engagement programs; and generate revenues to be self-
sufficient and financially viable.
Learning Plan

Module 1
The Nature of Analytical Chemistry

Lesson 1
What is Analytical Chemistry?

Learning Outcomes
At the end of the lesson, you must be able to:
1. Describe what analytical chemistry is.
2. Distinguish between analytical chemistry and chemical analysis.
3. Verify the implication of a given article in everyday life.

Introduction

Analytical Chemistry
Have you ever noticed that milk will say ''vitamin D added''? Or looked at a cereal box with so many
vitamins and minerals listed and wondered where they all came from? The ingredient declaration
simply says, vitamin E or zinc. How are they getting this vitamin E to add into the cereal? Where
does the vitamin D in milk come from? Some of these compounds are created in the laboratory
using other chemicals. Other times, chemists isolate these vitamins and minerals from other food
until they only have the vitamin or mineral that they need.
Analytical chemistry is the process of isolating specific compounds, identifying those compounds,
and determining how much of the compounds are in a product. Analytical chemistry is used in
many different areas of science. It can be used to determine how much cholesterol is in your blood,
to identify an unknown compound found at a crime scene, or to purify the oil you put into your car.

History of Analytical Chemistry

Analytical chemistry has been important since the early days of chemistry, providing methods for
determining which elements and chemicals are present in the object in question. Chemists such as
Justus von Liebig, Robert Bunsen, and Gustav Kirchoff developed methods to identify and isolate
specific compounds.it includes the development of systematic elemental analysis, and systematized
organic analysis based on the specific reactions of functional groups.
Justus von Liebig developed a system to identify elements. He also determined that specific
functional groups, such as aldehydes, tend to react in similar ways. Robert Bunsen and Gustav
Kirchoff worked together to develop the first instrument that could analyze compounds and
determine the elements in that compound. This instrument was a flame spectrometer. The flame
spectrometer was the precursor to our modern-day spectrometers that are used to analyze
compounds.
Today methods such as mass spectrometry, NMR-chromatography, and high-performance liquid
chromatography (HPLC) are used in analytical chemistry.

What Do Analytical Chemists Do?

Analytical chemistry is used in many different fields. Much of this work is done using complex
instruments. Analytical chemists need to know how to operate these instruments and how to
understand the output.
For example, let's look at NMR-chromatography. In order to use this method, the analytical chemist
needs to know how to prepare the compound. They need to know if it will it be mixed with anything
first to isolate elements, or how much should be put into the machine, or what settings are needed.
Then once the NMR prints out the following information an analytical chemist needs to know how
to understand it:

Ethanol NMR

To you this might just look like a bunch of lines, but an analytical chemist would know that this is
ethanol.
Today everyone has to know what’s in the food? What’s in the water? What’s in the air? This is truly
the golden age of analytical chemistry.

Let’s Begin! (Activity)

1. From the various definitions of analytical chemistry, what common points of view about it?
Definition/Author Common Points of View

2. Read the article “Analytical chemistry for a sustainable society – trends and implications” by
Bergquist, J. and Turner, C. (2018) then answer the questions that follow.
 a. What is the role of analytical chemistry in our society. Illustrate an example.
b. How it is important and relevant to you?

Discussion

What is other appropriate description of analytical chemistry?

• “Analytical chemistry is a measurement science consisting of a set of powerful ideas and methods
that are useful in all fields of science and medicine.”

Some exciting illustrations of the power and significance of analytical chemistry have occurred, are
occurring, and will occur during NASA’s rover explorations of the planet Mars.

•On July 4, 1997, the Pathfinder spacecraft delivered the Sojourner rover to the Martian surface.
• Analytical instruments returned information on the chemical composition of rocks and soil.
•Investigations by the lander and rover suggested that Mars was at one time in its past warm and
wet with liquid water on the surface and water vapor in the atmosphere.

In January 2004, the Mars rovers Spirit and Opportunity arrived on Mars for a 3 month mission.
• A major result from Spirit’s alpha particle X-ray spectrometer (APXS) and Mossbauer
spectrometer was finding concentrated deposits of silica and, at a different site, high concentrations
of carbonate.
• Spirit continued to explore and transmit data until 2010, outliving even the most optimistic
predictions.
• Even more amazing, Opportunity continues to travel the surface of Mars and, by March, 2012, had
covered more than 21 miles exploring and transmitting images of craters, small hills, and other
features.

• In late 2011, the Mars Science Laboratory aboard the rover Curiosity. It arrived on August 6, 2012
with a host of analytical instruments on board.
• The Chemistry and Camera package (CHEMCAM) (LIBS) + remote micro imager. The LIBS
instrument will provide determination of many elements with no sample preparation. It can
determine the identity and amounts of major, minor, and trace elements and can detect hydrated
minerals. The sample analysis package contains a quadruple mass spectrometer, a gas
chromatograph, and a tunable laser spectrometer. Its goals are to survey carbon compound
sources, search for organic compounds important to life, reveal the chemical and isotopic states of
several elements, determine the composition of the Martian atmosphere, and search for noble gas
and light element isotopes.

• These examples demonstrate that both qualitative and quantitative information are required in
an analysis. –
1. Qualitative Analysis – reveals chemical identity of elements and compounds in a sample. –
2. Quantitative Analysis – determines the relative amounts of each substance in a sample. –
3. Analytes – components of a sample that are to be determined.

The Role of Analytical Chemistry

•Analytical chemists use science and technology to solve practical problems.

•Analytical chemistry is applied in all areas of science, industry, and medicine.
–The concentrations of O2 and of CO2 in blood samples.
– Quantities of hydrocarbons, nitrogen oxides, and carbon monoxide in automobile exhaust gases
for emission-control devices.
–Quantitative measurements of ionized calcium in blood serum help diagnose parathyroid disease
in humans.
– Quantitative determination of nitrogen in foods: protein content and thus their nutritional value.
– Analysis of steel during its production for carbon, nickel, and chromium to achieve a desired
strength, hardness, corrosion resistance, and ductility.
– The mercaptan content of household gas supplies to warn of dangerous leaks.
– Farmers tailor fertilization and irrigation schedules to meet changing plant needs during the
growing

Chemistry: The Central Science; all sub-disciplines rely on analytical chemistry to function.

The interdisciplinary nature of chemical analysis makes it a vital tool in medical, industrial,
government, and academic laboratories throughout the world.

Application/Assessment
1. What is your conceptual understanding of analytical chemistry?
2. Verify the statement “Analytical chemistry is what analytical chemists do.”
3. How does analytical chemistry apply to everyday life.

Summary
Analytical chemists work to improve the ability of all chemists to make meaningful measurements.
Chemist working in medical chemistry, clinical chemistry, forensic chemistry, and environmental
chemistry, as well as the more traditional areas of chemistry, need better tools for analysing
materials. The need to work with smaller quantities of material, with more complex materials, with
processes occurring on shorter time scales, and with species present at lower concentrations
challenges analytical chemists to improve existing analytical methods and to develop new analytical
techniques.

Key Terms/Concept

Analytical chemistry
Chemical analysis
Qualitative analysis
Quantitative analysis
Analytical chemists

References
1. Harvey, D. Modern Analytical Chemistry. (2016). University of Minnessota.Mc Graw Hill.
2. Skoog, D. A., et.al.(2014). Fundamentals of Analytical Chemistry. 9 th ed. Thomson
Brooks/Cole.
3. Skoog, D. A., et.al.( 2006). Analytical Chemistry – An Introduction. 8 th ed. Saunders College
Publishing.
4. Harvey, D. (2016). What is Analytical Chemistry?-Definition and Impact. Retrieved on
August 20, 2017 from https://study.com/academy/lesson/what-is-analytical-chemistry-
definition-impact.html.

Lesson 2
The Analytical Perspective

Learning Outcomes
At the end of the lesson, you must be able to;
1. Apply the model of the analytical approach to a real problem.

Introduction
Perspective is like standing aside and watching what is happening, or being asked of somebody
else. It is much easier to think about, and have a clearer answer to the questions asked of that
person because it is not you on the spot.

Activity
Read the article “When Machine Tastes Coffee: Instrumental Approach to Predict the Sensory
Profile of Espresso Coffee,” by several scientists working at the Nestle Research Center in Lausanne,
Switzerland.
You will find the article on pages 1574-1581 in Volume 0 of analytical Chemistry, published in
2008.
Guide questions:
1. What is the analytical problem and why is it important?
2. What criteria did the authors consider in designing their experiments?
3. What is the basic experimental procedure?
4. What interferences were considered and how did they overcome them?
5. How did the authors calibrate the assay?
6. How did the authors validate their experimental method?
7. Is there any evidence of repeating the steps of the analytical approach?

Discussion

Having noted that each field of chemistry brings a unique perspective to the study of chemistry, we
now ask a second deceptively simple question. What is 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 purposes to treat it as a five-step process:
1. Identify and define the problem
2. Design the experimental procedure.
3. Conduct an experiment, and gather data.
4. Analyse the experimental data.
5. Propose a solution to the problem.
Three general features of this approach deserve attention. First, steps 1 and 5 provide
opportunities for analytical chemist to collaborate with individuals outside the realm of analytical
chemistry. In fact, many problems on which analytical chemists work originate in other fields.
Second, the analytical approach is not linear, but incorporates a “feedback loop” consisting of steps
2, 3, and 4, in which the outcome of one step may cause a reevaluation of the other two steps.
Finally, the solution to one problem often suggests a new problem.
Analytical chemistry begins with a problem, an example of this is the evaluation of the amount of
dust and soil ingested by children as an indicator of environmental exposure to particulate based
pollutants. At this point the analytical approach involves collaboration between the analytical
chemist and the individuals responsible for the problem. Together they decide what information is
needed. It is also necessary for the analytical chemist to understand how the problem relates to
broader research goals. The type of information needed and the problem’s context are essential to
designing an appropriate experimental procedure.
To design an experimental procedure involves selecting an appropriate method of analysis based
on established criteria, such as accuracy, precision, sensitivity, and detection limit; the urgency with
which results are needed; the cost of a single analysis; the number of samples to be analysed; and
the amount of sample available for analysis. Finding an appropriate balance these parameters is
frequently complicated by their interdependence. For example, improving the precision of an
analysis may require a larger sample. Consideration is also given to collecting, storing, and
preparing samples, and together chemical or physical interferences will affect the analysis. Finally,
a good experimental procedure may still yield useless information if there is no method for
validating the results.
The figure below shows an outline of the analytical approach along with some important
considerations at each step.

Application/Assessment

Read the article “Tracing Aerosol Pollutants with Rare Earth Isotopes” by Ondov, J.M.; Kelly.
W.R..Anal Chem, 1991, 63, 691A-697a. Adapt the model of the analytical approach by locating the
discussions pertaining to each of the five steps. Answer the following questions that follow.
1. What is the analytical problem?
2. What type of information is needed to solve the problem?
3. How will the solution to this problem be used?
4. What criteria were considered in designing the experimental procedure?
5. Were there any potential interferences that had to be eliminated? If so, how were they
treated?
6. Is there a plan for validating the experimental method?
7. How were the samples collected?
8. Is there evidence that steps 2, 3, and 4 of the analytical approached are repeated more than
once?
 9. Was there a successful conclusion to the problem?

Assignment

Read a recent article from the column “Analytical Approach” published in Analytical Chemistry, and
write an essay summarizing the nature of the problem and how it was solved. As a guide, refer to
the model of the analytical approach.

Key Terms/Concept

Analytical perspective
Analytical approach

References
5. Harvey, D. Modern Analytical Chemistry. (2016). University of Minnessota.Mc Graw Hill.
6. Skoog, D. A., et.al.(2014). Fundamentals of Analytical Chemistry. 9 th ed. Thomson
Brooks/Cole.
7. Skoog, D. A., et.al.( 2006). Analytical Chemistry – An Introduction. 8 th ed. Saunders College
Publishing.
8. Harvey, D. (2016). What is Analytical Chemistry?-Definition and Impact. Retrieved on
August 20, 2017 from https://study.com/academy/lesson/what-is-analytical-chemistry-
definition-impact.html.

Lesson 3
A Typical Quantitative Analysis

Learning Outcomes
At the end of the lesson, you must be able to:
1. Identify the method of analysis in solving analytical problems.
2. Illustrate the use of the sequence of steps of a typical quantitative analysis in solving an
important and practical analytical problem.

Introduction
A typical quantitative analysis includes the sequence of steps shown in the diagram. In some
instances, one or more of these steps can be omitted. For example, if the sample is already a liquid,
we can avoid the dissolution step.
To compute the results of a typical quantitative analysis from two measurements. One is the mass
or the volume of sample being analysed. The second measurements of some quantity that is
proportional to the amount of analyte in the sample such as mass, volume, intensity of light, or
electrical charge.

A brief overview of each of the nine steps are presented in the discussion. To illustrate the use of
these steps a case study is presented in solving an important and practical analytical problem.

Let’s Begin! (Activity)

For each of the following problems indicate whether its solution requires a qualitative or
quantitative study. More than one type of analysis may be appropriate for some problems.
1. The residents in a neighbourhood near a hazardous-waste disposal site are concerned that
it is leaking contaminants into their groundwater.
2. An art museum is concerned that a recently acquired oil painting is a forgery.
3. Airport security needs a more reliable method for detecting the presence of explosive
materials in luggage.
4. A new law requires a method for evaluating whether automobiles are emitting too much
carbon monoxide.
5. The structure of a newly discovered virus (covid-19) needs to be determined.

Discussion

A Typical Quantitative Analysis

A typical quantitative analysis includes the sequence of steps. In some instances, one or more of
these steps can be omitted. For example, if the sample is already a liquid, we can avoid the
dissolution step.

In the paragraphs that follow, you will find a brief overview of each of the steps.

1. Choosing a Method: The choice is sometimes difficult and requires experience as well as
intuition. - level of accuracy :investment on time and money - Number of samples analyzed
and number of components in the sample
2. Acquiring the Sample: - an analysis must be performed on a sample that has the same
composition as the bulk of material from which it was taken. When the bulk is large and
heterogeneous, great effort is required to get a representative sample. - The collection of
specimens from biological sources represents a second type of sampling problem.
3. Processing the Sample:
- Preparing a Laboratory Sample: grounding, mixing, storing
- Defining Replicate Samples: Replicate samples, or replicates, are portions of a material of
approximately the same size that are carried through an analytical procedure at the same time and
in the same way.
Preparing Solutions: Physical and Chemical Changes
-Converting the sample into a soluble form:acid-base addition, ignition, high temperature
fusion.
- Converting the sample into a form suitable for the measurement step. For example, Mn to
MnO4- - colored solution
 4. Eliminating Interferences: An interference or interferent is a species that causes an error in
an analysis by enhancing or attenuating (making smaller) the quantity being measured. The
matrix, or sample matrix, is the collection of all of the components in the sample containing an
analyte.

5.Calibrating and Measuring Concentration: Ideally, the measurement of the property is directly
proportional to the concentration, that is, cA= kX where k is a proportionality constant. The
process of determining k is called a calibration.
6. Calculating Results

7. Evaluating Results by Estimating Reliability

Sample Problem:

Deer Kill: A Case Study Illustrating the Use of Analytical Chemistry to Solve a Problem in Toxicology

•to find the cause of death so that further deer kills might be prevented, they searched 2 acres of
area. • The investigators noticed that grass surrounding nearby power line poles was wilted and
discolored.

They speculated that a herbicide might have been used on the grass. A common ingredient in
herbicides is arsenic in any one of a variety of forms, including arsenic trioxide, sodium arsenite,
monosodium methanearsenate, and disodium methanearsenate.

The Problem : A dead whitetail deer near a pond in the Land between the Lakes National
Recreational area in Kentucky.

Selecting a Method
A scheme for the quantitative determination of arsenic in biological samples is found in the
published methods of the Association of Official Analytical Chemists (AOAC). In this method, arsenic
is distilled as arsine, AsH3 , and is then determined by colorimetric measurements.
Processing the Sample:
Obtaining Representative Samples Back at the laboratory, the deer were dissected, and the kidneys
were removed for analysis. The kidneys were chosen because the suspected pathogen (arsenic) is
rapidly eliminated from an animal through its urinary tract.
Processing the Sample:
Preparing a Laboratory Sample Each kidney was cut into pieces and homogenized in a high speed
blender. This step served to reduce the size of the pieces of tissue and to homogenize the sample.

Processing the Sample:

Defining Replicate Samples Three 10-g samples of the homogenized tissue from each deer were
placed in porcelain crucibles. These served as replicates for the analysis.

Doing Chemistry:
Dissolving the Samples - to convert organic matrix to carbon dioxide and water: dry ashing. - This
process involved heating each crucible and sample cautiously over an open flame until the sample
stopped smoking. The crucible was then placed in a furnace and heated at 555°C for two hours. Dry
ashing served to free the analyte from organic material and convert it to arsenic pentoxide. The dry
solid in each sample crucible was then dissolved in dilute HCl, which converted the As2O5 to
soluble H3AsO4 .

Eliminating Interferences -Arsenic can be separated from other substances that might interfere in
the analysis by converting it to arsine, AsH3 , a toxic, colorless gas that is evolved when a solution of
H3AsO3 is treated with zinc. The solutions resulting from the deer and grass samples were
combined with Sn2+, and a small amount of iodide ion was added to catalyze the reduction of
H3AsO4 to H3AsO3 . - The H3AsO3 was then converted to AsH3 by the addition of zinc metal as
follows: H3AsO3+ 3Zn + 6HCl AsH3 (g) + 3ZnCl2 + 3H2O
- The entire reaction was carried out in flasks equipped with a stopper and delivery tube so that
the arsine could be collected in the absorber solution as shown in Figure 1F-1. The arrangement
ensured that interferences were left in the reaction flask and that only arsine was collected in the
absorber in special transparent containers called cuvettes. Arsine bubbled into the solution in the
cuvette reacts with silver diethyldithiocarbamate to form a colored complex compound according
to the equation.

Measuring the Amount of the Analyte

The amount of arsenic in each sample was determined by measuring the intensity of the red color
formed in the cuvettes with an instrument called a spectrophotometer. A spectrophotometer
provides a number called absorbance that is directly proportional to the color intensity, which is
also proportional to the concentration of the species responsible for the color.

To use absorbance for analytical purposes, a calibration curve must be generated by measuring the
absorbance of several solutions that contain known concentrations of analyte.
The upper part of Figure 1F-2 shows that the color becomes more intense as the arsenic content of
the standards increases from 0 to 25 parts per million (ppm).
Figure 1F-2 Constructing and using a calibration curve to determine the concentration of arsenic.
The absorbance values are plotted against the concentrations of the solutions in the cuvettes.
Finally, the concentrations of the unknown solutions are read from the plot, as shown by the dark
arrows.

Conclusion: Arsenic in kidney tissue of an animal is toxic at levels above about 10 ppm, so it was
probable that the deer were killed by ingesting an As compound. The tests also showed that the
samples of grass contained about 600 ppm arsenic.
Note: As much as possible kindly view this powerpoint presentation on the internet using the link
below:
http://web.iyte.edu.tr/~serifeyalcin/lectures/chem201/cn_1.pdf

Application

Read an article: Nuclear Waste Disposal Case Study

Analytical Chemistry Issues:
Guide questions:
1. What do we need to know?
2. What species to be measured?
3. What precision is required?
4. What does the Analytical Chemist need to know to solve these problems?
5. What measurement technique used?
6. What are the sources of error?

Assessment

Find an analytical problem then use the sequence of steps of a typical quantitative analysis
in solving this.

References
8. Harvey, D. Modern Analytical Chemistry. (2016). University of Minnessota.Mc Graw Hill.
9. Skoog, D. A., et.al.(2014). Fundamentals of Analytical Chemistry. 9 th ed. Thomson
Brooks/Cole.
10. Skoog, D. A., et.al.( 2006). Analytical Chemistry – An Introduction. 8 th ed. Saunders College
Publishing.
11. Harvey, D. (2016). What is Analytical Chemistry?-Definition and Impact. Retrieved on
August 20, 2017 from https://study.com/academy/lesson/what-is-analytical-chemistry-
definition-impact.html.