Analytical chemistry

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Analytical chemistry is the study of the separation, identification, and quantification of the chemical components of natural and artificial materials.[1] Qualitative analysis gives an indication of the identity of the chemical species in the sample and quantitative analysis determines the amount of one or more of these components. The separation of components is often performed prior to analysis.

Analytical methods can be separated into classical and instrumental.[2] Classical methods (also known as wet chemistry methods) use separations such as precipitation, extraction, and distillation and qualitative analysis by color, odor, or melting point. Quantitative analysis is achieved by measurement of weight or volume. Instrumental methods use an apparatus to measure physical quantities of the analyte such as light absorption, fluorescence, or conductivity. The separation of materials is accomplished using chromatography or electrophoresis methods.

Analytical chemistry is also focused on improvements in experimental design, chemometrics, and the creation of new measurement tools to provide better chemical information. Analytical chemistry has applications in forensics, bioanalysis, clinical analysis, environmental analysis, and materials analysis.

HistoryEdit

Analytical chemistry has been important since the early days of chemistry, providing methods for determining which elements and chemicals are present in the world around us. During this period significant analytical contributions to chemistry include the development of systematic elemental analysis by Justus von Liebig and systematized organic analysis based on the specific reactions of functional groups.

The first instrumental analysis was flame emissive spectrometry developed by Robert Bunsen and Gustav Kirchhoff who discovered rubidium (Rb) and caesium (Cs) in 1860.[3]

Most of the major developments in analytical chemistry take place after 1900. During this period instrumental analysis becomes progressively dominant in the field. In particular many of the basic spectroscopic and spectrometric techniques were discovered in the early 20th century and refined in the late 20th century.[4]

The separation sciences follow a similar time line of development and also become increasingly transformed into high performance instruments.[5] In the 1970s many of these techniques began to be used together to achieve a complete characterization of samples.

Starting in approximately the 1970s into the present day analytical chemistry has progressively become more inclusive of biological questions (bioanalytical chemistry), whereas it had previously been largely focused on inorganic or small organic molecules. Lasers have been increasingly used in chemistry as probes and even to start and influence a wide variety of reactions. The late 20th century also saw an expansion of the application of analytical chemistry from somewhat academic chemical questions to forensic, environmental, industrial and medical questions, such as in histology.[6]

Modern analytical chemistry is dominated by instrumental analysis. Many analytical chemists focus on a single type of instrument. Academics tend to either focus on new applications and discoveries or on new methods of analysis. The discovery of a chemical present in blood that increases the risk of cancer would be a discovery that an analytical chemist might be involved in. An effort to develop a new method might involve the use of a tunable laser to increase the specificity and sensitivity of a spectrometric method. Many methods, once developed, are kept purposely static so that data can be compared over long periods of time. This is particularly true in industrial quality assurance (QA), forensic and environmental applications. Analytical chemistry plays an increasingly important role in the pharmaceutical industry where, aside from QA, it is used in discovery of new drug candidates and in clinical applications where understanding the interactions between the drug and the patient are critical.

Classical methodsEdit

Although modern analytical chemistry is dominated by sophisticated instrumentation, the roots of analytical chemistry and some of the principles used in modern instruments are from traditional techniques many of which are still used today. These techniques also tend to form the backbone of most undergraduate analytical chemistry educational labs.

Qualitative analysisEdit

A qualitative analysis determines the presence or absence of a particular compound, but not the mass or concentration. That is, it is not related to quantity.

Chemical testsEdit

For more details on this topic, see Chemical test.

There are numerous qualitative chemical tests, for example, the acid test for gold and the Kastle-Meyer test for the presence of blood.

Flame testEdit

For more details on this topic, see Flame test.

Inorganic qualitative analysis generally refers to a systematic 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. Sometimes small carbon containing ions are included in such schemes. With modern instrumentation these tests are rarely used but can be useful for educational purposes and in field work or other situations where access to state-of-the-art instruments are not available or expedient.

Gravimetric analysisEdit

For more details on this topic, see Gravimetric analysis.

Gravimetric analysis involves determining the amount of material present by weighing the sample before and/or after some transformation. A common example used in undergraduate education is the determination of the amount of water in a hydrate by heating the sample to remove the water such that the difference in weight is due to the loss of water.

Volumetric analysisEdit

For more details on this topic, see Titration.

Titration involves the addition of a reactant to a solution being analyzed until some equivalence point is reached. Often the amount of material in the solution being analyzed may be determined. Most familiar to those who have taken college chemistry is the acid-base titration involving a color changing indicator. There are many other types of titrations, for example potentiometric titrations. These titrations may use different types of indicators to reach some equivalence point.

Instrumental methodsEdit

Main article: Instrumental analysis

SpectroscopyEdit

For more details on this topic, see 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, dual polarisation interferometry, nuclear magnetic resonance spectroscopy, photoemission spectroscopy, Mössbauer spectroscopy and so on.

Mass spectrometryEdit

For more details on this topic, see Mass spectrometry.

Mass spectrometry measures mass-to-charge ratio of molecules using electric and magnetic fields. There are several ionization methods: electron impact, chemical ionization, electrospray, fast atom bombardment, matrix assisted laser desorption ionization, and others. Also, mass spectrometry is categorized by approaches of mass analyzers: magnetic-sector, quadrupole mass analyzer, quadrupole ion trap, time-of-flight, Fourier transform ion cyclotron resonance, and so on.

Electrochemical analysisEdit

For more details on this topic, see Electroanalytical method.

Electroanalytical methods measure the potential (volts) and/or current (amps) in an electrochemical cell containing the analyte.[7][8] These methods can be categorized according to which aspects of the cell are controlled and which are measured. The three main categories are potentiometry (the difference in electrode potentials is measured), coulometry (the cell's current is measured over time), and voltammetry (the cell's current is measured while actively altering the cell's potential).

Thermal analysisEdit

Further information: Calorimetry, thermal analysis

Calorimetry and thermogravimetric analysis measure the interaction of a material and heat.

SeparationEdit

Further information: Separation process, Chromatography, electrophoresis

Separation processes are used to decrease the complexity of material mixtures. Chromatography and electrophoresis are representative of this field.

Hybrid techniquesEdit

Combinations of the above techniques produce a "hybrid" or "hyphenated" technique.[9][10][11][12][13] Several examples are in popular use today and new hybrid techniques are under development. For example, gas chromatography-mass spectrometry, gas chromatography-infrared spectroscopy, liquid chromatography-mass spectrometry, liquid chromatography-NMR spectroscopy. liquid chromagraphy-infrared spectroscopy and capillary electrophoresis-mass spectrometry.

Hyphenated separation techniques refers to a combination of two (or more) techniques to detect and separate chemicals from solutions. Most often the other technique is some form of chromatography. Hyphenated techniques are widely used in chemistry and biochemistry. A slash is sometimes used instead of hyphen, especially if the name of one of the methods contains a hyphen itself.

MicroscopyEdit

For more details on this topic, see Microscopy.

The visualization of single molecules, single cells, biological tissues and nanomaterials is an important and attractive approach in analytical science. Also, hybridization with other traditional analytical tools is revolutionizing analytical science. Microscopy can be categorized into three different fields: optical microscopy, electron microscopy, and scanning probe microscopy. Recently, this field is rapidly progressing because of the rapid development of the computer and camera industries.

Lab-on-a-chipEdit

Further information: microfluidics, lab-on-a-chip

Devices that integrate (multiple) laboratory functions on a single chip of only millimeters to a few square centimeters in size and that are capable of handling extremely small fluid volumes down to less than pico liters.

StandardsEdit

Standard curveEdit

A general method for analysis of concentration involves the creation of a calibration curve. This allows for determination of the amount of a chemical in a material by comparing the results of unknown sample to those of a series known standards. If the concentration of element or compound in a sample is too high for the detection range of the technique, it can simply be diluted in a pure solvent. If the amount in the sample is below an instrument's range of measurement, the method of addition can be used. In this method a known quantity of the element or compound under study is added, and the difference between the concentration added, and the concentration observed is the amount actually in the sample.

Internal standardsEdit

Sometimes an internal standard is added at a known concentration directly to an analytical sample to aid in quantitation. The amount of analyte present is then determined relative to the internal standard as a calibrant.

The method of standard addition is used in instrumental analysis to determine concentration of a substance (analyte) in an unknown sample by comparison to a set of samples of known concentration, similar to using a calibration curve. Standard addition can be applied to most analytical techniques and is used instead of a calibration curve to solve the matrix effect problem.

Signals and noiseEdit

One of the most important components of analytical chemistry is maximizing the desired signal while minimizing the associated noise.[15] The analytical figure of merit is known as the signal-to-noise ratio (S/N or SNR).

Noise can arise from environmental factors as well as from fundamental physical processes.

Thermal noiseEdit

Main article: Johnson–Nyquist noise

Thermal noise results from the motion of charge carriers (usually electrons) in an electrical circuit generated by their thermal motion. Thermal noise is white noise meaning that the power spectral density is constant throughout the frequency spectrum.

The root mean square value of the thermal noise in a resistor is given by[15]

$v_{{RMS}} = \sqrt { 4 k_B T R \Delta f },$

where kB is Boltzmann's constant, T is the temperature, R is the resistance, and $\Delta f$ is the bandwidth of the frequency $f$.

Shot noiseEdit

Main article: Shot noise

Shot noise is a type of electronic noise that occurs when the finite number of particles (such as electrons in an electronic circuit or photons in an optical device) is small enough to give rise to statistical fluctuations in a signal.

Shot noise is a Poisson process and the charge carriers that make up the current follow a Poisson distribution. The root mean square current fluctuation is given by[15]

$i_{{RMS}}=\sqrt{2\,e\,I\,\Delta f}$

where e is the elementary charge and I is the average current. Shot noise is white noise.

Flicker noiseEdit

Main article: flicker noise

Flicker noise is electronic noise with a 1/ƒ frequency spectrum; as f increases, the noise decreases. Flicker noise arises from a variety of sources, such as impurities in a conductive channel, generation and recombination noise in a transistor due to base current, and so on. This noise can be avoided by modulation of the signal at a higher frequency, for example through the use of a lock-in amplifier.

Environmental noiseEdit

Environmental noise arises from the surroundings of the analytical instrument. Sources of electromagnetic noise are power lines, radio and television stations, wireless devices and electric motors. Many of these noise sources are narrow bandwidth and therefore can be avoided. Temperature and vibration isolation may be required for some instruments.

Noise reductionEdit

Noise reduction can be accomplished either in hardware or software. Examples of hardware noise reduction are the use of shielded cable, analog filtering, and signal modulation. Examples of software noise reduction are digital filtering, ensemble average, boxcar average, and correlation methods.[15]

ApplicationsEdit

Analytical chemistry research is largely driven by performance (sensitivity, selectivity, robustness, linear range, accuracy, precision, and speed), and cost (purchase, operation, training, time, and space). Among the main branches of contemporary analytical atomic spectrometry, the most widespread and universal are optical and mass spectrometry.[16] In the direct elemental analysis of solid samples, the new leaders are laser-induced breakdown and laser ablation mass spectrometry, and the related techniques with transfer of the laser ablation products into inductively coupled plasma. Advances in design of diode lasers and optical parametric oscillators promote developments in fluorescence and ionization spectrometry and also in absorption techniques where uses of optical cavities for increased effective absorption pathlength are expected to expand. Steady progress and growth in applications of plasma- and laser-based methods are noticeable. An interest towards the absolute (standardless) analysis has revived, particularly in the emission spectrometry.

A lot of effort is put in shrinking the analysis techniques to chip size. Although there are few examples of such systems competitive with traditional analysis techniques, potential advantages include size/portability, speed, and cost. (micro Total Analysis System (µTAS) or Lab-on-a-chip). Microscale chemistry reduces the amounts of chemicals used.

Much effort is also put into analyzing biological systems. Examples of rapidly expanding fields in this area are:

• Genomics - DNA sequencing and its related research. Genetic fingerprinting and DNA microarray are very popular tools and research fields.
• Proteomics - the analysis of protein concentrations and modifications, especially in response to various stressors, at various developmental stages, or in various parts of the body.
• Metabolomics - similar to proteomics, but dealing with metabolites.
• Transcriptomics - mRNA and its associated field
• Lipidomics - lipids and its associated field
• Peptidomics - peptides and its associated field
• Metalomics - similar to proteomics and metabolomics, but dealing with metal concentrations and especially with their binding to proteins and other molecules.

Analytical chemistry has played critical roles in the understanding of basic science to a variety of practical applications, such as biomedical applications, environmental monitoring, quality control of industrial manufacturing, forensic science and so on.

The recent developments of computer automation and information technologies have innervated analytical chemistry to initiate a number of new biological fields. For example, automated DNA sequencing machines were the basis to complete human genome projects leading to the birth of genomics. Protein identification and peptide sequencing by mass spectrometry opened a new field of proteomics. Furthermore, a number of ~omics based on analytical chemistry have become important areas in modern biology.

Also, analytical chemistry has been an indispensable area in the development of nanotechnology. Surface characterization instruments, electron microscopes and scanning probe microscopes enables scientists to visualize atomic structures with chemical characterizations.

Among active contemporary analytical chemistry research fields, micro total analysis system is considered as a great promise of revolutionary technology. In this approach, integrated and miniaturized analytical systems are being developed to control and analyze single cells and single molecules. This cutting-edge technology has a promising potential of leading a new revolution in science as integrated circuits did in computer developments.

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ReferencesEdit

1. Holler, F. James; Skoog, Douglas A.; West, Donald M. (1996). Fundamentals of analytical chemistry, Philadelphia: Saunders College Pub.
2. Nieman, Timothy A.; Skoog, Douglas A.; Holler, F. James (1998). Principles of instrumental analysis, Pacific Grove, CA: Brooks/Cole.
3. ANALYTICAL SCIENCES 2001, VOL.17 SUPPLEMENT [1], Basic Education in Analytical Chemistry
4. Talanta Volume 51, Issue 5, p921-933 [2], Review of analytical next term measurements facilitated by drop formation technology
5. TrAC Trends in Analytical Chemistry Volume 21, Issues 9-10, Pages 547-557 [3], History of gas chromatography
6. Talanta, Volume 36, Issues 1-2, January–February 1989, Pages 1-9 [4] History of analytical chemistry in the U.S.A.
7. Bard, A.J.; Faulkner, L.R. Electrochemical Methods: Fundamentals and Applications. New York: John Wiley & Sons, 2nd Edition, 2000.
8. Skoog, D.A.; West, D.M.; Holler, F.J. Fundamentals of Analytical Chemistry New York: Saunders College Publishing, 5th Edition, 1988.
9. Wilkins CL (1983). Hyphenated techniques for analysis of complex organic mixtures. Science 222 (4621): 291–6.
10. Holt RM, Newman MJ, Pullen FS, Richards DS, Swanson AG (1997). High-performance liquid chromatography/NMR spectrometry/mass spectrometry: further advances in hyphenated technology. Journal of mass spectrometry : JMS 32 (1): 64–70.
11. Ellis LA, Roberts DJ (1997). Chromatographic and hyphenated methods for elemental speciation analysis in environmental media. Journal of chromatography. A 774 (1–2): 3–19.
12. Guetens G, De Boeck G, Wood M, Maes RA, Eggermont AA, Highley MS, van Oosterom AT, de Bruijn EA, Tjaden UR (2002). Hyphenated techniques in anticancer drug monitoring. I. Capillary gas chromatography-mass spectrometry. Journal of chromatography. A 976 (1–2): 229–38.
13. Guetens G, De Boeck G, Highley MS, Wood M, Maes RA, Eggermont AA, Hanauske A, de Bruijn EA, Tjaden UR (2002). Hyphenated techniques in anticancer drug monitoring. II. Liquid chromatography-mass spectrometry and capillary electrophoresis-mass spectrometry. Journal of chromatography. A 976 (1–2): 239–47.
14. (2008). Subdiffraction Multicolor Imaging of the Nuclear Periphery with 3D Structured Illumination Microscopy. Science 320 (5881): 1332.
15. 15.0 15.1 15.2 15.3 Crouch, Stanley; Skoog, Douglas A. (2007). Principles of instrumental analysis, Australia: Thomson Brooks/Cole.
16. (2006). Prospects in analytical atomic spectrometry. Russian Chemical Reviews 75 (4): 289.