Analytical Chemistry Basics
This index provides an introduction to some of the fundamental concepts and methods of
analytical chemistry. The topics are arranged in the order in which they are commonly presented
in an undergraduate analytical chemistry course. Many of the documents listed here contain links
to introductory material and related topics.
General steps in a chemical analysis
An introduction to the processes and protocols of analytical chemistry
Chemical equilibrium
Review of chemical equilibrium and equilibrium constants.
Gravimetric analysis
Introduction to gravimetric analysis and solubility products with links to precipitation
reactions.
Titration
Introduction to titrations with links to acid-base chemistry.
Electrochemistry
Introduction to electrochemistry with links to oxidation-reduction reactions.
Spectroscopy
Introduction to spectroscopy with descriptions of absorption, emission, scattering, and
links to the Beer-Lambert Law and advanced examples.
Separations
Introduction to separation science with basic descriptions of partitioning, extractions,
chromatography, and electrophoresis.
Appendix: Data Analysis
Definitions of accuracy and precision, and basic rules for significant figures and errors.
Introduction to treatment of experimental data and graphs and graphical methods. Links
to statistical methods pages.
Appendix: Analytical Standards
Definitions of primary and secondary standards, and working curves.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
General Steps in a Chemical Analysis
Introduction
The analytical process often begins with a question that is not phrased in terms of a chemical
analysis. The question could be "Does lead in petrol enter our food supply?" or "Is this water safe
to drink?" or "Does emission testing of automobiles reduce air pollution?" A scientist translates
such questions into the need for particular measurements. An analytical chemist then must
choose or invent a procedure to carry out those measurements,
When the analysis is complete, the analyst must translate the results into terms that can be
understood by others preferably by the general public. A most important feature of any results is
its limitations. What is the statistical uncertainty in reported results? If you took samples in a
different manner, would you obtain the same results? Is a tiny amount (a trace) of analyte found
in a sample really there or is it contamination? Once all interested parties understand the results
and their limitations, then they can draw conclusions and reach decisions.
The Process
Formulating 1. Translate general questions into specific questions amenable to being
the question answered through chemical measurements.
Selecting 2. Search the chemical literature to find appropriate procedures or, if
analytical necessary, develop original procedures to make the required measurements.
procedures
Sampling 3. Obtain a representative bulk sample from the lot.
4. Extract from the bulk sample a homogeneous laboratory sample.
Sample 5. Convert the laboratory sample into a form suitable for analysis, which
preparation usually means dissolving the sample. Samples with a low concentration of
analyte may need to be concentrated prior to analysis.
6. Remove or mask species that interfere with the chemical analysis.
Analysis 7. Measure the concentration of analyte in several aliquots. The purpose of
replicate measurements (repeated measurements) is to assess the variability
(uncertainty) in the analysis and to guard against a gross error in the
analysis of a single aliquot. The uncertainty of a measurement is as
important as the measurement itself, because it tells us how reliable a
measurement is. If necessary, use different analytical methods on similar
samples to make sure that each method gives the same result and that the
choice of analytical method is not biasing the result. You may also wish to
construct and analyse several different bulk samples to see what variations
arise from your sampling procedure.
Reporting and 8. Deliver a clearly written, complete report of your results, highlighting any
interpretation special limitations that you attach to them. Your report might be written to
be read only by a specialist (such as your instructor), or it might be written
for a general audience (such as your mother). Be sure the report is
appropriate for its intended audience.
Drawing 9. Once a report is written, the analyst might or might not be further involved
conclusions in what is done with the information, such as modifying the raw material
supply for a factory or creating new laws to regulate food additives. The
more clearly a report is written, the less likely it is to be misinterpreted by
those who use it. The analyst should at least have the responsibility to
ensure that conclusions drawn from his or her data are consistent with the
data.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Introduction to Chemical Equilibrium
Introduction
A chemical specie will always exist in equilibrium with other forms of itself. The other forms
may exist in undetectable amounts but they are always present. These other forms arise due to
the natural disorder of nature that we call entropy (it's impossible to be perfect). As an example,
pure water consists of the molecular compound and dissociated ions that exist together in
equilibrium:
H2O(l) H+(aq) + OH-(aq)
The (l) subscript refers to the liquid state, and the (aq) subscript refers to ions in aqueous
solution.
Equilibrium Constant
The equilibrium between reactants and products is described by an equilibrium constant. For the
balanced reaction:
aA + bB cC + dD
The equilibrium constant, Keq is defined as:
[C]c [D]d
Keq = ---------
[A]a [B]b
where the [] brackets indicate the concentration of the chemical species.
For the example of water, H2O H+ + OH-, the equilibrium constant is:
[H+] [OH-]
Keq = ----------
[H2O]
The concentration of water in a water solution is constant and this expression simplifies to:
Kw = (55.56 M)*Keq = [H+] [OH-]
where Kw is called the dissociation constant of water and equals 1.00x10-14 at room temperature.
The concentrations of [H+] and [OH-] therefore equal 1.00x10-7 M.
Rules for Writing K Expressions
1. Products are always in the numerator.
2. Reactants are always in the denominator.
3. Express gas concentrations as partial pressure, P, and dissolved species in molar
concentration, [].
4. The partial pressures or concentrations are raised to the power of the stoichiometric
coefficient for the balanced reaction.
5. Leave out pure solids or liquids and any solvent.
Example:
Zn (s) + 2 H+(aq) Zn2+(aq) + H2 (g)
PH2 [Zn2+]
K = -----------
[H+]2
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Gravimetry
Introduction
Gravimetry is the quantitative measurement of an analyte by weighing a pure, solid form of the
analyte. Since gravimetric analysis is an absolute measurement, it is the principal method for
analyzing and preparing primary standards.
A typical experimental procedure to determine an unknown concentration of an analyte in
solution is as follows:
• quantitatively precipitate the analyte from solution
• collect the precipitate by filtering and wash it to remove impurities
• dry the solid in an oven to remove solvent
• weigh the solid on an analytical balance
• calculate the analyte concentration in the original solution based on the weight of the
precipitate
Examples of Gravimetric Lab Procedures
Gravimetric Determination of Iron
1. Determine constant weight of the crucibles
2. Oxidation of iron sample
3. Precipitation of iron hydroxide
4. Ignition of iron hydroxide to iron oxide
5. Determine constant weight of the crucibles plus iron oxide
6. Calculation of iron in the sample
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Titration
Introduction
Titration is the quantitative measurement of an analyte in solution by completely reacting it with
a reagent.
The point at which all of the analyte is consumed is called the endpoint and is determined by
some type of indicator that is also present in the solution. For acid-base titrations, indicators are
available that change color when the pH changes. When all of the analyte is neutralized, further
addition of the titrant causes the pH of the solution to change causing the color of the indicator to
change.
The analyte concentration is calculated from the reaction stoichiometry and the amount of
reagent that was required to react with all of the analyte.
Instrumentation
Manual titration is done with a burette, which is a long graduated tube to hold the titrant. The
amount of titrant used in the titration is found by reading the volume of titrant in the burette
before beginning the titration and when the endpoint is reached, and taking the difference. The
most important factor for making accurate titrations is to read the burette volumes reproducibly.
The figure shows how to do so by using the bottom of the meniscus to read the reagent volume
in the burette.
For repetitive titrations, autotitrators with microprocessors are available that deliver the titrant,
stop at the endpoint, and calculate the concentration of the analyte. The endpoint is usually
detected by some type of electrochemical measurement. Some examples of titrations for which
autotitrators are available include:
• Acid or base determination by pH measurement with potentiometric detection.
• Determination of water by Karl Fischer reagent (I2 and SO2 in methyl alcohol and
pyridine) with coulometric detection.
• Determination of Cl in aqueous solution with phenylarsene oxide using amperometric
detection.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Electrochemistry
Introduction
Electrochemistry can be broadly defined as the study of charge-transfer phenomena. As such, the
field of electrochemistry includes a wide range of different chemical and physical phenomena.
These areas include (but are not limited to): battery chemistry, photosynthesis, ion-selective
electrodes, coulometry, and many biochemical processes. Although wide ranging,
electrochemistry has found many practical applications in analytical measurements.
Electroanalytical chemistry
A good working definition of the field of electroanalytical chemistry would be that it is the field
of electrochemistry that utilizes the relationship between chemical phenomena which involve
charge transfer (e.g. redox reactions, ion separation, etc.) and the electrical properties that
accompany these phenomena for some analytical determination. This relationship is further
broken down into fields based on the type of measurement that is made.
Potentiometry involves the measurement of potential for quantitative analysis, and electrolytic
electrochemical phenomena involve the application of a potential or current to drive a chemical
phenomenon, resulting in some measurable signal which may be used in an analytical
determination.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Potentiometry
Introduction
Potentiometry is the field of electroanalytical chemistry in which potential is measured under the
conditions of no current flow. The measured potential may then be used to determine the
analytical quantity of interest, generally the concentration of some component of the analyte
solution. The potential that develops in the electrochemical cell is the result of the free energy
change that would occur if the chemical phenomena were to proceed until the equilibrium
condition has been satisfied.
This concept is typically introduced in quantitative analysis courses in relation to
electrochemical cells that contain an anode and a cathode. For these electrochemical cells, the
potential difference between the cathode electrode potential and the anode electrode potential is
the potential of the electrochemical cell.
If the reaction is conducted under standard state conditions, this equation allows the calculation
of the standard cell potential. When the reaction conditions are not standard state, however, one
must utilize the Nernst equation to determine the cell potential.
Physical phenomena which do not involve explicit redox reactions, but whose initial conditions
have a non-zero free energy, also will generate a potential. An example of this would be ion
concentration gradients across a semi-permeable membrane. This can also be a potentiometric
phenomena, and is the basis of measurements that use ion-selective electrodes.
Instrumentation
See the documents on ion-selective electrodes and pH meters.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Coulometry
Introduction
Coulometry is an analytical method for measuring an unknown concentration of an analyte in
solution by completely converting the analyte from one oxidation state to another. Coulometry is
an absolute measurement similar to gravimetry or titration and requires no chemical standards or
calibration. It is therefore valuable for making absolute concentration determinations of
standards.
Coumetry uses a constant current source to deliver a measured amount of charge. One mole of
electrons is equal to 96,485 coulombs of charge, and is called a faraday.
Schematic of a coulometric cell
Coulometric Titration
Due to concentration polarization it is very difficult to completely oxidize or reduce a chemical
species at an electrode. Coulometry is therefore usually done with an intermediate reagent that
quantitatively reacts with the analyte. The intermediate reagent is electrochemically generated
from an excess of a precursor so that concentration polarization does not occur. An example is
the electrochemical oxidation of I- (the precursor) to I2 (the intermediate reagent). I2 can then be
used to chemically oxidize organic species such as ascorbic acid.
The point at which all of the analyte has been converted to the new oxidation state is called the
endpoint and is determined by some type of indicator that is also present in the solution. For the
coulometric titration of ascorbic acid, starch is used as the indicator. At the endpoint, I2 remains
in solution and binds with the starch to form a dark purple complex.
The analyte concentration is calculated from the reaction stoichiometry and the amount of charge
that was required to produce enough reagent to react with all of the analyte.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Spectroscopy
Absorption | Emission | Scattering
Introduction
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic radiation by
atoms or molecules (or atomic or molecular ions) to qualitatively or quantitatively study the
atoms or molecules, or to study physical processes. The interaction of radiation with matter can
cause redirection of the radiation and/or transitions between the energy levels of the atoms or
molecules. A transition from a lower level to a higher level with transfer of energy from the
radiation field to the atom or molecule is called absorption. A transition from a higher level to a
lower level is called emission if energy is transfered to the radiation field, or nonradiative decay
if no radiation is emitted. Redirection of light due to its interaction with matter is called
scattering, and may or may not occur with transfer of energy, i.e., the scattered radiation has a
slightly different or the same wavelength.
Absorption
When atoms or molecules absorb light, the incoming energy excites a quantized structure to a
higher energy level. The type of excitation depends on the wavelength of the light. Electrons are
promoted to higher orbitals by ultraviolet or visible light, vibrations are excited by infrared light,
and rotations are excited by microwaves.
An absorption spectrum is the absorption of light as a function of wavelength. The spectrum of
an atom or molecule depends on its energy level structure, and absorption spectra are useful for
identifying of compounds.
Measuring the concentration of an absorbing species in a sample is accomplished by applying the
Beer-Lambert Law.
Emission
Atoms or molecules that are excited to high energy levels can decay to lower levels by emitting
radiation (emission or luminescence). For atoms excited by a high-temperature energy source
this light emission is commonly called atomic or optical emission (see atomic-emission
spectroscopy), and for atoms excited with light it is called atomic fluorescence (see atomic-
fluorescence spectroscopy) or molecular fluorescence (see molecular fluorescence spectroscopy).
For molecules it is called fluorescence if the transition is between states of the same spin and
phosphorescence if the transition occurs between states of different spin.
The emission intensity of an emitting substance is linearly proportional to analyte concentration
at low concentrations, and is useful for quantitating emitting species.
Scattering
When electromagnetic radiation passes through matter, most of the radiation continues in its
original direction but a small fraction is scattered in other directions. Light that is scattered at the
same wavelength as the incoming light is called Rayleigh scattering. Light that is scattered in
transparent solids due to vibrations (phonons) is called Brillouin scattering. Brillouin scattering
is typically shifted by 0.1 to 1 cm-1 from the incident light. Light that is scattered due to
vibrations in molecules or optical phonons in solids is called Raman scattering. Raman scattered
light is shifted by as much as 4000 cm-1 from the incident light.
Related topics
Optics
Descriptions of the optical components in spectroscopic instrumentation.
Interaction of light with matter
A qualitative quantum mechanical description.
Spectroscopic techniques
The spectroscopy section of the Contents.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Electromagnetic Radiation
Introduction
Electromagnetic radiation is a transverse energy wave Schematic of an electromagnetic wave
that is composed of an oscillating electric field
component, E, and an oscillating magnetic field
component, M. The electric and magnetic fields are
orthogonal to each other, and they are orthogonal to the
direction of propogation of the wave. A wave is
described by the wavelength, , which is the physical
length of one complete oscillation, and the frequency,
, which is the number of oscillations per second. The
figure shows one wavelength of a wave of light. The
names we give electromagnetic radiation for different
wavelength and frequency ranges are listed in the
electromagnetic spectrum document.
Velocity of light
Electromagnetic waves travel through a vacuum at a constant velocity of 2.99792x108 m/s,
which is known as the speed of light, c. The relationship between the speed of light, wavelength,
and frequency is:
c=
When light passes through other media, the velocity of light decreases. For a given frequency of
light, the wavelength also must decrease. This decrease in velocity is quantitated by the
refractive index, n, which is the ratio of c to the velocity of light in another medium, v:
n=c/v
Since the velocity of light is lower in other media than in a vacuum, n is medium n*
always a number greater than one. The table lists the refractive index of
several examples. Refractive index is an intrinsic physical property of a air 1.0003
substance, and can be used to monitor purity or the concentration of a water 1.333
solute in a solution. The refractive index of a material is measured with a
refractometer, and is usually made versus air. If the precision warrants, 50% sucrose
1.420
the measurements can be corrected for vacuum. Note that the difference in water
between nair and nvacuum is only significant in the fourth decimal place. carbon
1.628
disulfide
For anisotropic materials, such as quartz crystals, light of different
polarizations (see below) will experience different refractive indices. crystalline 1.544
These indices are called the ordinary refractive index, no, and the quartz (no)
extraordinary refractive index, ne. 1.553
(ne)
diamond 2.417
*measured with 589.3
nm light
Polarization
An incoherent light source, such as the hot filament of a light bulb, consists of multiple,
randomly oriented light emitters, which produce electromagnetic waves with their electric-field
vector oriented in all directions. The resulting light emission is called unpolarized light.
Linearly (or plane) polarized light is light in which the electric-field vector is oscillating in only
one direction. Linearly polarized light is produced by isolating one orientation of the electric
field with a polarizer, or from lasers that contain polarized optical components.
Circularly polarized light is light in which the electric field vector is rotating around the axis of
light propogation. The electric field vector can rotate in either the right or left direction (as
viewed in the direction of light propogation), and the light is called right circularly polarized or
left circularly polarized, respectively.
Wave-particle duality
Electromagnetic radiation shows both wave and particle characteristics depending on how the
radiation is observed. Einstein first postulated that the energy of radiation is quantized and that
radiation is composed of energy packets that were later named photons. The energy, E, of one
photon depends on its frequency (or wavelength):
E=h = hc /
where h is Planck's constant (6.62618x10-34 Js), is the frequency of the radiation, c is the speed
of light, and is wavelength.
de Broglie equation
Moving particles; such as electrons, protons, and neutrons; have wave properties as described by
the de Broglie equation:
=h/p
where is wavelength, h is Planck's constant, and p is the momentum of the particle. Beams of
particles can therefore show wave effects such as interference.
Related topics
• Electromagnetic Spectrum
• Introduction to Spectroscopy
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Electromagnetic Spectrum
Visible Spectrum
Electromagnetic Spectrum
Type of Frequency Range Wavelength
Type of Transition
Radiation (Hz) Range
20 24 -12
gamma-rays 10 -10 <10 m nuclear
x-rays 1017-1020 1 nm-1 pm inner electron
ultraviolet 1015-1017 400 nm-1 nm outer electron
visible 4-7.5x1014 750 nm-400 nm outer electron
near-infrared 1x1014-4x1014 2.5 um-750 nm outer electron molecular vibrations
infrared 1013-1014 25 um-2.5 um molecular vibrations
molecular rotations, electron spin
microwaves 3x1011-1013 1 mm-25 um
flips*
radio waves <3x1011 >1 mm nuclear spin flips*
*energy levels split by a magnetic field
Related topics
• Electromagnetic radiation
• Introduction to spectroscopy
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Separations
Introduction
A sample that requires analysis is often a mixture of many components in a complex matrix. For
samples containing unknown compounds, the components must be separated from each other so
that each individual component can be identified by other analytical methods. The separation
properties of the components in a mixture are constant under constant conditions, and therefore
once determined they can be used to identify and quantify each of the components. Such
procedures are typical in chromatographic and electrophoretic analytical separations.
A mixture can be separated using the the differences in physical or chemical properties of the
individual components. As an example, dumping spaghetti and water in a colander separates the
two components because the liquid water can run through the colander but the solid spaghetti
cannot (assuming that it is not grossly overcooked as prepared in some university dining halls).
Some water will stick to the spaghetti and some spaghetti may go down the drain because the
colander is not 100% efficient. An analagous example is the filtering of a solid precipitate to
separate it from a solution. These separations are based on the states of matter of the two
components, other physical properties that are useful for separations are density and size. Some
useful chemical properties by which compounds can be separated are solubility, boiling point,
and vapor pressure.
Simple separation procedures
• Centrifugation
• Crystallization
• Distillation
• Extraction
• Filtering
Instrumental separation procedures
• Chromatography
• Electrophoresis
<
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures | Data
Analysis
Extraction
Introduction
Extractions use two immiscible phases to separate a solute from one phase into the other. The
distribution of a solute between two phases is an equilibrium condition described by partition
theory. Boiling tea leaves in water extracts the tannins, theobromine, and caffeine (the good
stuff) out of the leaves and into the water. More typical lab extractions are of organic compounds
out of an aqueous phase and into an organic phase.
Illustration of an extraction in a separatory funnel
Analytical Extractions
Elemental analysis generally requires fairly simple (not necessarily easy) sample preparation.
Solids are usually dissolved or digested in caustic solution and liquids are sometimes extracted to
separate the analyte from interferences.
Organic analysis is often much more complicated. Real-world samples can be very complicated
matrices that require careful extraction procedures to obtain the analyte(s) in a form that can be
analyzed.
Department of Chemistry
Stage 2 Chemistry Social Relevance Projects.
Home | Contents | Cross Referenced Index | Experimental Procedures
Data Analysis
Introduction
Since analytical chemistry is the science of making quantitative measurements, understanding
the difference between accuracy and precision is vital. Also, it is important that raw data is
manipulated and reported correctly to give a realistic estimate of the uncertainty in a result.
Presentation of data in the form of graphs is extremely useful.
Simple data manipulations may only require keeping track of significant figures. More
complicated calculations require propagation-of-error methods.
The uncertainity in a result can be categorized into random error and systematic error.
See the statistical formula document for more quantitative descriptions of describing and testing
data sets.
See the statistics of sampling document for information about uncertainty involved in sampling.
