Chem 26: Analytical

Chemistry

Chapter 1
The Nature of Analytical
Chemistry

Department of Chemistry
College of Mathematics and Natural Sciences
Caraga State University
Lecture Outline:

A. Nature, scope and importance of analytical chemistry

B. Classification of analyses
1. Sample size: Macro, Semi-macro and Micro
2. Type of Constituents:
ü Major, Minor and Trace constituent
3. Ultimate, Proximate, Single-component
4. Method in qualitative analysis
ü Gravimetric, Volumetric, Instrumental
Intended Learning Outcomes:
Recognize the importance of analytical chemistry in
different fields of sciences, industry, medicine, and
many other disciplines.
Acknowledge the relationship between analytical
chemistry, other branches of chemistry, and other
sciences.

Explain the two (2) areas of analysis: Qualitative

analysis and Quantitative analysis

Illustrate the examples of the two (2) areas of

analysis.

Classify the different types of analyses according to

sample size, method, sample availability, and analyte
level
Intended Learning Outcomes:
Compare the differences of sample sizes: Macro,
Semi-macro and Micro

Relate the connection of the type of constituents

from the sample size.

Classify the differences of ultimate, proximate and

single-component.

Show some application of both classical method

(gravimetric and volumetric) and instrumental method
 Analytical Chemistry
l a measurement science
l consist of a set of powerful ideas and methods
l useful in all fields of science and medicine

On July 4, 1997, the Mars Pathfinder

spacecraft delivered the Sojourner rover
on Ares Vallis, Mars in its quest for
information on the nature of the red planet.

Mars: Through the eyes of the Sojourner rover

5
Analytical Chemistry
is a measurement science consisting of a
set of powerful ideas and methods that are
useful in all fields of science, engineering,
and medicine.

Two types of analysis in Analytical

Chemistry
1. Qualitative analysis establishes the
chemical identity of the species in the
sample.
2. Quantitative analysis determines the
relative amounts of these species, or
analytes, in numerical terms.

Analytes are the components of a sample

that are determined.
The Central Role of Analytical Chemistry

• Chemical analysis is a
vital tool in medical,
industrial,
government, and
academic
laboratories

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Quantitative Analytical Methods

Complete (or Ultimate) analysis

Ø the amounts of all the constituents in the
sample are determined

Partial analysis
Ø the amounts of only some of the
constituents in the sample are determined

Elemental and molecular analysis

Ø the determination of the amounts of
elements and molecules

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 Quantitative Analytical Methods

Major-constituent (macro) analysis

Ø the constituent determined is present
in high concentration

Trace analysis
Ø the constituent determined is present
in low concentration

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 Quantitative Analytical Methods

Five Classification of Analytical Methods

1. Gravimetric Method
determine the mass of the analyte or
some compound chemically related to it.

2. Volumetric Method
measure the volume of a solution
containing sufficient reagent to react
completely with the analyte.
3. Electroanalytical Method
Ø measure electrical properties such
as potential, current, resistance,
and quantity of electrical charge.
4. Spectroscopic Method
Ø The interaction between
electromagnetic radiation and analyte
atoms or molecules or the emission
of radiation by analytes.
5.Miscellaneous Method
Ø measure such quantities as mass-to-
charge ratio of ions by mass
spectrometry, rate of radioactive
decay, heat of reaction, rate of
reaction, sample thermal conductivity,
optical activity, and refractive index.
A Typical Quantitative Method

A typical quantitative analysis includes the

sequence of steps shown in the flow diagram.
Steps in Quantitative Analysis
1. Choosing Method or
Method selection

ü the essential first step in any

quantitative analysis is the
selection of a method.

ü the choice is sometimes difficult

and requires experience as well
as intuition.

ü the selected method usually

represents a compromise
between the accuracy required
and the time and money
available for the analysis.

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Steps in Quantitative Analysis
2. Acquiring Sample
r To produce meaningful information, an

analysis must be performed on a

sample that has the same composition
as the bulk of material from which it
was taken.

r When the bulk is large and

heterogeneous, great effort is
required to get a representative
sample.

A material is heterogeneous if its

constituent parts can be distinguished
visually or with the aid of a microscope.
Coal, animal tissue, and soil are
heterogeneous.
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 Steps in Quantitative Analysis
2. Acquiring Sample
Sampling Homogeneous vs Heterogeneous materials
Homogeneous material Heterogeneous material

• easy • more difficult

• composition is uniform • requires carefully
prescribed procedures
– select only the desired that are designed to
size of the sample for the ensure proper
laboratory representation in the
final sample

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An assay is the process of determining Sampling is the process of collecting a
how much of a given sample is the small mass of a material whose
material by its indicated name. For composition accurately represents the
example, a zinc alloy is assayed for its bulk of the material being sampled.
zinc content, and its assay is a
particular numerical value.

Acceptable Methods for Sampling

Bulk Materials
1. American Society for Testing and
Materials (ASTM)
2. National Institute of Standards and
Technology (NIST)
3. Association of Official Analytical
Chemists (AOAC)
4. American Oil Chemists Society (AOCS)
 Steps in Quantitative Analysis
2. Acquiring Sample
Sampling Bulk Materials

1. Obtaining a gross sample

2. Reducing the gross sample to a

transportable size

3. Obtaining a laboratory sample

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 Steps in Quantitative Analysis
2. Acquiring Sample
Sampling Bulk Materials
1. Obtaining a gross sample

– A chute may be designed that siphons off a certain fraction

of the material (~1 ton) which , taken as a whole must be
representative of the entire load of ore
2. Reduce gross sample to a size suitable for transportation

– Crushing sample to get uniform size followed by sampling

procedure that removes a fixed portion of the gross sample

• Cone and quarter method

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 Steps in Quantitative Analysis
2. Acquiring Sample
Cone and Quarter Method

1. The gross sample is piled into a cone which is

flattened and quartered

2. Opposite quarters are retained, mixed, and the

procedure repeated until an appropriate sample is
obtained (5-25 lbs)

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 Steps in Quantitative Analysis
2. Acquiring Sample
Sampling Bulk Materials
3. Obtaining a Laboratory sample:
In the laboratory a similar procedure is used to
further reduce the sample size that can be analyzed:
• 3 or more samples are prepared and analyzed simultaneously
– more confidence can be placed in a number representing the
results of 3 measurements than in one representing 1
measurement
– in case a sample is ruined during the analysis, the analysis can be
continued with the remaining 2 samples

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 Steps in Quantitative Analysis
2. Acquiring Sample
Sampling Bulk Materials
3. Obtaining a Laboratory sample:
In the laboratory a similar procedure is used to
further reduce the sample size that can be analyzed:
• Prevent contamination during the sample collection process
(especially when the constituents to be determined are present in very
low concentration – trace analysis)
– All sample-handling equipment must be cleaned before use
– Special care is required in handling corrosive substances (they
often react with their containers and the equipment used to handle
them)

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Steps in Quantitative Analysis

3. Processing Sample

Ø The first step in processing the sample is often

the preparation of a laboratory sample.

Preparing a Laboratory Sample

• A solid laboratory sample is ground to

decrease particle size, mixed to ensure
homogeneity, and stored for various
lengths of time before analysis begins.

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 Steps in Quantitative Analysis
3. Processing Sample
• Any loss or gain of water changes the
chemical composition of solids, it is a
good idea to dry samples just before
starting an analysis.

• the moisture content of the sample can

be determined at the time of the
analysis in a separate analytical
procedure

A wet basis is a measure of the water in a solid, expressed as

the weight of water as a percentage of the wet solid.
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 Steps in Quantitative Analysis
3. Processing Sample
• If such samples are allowed to stand
in open containers, the solvent may
evaporate and change the
concentration of the analyte.

• If the analyte is a gas dissolved in a

liquid, as in our blood gas example, the
sample container must be kept inside a
second sealed container, perhaps
during the entire analytical procedure,
to prevent contamination by
atmospheric gases.

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 Steps in Quantitative Analysis
3. Processing Sample

Preparing Solid Sample

1. Grinding to decrease particle size

2. Mixing to ensure homogeneity

3. Storing for various lengths of time before analysis*

4. Drying samples before starting an analysis

(alternatively, the moisture content of the sample can be
determined at the time of the analysis in a separate
analytical procedure)
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*any loss or gain of water changes the chemical composition of the solid
 Steps in Quantitative Analysis
3. Processing Sample
Replicate samples, or replicates
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

• Replication improves the quality of the results and

provides a measure of reliability

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 Steps in Quantitative Analysis
3. Processing Sample
Preparing Solutions: Physical and Chemical Changes

• Ideally, the solvent should dissolve the • Replication improves the quality of
entire sample, including the analyte, the results and provides a measure
rapidly and completely. of their reliability.

• the conditions of dissolution should be • Quantitative measurements on

sufficiently mild that loss of the analyte replicates are usually averaged, and
cannot occur. various statistical tests are performed
on the results to establish their
reliability.

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 Steps in Quantitative Analysis
3. Processing Sample
Preparing Solutions: Physical and Chemical Changes
• If the samples (silicate minerals, • Once the analyte is made
high-molecular-mass polymers, soluble, we then ask whether
and specimens of animal tissue) the sample has a property that is
are not soluble in common proportional to analyte
solvents, may require heating concentration and that we can
with aqueous solutions of strong measure.
acids, strong bases, oxidizing
agents, reducing agents, some
combination of such reagents.

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Sample Size

Classification of Constituent Type by Sample Size

Steps in Quantitative Analysis
4. Eliminating Interferences
• Interference (or interferents) are species
other than the analyte that affect the final
measurement

– species that cause errors in analysis by

enhancing or attenuating (making small)
the quantity being measured

Methods in Eliminating Interferences:

• Selective Method – reactions that apply for a

few analytes

• Specific Method – reactions that works only

for one analyte

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 Steps in Quantitative Analysis
4. Eliminating Interference
a. Selecting Method

§ Know the general method of the sample to be analyzed

§ Know which methods possibly be used

§ Refer to “Standard” or “Accepted” methods of analysis, which this

method have been carefully tested and evaluated under controlled
conditions.
b. Masking

§ The elimination of an interference from a substance by converting it to a

non-interfering form.
Example: a method for determining copper based on measuring the amount of iodine produced
when Cu2+ reacts with iodide ion, Fe3+ interferes by also oxidizing iodide to iodine
Ferric ion can be masked by adding fluoride ion, which forms a stable complex ion with iron (III),
FeF63- and prevent its reduction. 2Fe3+ + 2I- ® 2Fe2+ + I2 , FeF63- + I- ® no reaction

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 Steps in Quantitative Analysis
4. Eliminating Interference
c. Separation

• Precipitation • Ion Exchange

• Extraction • Chromatography
• Volatilization

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Steps in Quantitative Analysis
5. Treating the sample and measuring the analyte

• Most methods require the analyte to be

in a particular form that is suitable for
measurement
• The exact property or substance
measured depends on the type of
method selected

• Redox titration: the analyte must be in a

particular oxidation state before the
titration begins
• Colorimetric method: a colorless analyte
must be converted to a colored product for
the measurement.

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Steps in Quantitative Analysis
6. Calculating the amount

• The procedure used to calculate the

amount or concentration of an analyte
depends on the analysis method
– absolute measurements where the
amount or concentration of analyte is
determined directly from the measured
value
– relative measurements where the
amount or concentration is determined
by comparison of the measured value
for the unknown with similar values
obtained for known amounts of analyte

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Steps in Quantitative Analysis
7. Estimate reliability of results

• Analytical results are complete only when

their reliability has been estimated. The
experimenter must provide some measure
of the uncertainties associated with
computed results if the data are to have
any value.

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 END OF
CHAPTER