STKK1702

Basic Analytical Chemistry

Kimia Analisis Asas
NURFAIZAH ABU TAHRIM
[email protected]
SCHOOL OF CHEMICAL SCIENCES AND FOOD TECHNOLOGY
FACULTY OF SCIENCE AND TECHNOLOGY

Course Content

Introduction What is analytical chemistry

Sample, sampling and sample treatment.
Error and small data analysis.
Acid-base concept and acid-base equilibrium.
Basic volumetric analytical methods such as
acid-base titration, precipitation,
compelxometry (EDTA) and redox titration.
Gravimetric and gravimetry analysis.
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What is Analytical Chemistry?

It is the Science of Chemical Measurements, providing methods
and tools needed for gaining insight into our material world.
There are four basic questions about a material sample?
What? (What is the identity of the substance in the sample?)
Where? (Does the sample contain substance X?)
How much? (How much of substance X is in the sample?)
What arrangement, structure or form?

The Division of Analytical Chemistry of the American Chemical

Society (ACS) provides a comprehensive definition of analytical
chemistry, which may be found on their website.
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What is Analytical Chemistry?

Discipline of analytical chemistry consists of qualitative analysis and
quantitative analysis.
Concern with the chemical characterization of matter and the
answer to two important questions:
1) What is it (qualitative)?
2) How much is it (quantitative)?
Deals with the identification of elements, ions, or compounds
present in a sample
Deals with the determination of how much of one or more
constituents is present.
Sample may be solid, liquid, gas or mixture.
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Why we need Analytical

Chemistry?
Everything is made of chemicals.

Analytical chemists determine what and how much!

Why we need Analytical

Chemistry?
Analytical Chemistry seeks ever improved means of
measuring the chemical composition of natural and
artificial materials.
The techniques of this science are used to identify the
substances which may present in a material and to
determine the exact amounts of the identified substance.
Provide proven methodologies to new kinds of materials
or to answer new questions about their composition and
their reactivity mechanisms.

Examples of Application Analytical

Chemistry
Nitrogen content of a fertilizer determines its value.
Food must be analyzed for contaminants (pesticide
residue) and for essential nutrients (vitamin content).
Blood glucose must be monitored in diabetics.
The presence of trace elements from gun powder on
a murder defendants hand will prove a gun was
fired.

Examples of Application of
Analytical Chemistry
Industry: means of testing raw materials and for assuring the quality
of finished products whose chemical composition is critical.
Household products such as fuels, paints, pharmaceuticals etc are
analyzed by the procedures developed by analytical chemists before
being sold to the consumer.
Environmental quality is often evaluated by testing for suspected
contaminants using the techniques of analytical chemistry.
Nutritional value of food is determined by chemical analysis for
major components such as protein and carbohydrates and trace
components such as vitamins and minerals.
Medicine: basis for clinical laboratory tests which help physicians
diagnose disease and chart progress in recovery.
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What Do Chemical Analysts Do?

Analyst: Applies known
measurement techniques to well
defined compositional or
characterization questions.
Analytical chemists work to improve
the reliability of existing techniques
to meet the demands for better
chemical measurements which
arise constantly in our society.
Research Analytical Chemist
-Creates and /or investigates novel techniques or principles for
chemical measurements.
-Conducts fundamental studies of chemical/physical phenomena
underlying chemical measurements.
-Develops new measurement methods on existing principles to
solve new analysis problems.

Example of analytical Chemists job

Qualitative and Quantitative

Analysis
Qualitative and Quantitative Analysis: What
does each tell us?

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Selectivity & Specificity

Terms selective and specific are used in
analytical chemistry, especially for qualitative
tests
A selective reaction or test is one that can occur
with other substances but exhibits a degree of
preference for the substance of interest.
A specific reaction or test is one that occurs only
with the substance of interest.
Qualitative/quantitative tests can be performed
by selective/specific chemical reactions or with
the use of instrumentation.
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Qualitative tests
Unfortunately few reactions are specific but
many exhibit selectivity.
Selectivity may be achieved by a number of
strategies:
Sample preparation (e.g extractions,
precipitation)
Instrumentation (selective detectors)
Target analyte derivatization
Chromatography, which provides powerful
separation
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Examples of Qualitative tests

Qualitative test very often based on observation
of colour change or spectra of the analyte
Analyte is the substance analyzed for. Its
concentration is determined.
Chemical reactions produce colors to indicate
the presence of classes of organic compounds,
for example ketones.
Infrared spectra will give fingerprints of organic
compounds of their functional groups.
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Quantitative analysis
A history of the sample composition will often be known.
Example it is known that blood contains glucose or else
the analyst will have performed a qualitative test prior to
performing the more difficult quantitative analysis.

Modern chemical measurement systems often exhibit

sufficient selectivity that a quantitative measurement can
also serve as a qualitative measurement.
However simple qualitative tests are usually more rapid
than quantitative procedures.
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Quantitative analysis Calibration Curve

For the purpose of
determine an unknown
analyte quantitatively
Standard solutions with
known concentrations of
analyte are used to
construct the calibration
curve, i.e. Response vs
concentration.
Linear response is desirable
for a calibration curve
The response of an
unknown analyte is
obtained from the
calibration curve

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Quantitative Analysis Standard Solution

When performing an analysis a chemist often

uses a standard solution.
A standard solution:
A solution that has a concentration of a
chemical that is known to a high degree of
certainty.
Prepared from a chemical that has been
designated as a primary standard.
Complies with standards established by the
Environmental Protection Agency, USA.
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Analytical process
An analysis involves several steps and
operations which depend on:

the particular problem

your expertise
the apparatus or equipment available.
The analyst should be involved in every step.

Analytical process
Define the problem

Select a method

Calculate the results and report

Obtain a representative
sample

Perform the measurement

Prepare the sample for

analysis

Perform any necessary

chemical separations

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Define the problem

What do we really need to know (not necessarily
everything)?
Information: by whom?
For what purpose?
What type of sample?
The analyst must have good communication with the
client.
Eg. of clients may be the Environmental Protection
Agency (EPA), an industrial client, an engineer etc.
Each will have different criteria or needs and different
understanding of what a chemical analysis involves or
means.
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Define the problem

The concept of safe or zero/nothing is one that is hard to define or
understand by many people.

Telling someone their water is safe is not for the analyst to say.
All you can do is present the analytical data. The client must decide
whether it is safe to drink, perhaps relying on other experts.
Also never report an answer zero but as less than the detection
limit which is based on the measurement device/instrument (ppm,
ppb, ppt).
We are limited by our methodology and equipment and that is all
that can be reported.
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Define the problem

A law may be passed that there should be zero
concentration of chemical effluent in water.
In practice, the acceptable level is defined by how low a
concentration can be detected; and the very low
detectability may be far below the natural occurrence of
the chemical or below the levels to which it can be
reasonably reduced.

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Define the problem

Once the problem is defined:
- how much is needed?
- how sensitive the method must be?
- how accurate and precise?
- what separations may be required to eliminate
interferences?
The analytical method to be used will depend on factors such as:
1) analysts skills and training in different techniques
instruments
2) facilities, equipments and instruments available
3) sensitivity and precision required
4) cost and budget available
5) time for analysis and how soon results are needed.

and

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Calculating the results and

reporting data
Once the concentration of analyte in the prepared
sample solution has been determined, the results are
used to calculate the amount of analyte in the original
sample.
Either an absolute or a relative amount may be reported.
Replicate analyses can be performed (three or more)
and a precision of the analysis may be reported,
standard deviation.
Acknowledge of the precision is important gives
degree of uncertainty in the result.

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The laboratory notebook

Notebook Your critical record
All data should be recorded permanently in ink when they are
collected.
When you go into the analytical laboratory, you will find that this
orderliness is to your advantage:
FIRST: Saving of time in not having to reorganize and rewrite the
data. Chances for a mistake are reduced.
SECOND: if you make an immediate record, you will be able to
detect possible errors in measurements or calculations.
Data will not be lost or transferred incorrectly if they are recorded
directly in a notebook instead of collected on scraps of paper.

The laboratory notebook

For practicing analytical chemists and on-the-job
applications, it is important to use the lab
notebooks for entering observations and
measurements directly.
Complete documentation is essential for forensic
or industrial laboratories for legal and patent
considerations.
In industrial research labs, the notebook must
generally be signed (witnessed) and dated by
another person familiar with the work to assure
legal patent priority if applicable.

Rules of laboratory notebook

Use a hardcover notebook (no loose leafs)
Label with number on pages consecutively
Record only in ink
Never tear out pages. If not used, put a line through
a page.
Date each page, sign it and have it signed and dated
by someone else, stating Read and Understood by
Record the name of the project, why it is being done,
and any literature references.
Record all data on the day you obtain it.

The laboratory notebook

Sampling (Obtaining sample) for analysis

Drainage water sampling

Collecting water samples

Blood sample

Forensic samples

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Sampling (Obtaining sample) for analysis

Sample can be solid, liquid or gas.
This process can be the most critical aspect of
an analysis.
The significance and accuracy of measurements
can be limited by the sampling process.
Many professional societies have specified
definite instructions for sampling given materials.
[American Society for Testing and Materials
(ASTM), American Public Health Association
(APHA)].
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Sampling processes
The problem involves obtaining a sample that is
representative of the whole. This sample is called gross
sample.
Once a representative gross sample is obtained, it may
have to be reduced to a sufficiently small size to be
handled. This is called sample.
Once the sample is obtained, an aliquot or portion of it
will be analyzed. This aliquot is called the analysis
sample. Several replicate analyses on the same sample
may be performed by taking separate aliquots.
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Steps in obtaining a laboratory sample

Identify the population

Collect a gross sample

Reduce the gross sample to a laboratory sample

Obtaining a representative sample

Homogeneous gaseous or liquid sample
No problem any sample representative.
Solid sample - no gross heterogeneity
Take a number of small samples at random from throughout the bulk - this will give a
suitable representative sample.
Solid sample - obvious heterogeneity
Take small samples from each homogeneous region and mix these in the same
proportions as between each region and the whole.
If it is suspected, but not certain, that a bulk material is heterogeneous, then it is
necessary to grind the sample to a fine powder, and mix this very thoroughly before
taking random samples from the bulk.
For a very large sample - a train-load of metal ore, or soil in a field - it is always
necessary to take a large number of random samples from throughout the whole.

Sampling: Procuring a representative

sample
Homogeneous: same throughout
Heterogeneous: differs from region to region

In a random heterogeneous material,

differences in composition occur
randomly and on a fine scale.

For a segregated heterogeneous

material (in which large regions have
obviously different compositions), a
representative composite sample
must be constructed.

Sampling processes
In the case of clinical analysis, e.g. collection of
biological fluids, the conditions under which the sample
is collected can be important, for example whether a
patient has just eaten.
Composition of blood varies considerably before and
after meals, for many analyses a sample is collected
after the patient has fasted for a number of hours.

certain precautions should be taken in handling and

storing samples to prevent or minimize contamination,
loss, decomposition or matrix change.
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Example of Water Sampling technique (video link)

https://www.youtube.com/watch?v=BlePFFPt4HE&list=PLMSa5d-iIl6PjYhV9cc4S_mNEteXts58&index=8

How to measure the caffeine content

of a chocolate bar?

Step 1: Sample Preparation

--transforming a sample into a state that is suitable for analysis

1. Weighing
2. Removing fat with organic solvent

3. Extracting caffeine and theobromine (analytes) with water

Step 2: Performing
analysis with liquid
chromatography

Principles of liquid
chromatography

Step 3: Preparing
calibration curves

A graph of detector response as a

function of analyte concentration is
called a calibration curve or a
standard curve.

Standard solution: containing known

concentrations of analytes.

Step 4: Analyzing the

results

Why Precautions?
In general must prevent contamination or alteration of
the sample by:
1) container
2) atmosphere
3) light
The sample may have to be protected from atmosphere
or from light.
Alkaline substance for example, will react with CO2 in the
air.
Blood samples to be analyzed for CO2 should be
protected from the atmosphere.
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What Precautions?
The stability of the samples must be considered. Examples:
Glucose is unstable and a preservative such as sodium
flouride is added to blood samples.
The preservation must not interfere in the analysis.
Proteins and enzymes tend to denature on standing and
should be analyzed without delay.
Urine samples are unstable and calcium phosphate
precipitates out, entrapping metal ions or other
substances of interest.
Precipitation can be prevented by keeping urine acidic
(pH 4.5) usually by adding 1 or 2 ml glacial acetic acid
per 100-ml sample. Store under refrigeration.
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Performing necessary chemical separations

One or more separation steps are required during
chemical analysis because:
To eliminate interferences,
To provide suitable selectivity in the
measurement or
To preconcentrate the analyte for more sensitive
or accurate measurement
It is preferable to separate the analyte away
from the sample matrix, in order to minimize
losses of the analyte.
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Methods for Separation Chemical Analysis

Examples of separation steps:
Precipitation
Extraction into an immiscible solvent
Chromatography
Dialysis
Distillation
Electrophoresis
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Why sample Preparation and Extraction?

May be many analytes present
May be small amounts of analyte(s) in bulk
material.
Need to concentrate these before analysis. e.g.
heavy metals in animal tissue, additives in
polymers, herbicide residues in flour etc. etc
May be helpful to concentrate complex mixtures
selectively.
Most general type of pre-treatment:
EXTRACTION
E.g. Soxhlet extraction, solid phase extraction

Measurement Techniques in Analytical Chemistry

As analyst, it is important to have good

communication and interaction with
the customer about what the
analysis represents.

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