Analytical Chemistry

- A sub discipline of chemistry that has the broad mission of understanding the chemical
composition of all matter and developing the tools to elucidate such compositions.
 What chemicals are present?
 What are the characteristics of those chemicals?
 In what quantities are those chemicals present?
- Limitation: It stops when it already answers those questions.

Brief History

- Early chemistry (1661-1990 AD) was basically analytical chemistry (elemental analyses)
 Development of systemic elemental analysis by Justus von Liebig
 First instrumental analysis was developed in 1860 by Robert Bunsen and Gustav
Kirchhoff
- Major developments came after 1900
 Instrumental analysis became dominant
 The progress of separation science (chromatography) was translated into high
performance analytical instruments
 Inclusion of biological systems as subject for analytical chemistry
 Scientists all over the world are still more interested in filling up the periodic table and
discovering more elements
 Before, anachem is protecting elements, today it can analyze more biological systems

Analytical Process

Steps of an analytical process

1. Sampling
2. Sample preparation
3. Separation
4. Measurement

Sample preparation

Analyte: The chemical substance being measured

- Suppose we want to measure calcium in unknown water sample.

- We precipitate all calcium using oxalate.
1. Take sample from river
2. Prepare sample to make the analyte accessible for measurement
*calcium ions are dissolved in water samples. Cannot be measured directly.

Precipitate – Turn the soluble substance into an insoluble substance

By adding sodium oxalate, we create calcium oxalate resulting to white solids of
calcium.
3. Separate through filtration.
4. Measure the weight of the precipitate (Use Stoichiometry)

Branches of Analytical Chemistry

1. Traditional Analytical Chemistry

 Qualitative (what is present?) and Quantitative analysis (how much is present?)
 o Qualitative Inorganic Analysis – seeks to establish/confirm the presence of a
given element or compound in a sample
o Qualitative Organic Analysis – seeks to establish the presence of a given
functional group or organic compound in a sample.
o Quantitative Analysis – seeks to establish the amount of a given element or
compound in a sample.

 Scientists manually work in the lab with minimal use of instruments to perform analysis
 Main diff of quali/quanti are concerned with different analytes
 Inorganic analytes are elements/compounds without carbon
 Organic analytes are compounds with carbon and its functional groups
a. Volumetric Analysis (Volumetric titration)
o Involves the addition of a reactant of known concentration to a solution
being analyzed until some equivalence point is reached.
o Usually, an acid-base indicator is used in this technique
Example: Acid-base titration, Redox titration
 Checks how much volume of a known substance (titrant) reacts with a specified
volume of a substance with unknown concentration (titer) to determine the
amount of analyte that is present in the titer.
 Indicator tells if the reaction has been whether or not completed. It tells if
titrant fully reacts by titer with the relative changes in pH.

 Use burette to dispense substance titrant. In the flask, we place a specific

volume of analyte of unknown concentration with the indicator. By dispensing
the titrant, it reacts with the analyte slowly. The indicator will start changing the
color of the solution.
 End point – indicator changes the color
 Equivalence point – analyte is fully reacted with titrant

 Steps in Titration
I. Using the pipette add unknown solution to flask
II. Add indicator in flask
III. Fill burette with known solution
IV. Record starting volume in burette
 V. Slowly add solution in burette to flask
VI. Shake flask slightly every after addition
VII. Stop adding when end point is reached (color change)
VIII. Record final volume in burette
IX. Initial volume – Final volume = Titre (solution added)
X. Repeat few times
 Titration Calculations
b. Gravimetry
o Involves determining the amount of material present by weighing the
sample before and/or after some transformation.
Example: Determination of amount of water in a hydrated salt
c. Potentiometric analysis
o Analysis of the analyte by measuring the changes in voltage potential it
undergoes with the addition of standard titrant
o DOES NOT NEED CHEMICAL INDICATORS
o Uses a potentiostat.
o Relates the concentration of an analyte to the difference of voltage potential
it generates.
d. Inorganic qualitative analysis
o Refers to a systemic scheme to confirm the presence of certain, usually,
aqueous, ions or elements by performing a series of reactions that eliminate
ranges of possibilities and then confirms suspected ions with a confirming
test.
o Addition of reagents. Confirming ion presence.
2. Modern Analytical Chemistry
 Instrumental analysis: use of instruments/equipment in measuring the amounts of
analyte in a particular sample.
 Use modern equipment to perform analysis
 Instrumental Analysis
 Spectroscopy
 Mass Spectrometry
 Crystallography
 Electrochemical analysis
 Thermal analysis
 Separation
 Hybrid techniques

o Spectroscopy
- Spectroscopy measures the interaction of the molecules with
electromagnetic radiation. Spectroscopy consists of many different
applications such as atomic absorption spectroscopy, atomic emission
spectroscopy, ultraviolet-visible spectroscopy, x-ray fluorescence
spectroscopy, infrared spectroscopy, Raman spectroscopy, etc.
  Light Source – provides electromagnetic radiation
 Monochromator – narrows down light to a single wavelength which is
specific for the analyte. *Light is composed of multiple wavelengths.
When a light ray of a single wavelength exists the mono, it bombards
the cuvette.
 Cuvette – it holds the sample
 Detector – calculates the amount of absorbed or transmitted light. That
is used to calculate the concentration of the analyte in the sample.

o Mass Spectrometry
- Mass spectrometry measures mass-to-charge ration of molecules using
electric and magnetic fields.
- There are several ionization methods: electron impact, chemical ionization,
electrospray, matrix assisted laser desorption ionization, and others. Also,
mass spectrometry is categorized by approaches of mass analyzers:
magnetic-sector, quadrupole ion trap, Time-of-flight, Fourier transform ion
cyclotron resonance, and so on.
- What happens inside a MS, your sample is heated to a very high
temperature and Is bombarded with electron beam. This process breaks
down the molecules to smaller fragments of itself which is then accelerated
through a quadrupole by an electromagnetic field. The fragmented ions are
caught by the detector. Mass to charge ratio is recorded. Mass-to-charge
ratio is similar to its molar mass.

o Crystallography
- Crystallography is a technique that characterizes the chemical structure of
materials at the atomic level by analyzing the diffraction patterns of usually
x-rays that have been deflected by atoms in the material. From the raw data
the relative placement of atoms in space may be determined.
- Determines the chemical structure of materials at an atomic level.
 - The diffracted rays are detected to a film which results in a diffraction
pattern. The diffraction pattern is calculated using a mathematical model
called Fourier Transform. Which eventually leads to the determination of
the 3d protein structure.

o Electrochemical analysis
- Electrochemical analysis measures the interaction of the material with an
electric field.
- Similar to Potentiometric Analysis. The main difference EA uses high
performance machine that measures the interaction of the material with an
electric film.
o Thermal analysis
- Calorimetry and thermogravimetric analysis measure the interaction of a
material and heat. Analyte with heat. Usually the energy ratings of the food
that we eat are also determined by calorimetry.
- The information that carbohydrates have a lower kilo calorie measurement
whereas protein and fatty acid rich food are high in kilo calorie
measurement are results of experiments utilizing thermal analysis.
o Separation
- Separation processes are used to decrease the complexity of material
mixtures. Chromatography and electrophoresis are representatives of this
field.
- Difference in the interaction of your analyte to the stationary phase
compared to the impurities or other interferences.
- Chromatography: Stationary Phase (Paper) and Mobile Phase (solvent)
 As the solvent goes up the paper, the analyte is separated from other
impurities. The difference in the interaction of the analyte to the stationary
phase on a molecular level.
If your analyte is a polar molecule and impurities are non-polar molecules,
since the paper is polar, analyte is attracted more to the paper than the
impurities.

- Electrophoresis: Different mobile phase. The driving force that pushes the
analyte is an electric field. These techniques are used in Medical Science
(DNA fingerprinting)

o Hybrid techniques
- Combinations of the above techniques produce “hybrid” or “hyphenated”
techniques. Several examples are in popular use today and new hybrid
techniques are under development. For example, GC-MS, LC-MS, GC-IR, LC-
NMR, CE-MS, and so on.
FORMATIVE ASSESSMENT QUESTIONS:

1.) What is the sub-discipline of chemistry that aims to understand the composition of all
matter and aims to develop the tools to elucidate such compositions? – Analytical
Chemistry
2.) What is the term used to denote the particular chemical substance that is being
analyzed/measured? – Analyte
3.) Who discovered the Bunsen burner? – Robert Bunsen
4.) Which step of the analytical process involves taking a representative part of a bulk which
would then be subjected to further analysis? - Sampling
5.) Which step of the analytical process involves taking a representative part of a bulk which
would then be subjected to further analysis? - Sampling
6.) What is the branch of traditional analytical chemistry that is concerned with determination
of the amount of analyte in a given sample? – Quantitative Analysis
7.) What is the branch of traditional analytical chemistry that is concerned with
establishing/confirming the presence of organic functional groups in a given sample? -
Qualitative Organic Analysis
8.) What is the main technique used in modern analytical chemistry that concerns with the
use of instruments/equipments in measuring the amount of the analyte in a particular
sample? – Instrumental Analysis
9.) What is the analytical technique that involves the determination of the amount of material
present by weighing the sample before and/or after some transformation? – Gravimetric
Analysis
10.) What is the analytical technique that involves the determination of the concentration of
the analyte (in an unknown sample) depending on the volume of the reagent (with known
concentration) that reacts to it? – Volumetric Analysis
11.) What is the analytical technique that involves the determination of the concentration of
the analyte based on its difference in voltage potential? – Potentiometric Analysis
12.) What is the analytical technique that involves the determination of the concentration of
the analyte based on its interaction with electromagnetic radiation? – Spectroscopy
13.)Which part of the UV-Vis spectrophotometer is involved in setting the light to a single
wavelength? – Monochromator
14.) In UV-Vis spectroscropy, what signals are measured by the detector to relate to the
concentration of the analyte in the sample? – Transmittance
15.) What is the most useful information that is given by the mass-spectrometer? – Molar
Mass
16.)What analytical technique measures the mass-to-charge ratio upon fragmentation of
molecules? – Mass Spectrometry
17.) What is the modern analytical technique that is concerned with the interaction of the
material (analyte) and heat? – Thermal Analysis
18.) What modern analytical technique uses X-ray beams to determine the diffraction patterns
of a crystalline sample, and relates the diffraction pattern to the structure of the sample
through Fourier transform calculations? – Crystallography
19.) What modern analytical technique makes use of the difference in interaction between the
analyte and the impurities to the stationary phase to discriminate it from the impurities? -
Chromatography