Composition Sensors

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Contents
Articles
Gas chromatography Voltammetry Photometer pH meter Electrometer Calorimeter Spectrometer Spectrophotometry 1 10 14 16 19 23 28 31

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Gas chromatography

Gas chromatography
Gas chromatography

A gas chromatograph with a headspace sampler Acronym Classification Analytes GC chromatography organic inorganic must be volatile

Manufacturers Agilent Bruker HTA PerkinElmer Shimadzu SRI Instruments Thermo Fisher Scientific LECO Corporation Alpha MOS - Perichrom VICI Valco Instruments Vernier Software & Technology Other techniques Related Thin layer chromatography High performance liquid chromatography Gas chromatography-mass spectrometry

Hyphenated

Gas chromatography (GC), is a common type of chromatography used in analytical chemistry for separating and analysing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, or separating the different components of a mixture (the relative amounts of such components can also be determined). In some situations, GC may help in identifying a compound. In preparative chromatography, GC can be used to prepare pure compounds from a mixture.[1] In gas chromatography, the mobile phase (or "moving phase") is a carrier gas, usually an inert gas such as helium or an unreactive gas such as nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid

Gas chromatography support, inside a piece of glass or metal tubing called a column (an homage to the fractionating column used in distillation). The instrument used to perform gas chromatography is called a gas chromatograph (or "aerograph", "gas separator"). The gaseous compounds being analyzed interact with the walls of the column, which is coated with different stationary phases. This causes each compound to elute at a different time, known as the retention time of the compound. The comparison of retention times is what gives GC its analytical usefulness. Gas chromatography is in principle similar to column chromatography (as well as other forms of chromatography, such as HPLC, TLC), but has several notable differences. Firstly, the process of separating the compounds in a mixture is carried out between a liquid stationary phase and a gas mobile phase, whereas in column chromatography the stationary phase is a solid and the mobile phase is a liquid. (Hence the full name of the procedure is "Gasliquid chromatography", referring to the mobile and stationary phases, respectively.) Secondly, the column through which the gas phase passes is located in an oven where the temperature of the gas can be controlled, whereas column chromatography (typically) has no such temperature control. Thirdly, the concentration of a compound in the gas phase is solely a function of the vapor pressure of the gas.[1] Gas chromatography is also similar to fractional distillation, since both processes separate the components of a mixture primarily based on boiling point (or vapor pressure) differences. However, fractional distillation is typically used to separate components of a mixture on a large scale, whereas GC can be used on a much smaller scale (i.e. microscale).[1] Gas chromatography is also sometimes known as vapor-phase chromatography (VPC), or gasliquid partition chromatography (GLPC). These alternative names, as well as their respective abbreviations, are frequently found in scientific literature. Strictly speaking, GLPC is the most correct terminology, and is thus preferred by many authors.[1]

History
Chromatography dates to 1903 in the work of the Russian scientist, Mikhail Semenovich Tswett. German graduate student Fritz Prior developed solid state gas chromatography in 1947. Archer John Porter Martin, who was awarded the Nobel Prize for his work in developing liquidliquid (1941) and paper (1944) chromatography, laid the foundation for the development of gas chromatography and he later produced liquid-gas chromatography (1950). Erika Cremer laid the groundwork, and oversaw much of Prior's work.

GC analysis
A gas chromatograph is a chemical analysis instrument for separating chemicals in a complex sample. A gas chromatograph uses a flow-through narrow tube known as the column, through which different chemical constituents of a sample pass in a gas stream (carrier gas, mobile phase) at different rates depending on their various chemical and physical properties and their interaction with a specific column filling, called the stationary phase. As the chemicals exit the end of the column, they are detected and identified electronically. The function of the stationary phase in the column is to separate different components, causing each one to exit the column at a different time (retention time). Other parameters that can be used to alter the order or time of retention are the carrier gas flow rate, column length and the temperature. In a GC analysis, a known volume of gaseous or liquid analyte is injected into the "entrance" (head) of the column, usually using a microsyringe (or, solid phase microextraction fibers, or a gas source switching system). As the carrier gas sweeps the analyte molecules through the column, this motion is inhibited by the adsorption of the analyte molecules either onto the column walls or onto packing materials in the column. The rate at which the molecules progress along the column depends on the strength of adsorption, which in turn depends on the type of molecule and on the stationary phase materials. Since each type of molecule has a different rate of progression, the various

Gas chromatography components of the analyte mixture are separated as they progress along the column and reach the end of the column at different times (retention time). A detector is used to monitor the outlet stream from the column; thus, the time at which each component reaches the outlet and the amount of that component can be determined. Generally, substances are identified (qualitatively) by the order in which they emerge (elute) from the column and by the retention time of the analyte in the column.

Physical components
Autosamplers
The autosampler provides the means to introduce a sample automatically into the inlets. Manual insertion of the sample is possible but is no longer common. Automatic insertion provides better reproducibility and time-optimization. Different kinds of autosamplers exist. Autosamplers can be classified in relation to sample capacity Diagram of a gas chromatograph. (auto-injectors vs. autosamplers, where auto-injectors can work a small number of samples), to robotic technologies (XYZ robot vs. rotating robot the most common), or to analysis: Liquid Static head-space by syringe technology Dynamic head-space by transfer-line technology Solid phase microextraction (SPME)

Traditionally autosampler manufacturers are different from GC manufacturers and currently no GC manufacturer offers a complete range of autosamplers. Historically, the countries most active in autosampler technology development are the United States, Italy, Switzerland, and the United Kingdom.

Inlets
The column inlet (or injector) provides the means to introduce a sample into a continuous flow of carrier gas. The inlet is a piece of hardware attached to the column head. Common inlet types are: S/SL (Split/Splitless) injector; a sample is introduced into a heated small chamber via a syringe through a septum the heat facilitates volatilization of the sample and sample matrix. The carrier gas then either sweeps the entirety (splitless mode) or a portion (split mode) of the sample into the column. In split mode, a part of the sample/carrier gas mixture in the injection chamber is exhausted through the split vent. Split injection is preferred when working with samples with high analyte concentrations (>0.1%) whereas splitless injection is best suited for trace analysis with low amounts of analytes (<0.01%). In splitless mode the split valve opens after a pre-set amount of time to purge heavier elements that would otherwise contaminate the system. This pre-set (splitless) time should be optimized, the shorter time (e.g., 0.2 min) ensures less tailing but loss in response, the longer time (2 min) increases tailing but also signal. On-column inlet; the sample is here introduced directly into the column in its entirety without heat.

Gas chromatography PTV injector; Temperature-programmed sample introduction was first described by Vogt in 1979. Originally Vogt developed the technique as a method for the introduction of large sample volumes (up to 250 L) in capillary GC. Vogt introduced the sample into the liner at a controlled injection rate. The temperature of the liner was chosen slightly below the boiling point of the solvent. The low-boiling solvent was continuously evaporated and vented through the split line. Based on this technique, Poy developed the Programmed Temperature Vaporising injector; PTV. By introducing the sample at a low initial liner temperature many of the disadvantages of the classic hot injection techniques could be circumvented. Gas source inlet or gas switching valve; gaseous samples in collection bottles are connected to what is most commonly a six-port switching valve. The carrier gas flow is not interrupted while a sample can be expanded into a previously evacuated sample loop. Upon switching, the contents of the sample loop are inserted into the carrier gas stream. P/T (Purge-and-Trap) system; An inert gas is bubbled through an aqueous sample causing insoluble volatile chemicals to be purged from the matrix. The volatiles are 'trapped' on an absorbent column (known as a trap or concentrator) at ambient temperature. The trap is then heated and the volatiles are directed into the carrier gas stream. Samples requiring preconcentration or purification can be introduced via such a system, usually hooked up to the S/SL port. The choice of carrier gas (mobile phase) is important, with hydrogen being the most efficient and providing the best separation. However, helium has a larger range of flowrates that are comparable to hydrogen in efficiency, with the added advantage that helium is non-flammable, and works with a greater number of detectors. Therefore, helium is the most common carrier gas used.

Detectors
Detectors are the flame ionization detector (FID) and the thermal conductivity detector (TCD). Both are sensitive to a wide range of components, and both work over a wide range of concentrations. While TCDs are essentially universal and can be used to detect any component other than the carrier gas (as long as their thermal conductivities are different from that of the carrier gas, at detector temperature), FIDs are sensitive primarily to hydrocarbons, and are more sensitive to them than TCD. However, an FID cannot detect water. Both detectors are also quite robust. Since TCD is non-destructive, it can be operated in-series before an FID (destructive), thus providing complementary detection of the same analytes. Other detectors are sensitive only to specific types of substances, or work well only in narrower ranges of concentrations. They include: catalytic combustion detector (CCD), which measures combustible hydrocarbons and hydrogen. discharge ionization detector (DID), which uses a high-voltage electric discharge to produce ions. dry electrolytic conductivity detector (DELCD), which uses an air phase and high temperature (v. Coulsen) to measure chlorinated compounds. electron capture detector (ECD), which uses a radioactive Beta particle (electron) source to measure the degree of electron capture. flame photometric detector (FPD) flame ionization detector (FID) Hall electrolytic conductivity detector (ElCD) helium ionization detector (HID) Nitrogen Phosphorus Detector (NPD) Infrared Detector (IRD) mass selective detector (MSD) photo-ionization detector (PID) pulsed discharge ionization detector (PDD)

Gas chromatography thermal energy(conductivity) analyzer/detector (TEA/TCD) thermionic ionization detector (TID) Some gas chromatographs are connected to a mass spectrometer which acts as the detector. The combination is known as GC-MS. Some GC-MS are connected to an NMR spectrometer which acts as a backup detector. This combination is known as GC-MS-NMR. Some GC-MS-NMR are connected to an infrared spectrophotometer which acts as a backup detector. This combination is known as GC-MS-NMR-IR. It must, however, be stressed this is very rare as most analyses needed can be concluded via purely GC-MS.

Methods
The method is the collection of conditions in which the GC operates for a given analysis. Method development is the process of determining what conditions are adequate and/or ideal for the analysis required. Conditions which can be varied to accommodate a required analysis include inlet temperature, detector temperature, column temperature and temperature program, carrier gas and carrier gas flow rates, the column's stationary phase, diameter and length, inlet type and flow rates, sample size and injection technique. Depending on the detector(s) (see below) installed on the GC, there may be a number of detector conditions that can also be varied. Some GCs also include valves which can change the route of sample and carrier flow. The timing of the opening and closing of these valves can be important to method development.

This image above shows the interior of a GeoStrata Technologies Eclipse Gas Chromatograph that runs continuously in three minute cycles. Two valves are used to switch the test gas into the sample loop. After filling the sample loop with test gas, the valves are switched again applying carrier gas pressure to the sample loop and forcing the sample through the Column for separation.

Carrier gas selection and flow rates

Typical carrier gases include helium, nitrogen, argon, hydrogen and air. Which gas to use is usually determined by the detector being used, for example, a DID requires helium as the carrier gas. When analyzing gas samples, however, the carrier is sometimes selected based on the sample's matrix, for example, when analyzing a mixture in argon, an argon carrier is preferred, because the argon in the sample does not show up on the chromatogram. Safety and availability can also influence carrier selection, for example, hydrogen is flammable, and high-purity helium can be difficult to obtain in some areas of the world. (See: Heliumoccurrence and production.) As a result of helium becoming more scarce, hydrogen is often being substituted for helium as a carrier gas in several applications. The purity of the carrier gas is also frequently determined by the detector, though the level of sensitivity needed can also play a significant role. Typically, purities of 99.995% or higher are used. The most common purity grades required by modern instruments for the majority of sensitivities are 5.0 grades, or 99.999% pure meaning that there is a total of 10ppm of impurities in the carrier gas that could affect the results. The highest purity grades in common use are 6.0 grades, but the need for detection at very low levels in some forensic and environmental applications has driven the need for carrier gases at 7.0 grade purity and these are now commercially available. Trade names for typical purities include "Zero Grade," "Ultra-High Purity (UHP) Grade," "4.5 Grade" and "5.0 Grade."

Gas chromatography The carrier gas linear velocity affects the analysis in the same way that temperature does (see above). The higher the linear velocity the faster the analysis, but the lower the separation between analytes. Selecting the linear velocity is therefore the same compromise between the level of separation and length of analysis as selecting the column temperature. The linear velocity will be implemented by means of the carrier gas flow rate, with regards to the inner diameter of the column. With GCs made before the 1990s, carrier flow rate was controlled indirectly by controlling the carrier inlet pressure, or "column head pressure." The actual flow rate was measured at the outlet of the column or the detector with an electronic flow meter, or a bubble flow meter, and could be an involved, time consuming, and frustrating process. The pressure setting was not able to be varied during the run, and thus the flow was essentially constant during the analysis. The relation between flow rate and inlet pressure is calculated with Poiseuille's equation for compressible fluids. Many modern GCs, however, electronically measure the flow rate, and electronically control the carrier gas pressure to set the flow rate. Consequently, carrier pressures and flow rates can be adjusted during the run, creating pressure/flow programs similar to temperature programs.

Stationary compound selection

The polarity of the solute is crucial for the choice of stationary compound, which in an optimal case would have a similar polarity than the solute. Common stationary phases in open tubular columns are cyanopropylphenyl dimethyl polysiloxane, carbowax polyethyleneglycol, biscyanopropyl cyanopropylphenyl polysiloxane and diphenyl dimethyl polysiloxane. For packed columns more options are available.[2]

Inlet types and flow rates

The choice of inlet type and injection technique depends on if the sample is in liquid, gas, adsorbed, or solid form, and on whether a solvent matrix is present that has to be vaporized. Dissolved samples can be introduced directly onto the column via a COC injector, if the conditions are well known; if a solvent matrix has to be vaporized and partially removed, a S/SL injector is used (most common injection technique); gaseous samples (e.g., air cylinders) are usually injected using a gas switching valve system; adsorbed samples (e.g., on adsorbent tubes) are introduced using either an external (on-line or off-line) desorption apparatus such as a purge-and-trap system, or are desorbed in the S/SL injector (SPME applications).

Gas chromatography

Sample size and injection technique

Sample injection The real chromatographic analysis starts with the introduction of the sample onto the column. The development of capillary gas chromatography resulted in many practical problems with the injection technique. The technique of on-column injection, often used with packed columns, is usually not possible with capillary columns. The injection system in the capillary gas chromatograph should fulfil the following two requirements: 1. The amount injected should not The rule of ten in gas chromatography overload the column. 2. The width of the injected plug should be small compared to the spreading due to the chromatographic process. Failure to comply with this requirement will reduce the separation capability of the column. As a general rule, the volume injected, Vinj, and the volume of the detector cell, Vdet, should be about 1/10 of the volume occupied by the portion of sample containing the molecules of interest (analytes) when they exit the column. Some general requirements which a good injection technique should fulfill are: It should be possible to obtain the columns optimum separation efficiency. It should allow accurate and reproducible injections of small amounts of representative samples. It should induce no change in sample composition. It should not exhibit discrimination based on differences in boiling point, polarity, concentration or thermal/catalytic stability. It should be applicable for trace analysis as well as for undiluted samples. '''Select dimensions of column for corresponding samples and GC System[Limit Temp]''[Dec-2009]'

Column selection
The choice of column depends on the sample and the active measured. The main chemical attribute regarded when choosing a column is the polarity of the mixture, but functional groups can play a large part in column selection. The polarity of the sample must closely match the polarity of the column stationary phase to increase resolution and separation while reducing run time. The separation and run time also depends on the film thickness (of the stationary phase), the column diameter and the column length.

Gas chromatography

Column temperature and temperature program

The column(s) in a GC are contained in an oven, the temperature of which is precisely controlled electronically. (When discussing the "temperature of the column," an analyst is technically referring to the temperature of the column oven. The distinction, however, is not important and will not subsequently be made in this article.) The rate at which a sample passes through the column is directly proportional to the temperature of the column. The higher the column temperature, the faster the sample moves through the column. However, the faster a sample moves through the column, the less it interacts with the stationary phase, and the less the analytes are separated. In general, the column temperature is selected to compromise between the length of the analysis and the level of separation.
A gas chromatography oven, open to show a capillary column

A method which holds the column at the same temperature for the entire analysis is called "isothermal." Most methods, however, increase the column temperature during the analysis, the initial temperature, rate of temperature increase (the temperature "ramp") and final temperature is called the "temperature program." A temperature program allows analytes that elute early in the analysis to separate adequately, while shortening the time it takes for late-eluting analytes to pass through the column.

Data reduction and analysis

Qualitative analysis: Generally chromatographic data is presented as a graph of detector response (y-axis) against retention time (x-axis), which is called a chromatogram. This provides a spectrum of peaks for a sample representing the analytes present in a sample eluting from the column at different times. Retention time can be used to identify analytes if the method conditions are constant. Also, the pattern of peaks will be constant for a sample under constant conditions and can identify complex mixtures of analytes. In most modern applications however the GC is connected to a mass spectrometer or similar detector that is capable of identifying the analytes represented by the peaks. Quantitative analysis: The area under a peak is proportional to the amount of analyte present in the chromatogram. By calculating the area of the peak using the mathematical function of integration, the concentration of an analyte in the original sample can be determined. Concentration can be calculated using a calibration curve created by finding the response for a series of concentrations of analyte, or by determining the relative response factor of an analyte. The relative response factor is the expected ratio of an analyte to an internal standard (or external standard) and is calculated by finding the response of a known amount of analyte and a constant amount of internal standard (a chemical added to the sample at a constant concentration, with a distinct retention time to the analyte). In most modern GC-MS systems, computer software is used to draw and integrate peaks, and match MS spectra to library spectra.

Gas chromatography

Application
In general, substances that vaporize below ca. 300 C (and therefore are stable up to that temperature) can be measured quantitatively. The samples are also required to be salt-free; they should not contain ions. Very minute amounts of a substance can be measured, but it is often required that the sample must be measured in comparison to a sample containing the pure, suspected substance known as a reference standard. Various temperature programs can be used to make the readings more meaningful; for example to differentiate between substances that behave similarly during the GC process. Professionals working with GC analyze the content of a chemical product, for example in assuring the quality of products in the chemical industry; or measuring toxic substances in soil, air or water. GC is very accurate if used properly and can measure picomoles of a substance in a 1 ml liquid sample, or parts-per-billion concentrations in gaseous samples. In practical courses at colleges, students sometimes get acquainted to the GC by studying the contents of Lavender oil or measuring the ethylene that is secreted by Nicotiana benthamiana plants after artificially injuring their leaves. These GC analyses hydrocarbons (C2-C40+). In a typical experiment, a packed column is used to separate the light gases, which are then detected with a TCD. The hydrocarbons are separated using a capillary column and detected with an FID. A complication with light gas analyses that include H2 is that He, which is the most common and most sensitive inert carrier (sensitivity is proportional to molecular mass) has an almost identical thermal conductivity to hydrogen (it is the difference in thermal conductivity between two separate filaments in a Wheatstone Bridge type arrangement that shows when a component has been eluted). For this reason, dual TCD instruments are used with a separate channel for hydrogen that uses nitrogen as a carrier are common. Argon is often used when analysing gas phase chemistry reactions such as F-T synthesis so that a single carrier gas can be used rather than 2 separate ones. The sensitivity is less but this is a tradeoff for simplicity in the gas supply.

GCs in popular culture

Movies, books and TV shows tend to misrepresent the capabilities of gas chromatography and the work done with these instruments. In the U.S. TV show CSI, for example, GCs are used to rapidly identify unknown samples. "This is gasoline bought at a Chevron station in the past two weeks," the analyst will say fifteen minutes after receiving the sample. In fact, a typical GC analysis takes much more time; sometimes a single sample must be run more than an hour according to the chosen program; and even more time is needed to "heat out" the column so it is free from the first sample and can be used for the next. Equally, several runs are needed to confirm the results of a study a GC analysis of a single sample may simply yield a result per chance (see statistical significance). Also, GC does not positively identify most samples; and not all substances in a sample will necessarily be detected. All a GC truly tells you is at which relative time a component eluted from the column and that the detector was sensitive to it. To make results meaningful, analysts need to know which components at which concentrations are to be expected; and even then a small amount of a substance can hide itself behind a substance having both a higher concentration and the same relative elution time. Last but not least it is often needed to check the results of the sample against a GC analysis of a reference sample containing only the suspected substance. A GC-MS can remove much of this ambiguity, since the mass spectrometer will identify the component's molecular weight. But this still takes time and skill to do properly. Similarly, most GC analyses are not push-button operations. You cannot simply drop a sample vial into an auto-sampler's tray, push a button and have a computer tell you everything you need to know about the sample. The operating program must be carefully chosen according to the expected sample composition.

Gas chromatography A push-button operation can exist for running similar samples repeatedly, such as in a chemical production environment or for comparing 20 samples from the same experiment to calculate the mean content of the same substance. However, for the kind of investigative work portrayed in books, movies and TV shows this is clearly not the case.

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References
[1] Pavia, Donald L., Gary M. Lampman, George S. Kritz, Randall G. Engel (2006). Introduction to Organic Laboratory Techniques (4th Ed.). Thomson Brooks/Cole. pp.797817. ISBN978-0-495-28069-9. [2] Harris, Daniel C. (1999). "24. Gas Chromatography". Quantitative chemical analysis (Chapter) (Fifth ed.). W. H. Freeman and Company. pp.675712. ISBN0-7167-2881-8.

External links
Gas Chromatography (http://www.dmoz.org/Science/Chemistry/Analytical/Separations_Science/ Gas_Chromatography/) at the Open Directory Project

Voltammetry
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied.[1][2]

Linear potential sweep

Potential as a function of time for anodic stripping voltammetry

Voltammetry

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Three electrode system

Voltammetry experiments investigate the half cell reactivity of an analyte. Voltammetry is the study of current as a function of applied potential. These curves I = f(E) are called voltammograms. The potential is varied arbitrarily either step by step or continuously, and the actual current value is measured as the dependent variable. The opposite, i.e., amperometry, is also possible but not common. The shape of the curves depends on the speed of potential variation (nature of driving force) and on whether the solution is stirred or quiescent (mass transfer). Most experiments control the potential (volts) of an electrode in contact with the analyte while measuring the resulting current (amperes).[3]

Three-electrode setup: (1) working electrode; (2) auxiliary electrode; (3) reference electrode

To conduct such an experiment requires at least two electrodes. The working electrode, which makes contact with the analyte, must apply the desired potential in a controlled way and facilitate the transfer of charge to and from the analyte. A second electrode acts as the other half of the cell. This second electrode must have a known potential with which to gauge the potential of the working electrode, furthermore it must balance the charge added or removed by the working electrode. While this is a viable setup, it has a number of shortcomings. Most significantly, it is extremely difficult for an electrode to maintain a constant potential while passing current to counter redox events at the working electrode. To solve this problem, the role of supplying electrons and referencing potential has been divided between two separate electrodes. The reference electrode is a half cell with a known reduction potential. Its only role is to act as reference in measuring and controlling the working electrodes potential and at no point does it pass any current. The auxiliary electrode passes all the current needed to balance the current observed at the working electrode. To achieve this current, the auxiliary will often swing to extreme potentials at the edges of the solvent window, where it oxidizes or reduces the solvent or supporting electrolyte. These electrodes, the working, reference, and auxiliary make up the modern three electrode system. There are many systems which have more electrodes, but their design principles are generally the same as the three electrode system. For example, the rotating ring-disk electrode has two distinct and separate working electrodes, a disk and a ring, which can be used to scan or hold potentials independently of each other. Both of these electrodes are balanced by a single reference and auxiliary combination for an over all four electrode design. More complicated experiments may add working electrodes as required and at times reference or auxiliary electrodes. In practice it can be very important to have a working electrode with known dimensions and surface characteristics. As a result, it is common to clean and polish working electrodes regularly. The auxiliary electrode can be almost anything as long as it doesn't react with the bulk of the analyte solution and conducts well. The reference is the most complex of the three electrodes, there are a variety of standards used and its worth investigating elsewhere. For non-aqueous work, IUPAC recommends the use of the ferrocene/ferrocenium couple as an internal standard.[4] In most voltammetry experiments, a bulk electrolyte (also known as a supporting electrolyte) is used to minimize solution resistance. It is possible to run an experiment without a bulk electrolyte, but the added resistance greatly reduces the accuracy of the results. With room temperature ionic liquids, the solvent can act as the electrolyte.

Voltammetry

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Theory
Data analysis requires the consideration of kinetics in addition to thermodynamics, due to the temporal component of voltammetry. Idealized theoretical electrochemical thermodynamic relationships such as the Nernst equation are modeled without a time component. While these models are insufficient alone to describe the dynamic aspects of voltammetry, models like the Nernst equation and Butler-Volmer equation lay the groundwork for the modified voltammetry relationships that relate theory to observed results.[5]

Types of voltammetry
Linear sweep voltammetry Staircase voltammetry Squarewave voltammetry Cyclic voltammetry - A voltammetric method that can be used to determine diffusion coefficients and half cell reduction potentials. Anodic stripping voltammetry - A quantitative, analytical method for trace analysis of metal cations. The analyte is deposited (electroplated) onto the working electrode during a deposition step, and then oxidized during the stripping step. The current is measured during the stripping step. Cathodic stripping voltammetry - A quantitative, analytical method for trace analysis of anions. A positive potential is applied, oxidizing the mercury electrode and forming insoluble precipitates of the anions. A negative potential then reduces (strips) the deposited film into solution. Adsorptive stripping voltammetry - A quantitative, analytical method for trace analysis. The analyte is deposited simply by adsorption on the electrode surface (i.e., no electrolysis), then electrolyzed to give the analytical signal. Chemically modified electrodes are often used. Alternating current voltammetry Polarography - a subclass of voltammetry where the working electrode is a dropping mercury electrode (DME), useful for its wide cathodic range and renewable surface. Rotated electrode voltammetry - A hydrodynamic technique in which the working electrode, usually a rotating disk electrode (RDE) or rotating ring-disk electrode (RRDE), is rotated at a very high rate. This technique is useful for studying the kinetics and electrochemical reaction mechanism for a half reaction. Normal pulse voltammetry Differential pulse voltammetry Chronoamperometry

History
The beginning of voltammetry was facilitated by the discovery of polarography in 1922 by the Nobel Prize winning chemist Jaroslav Heyrovsk. Early voltammetric techniques had many problems, limiting their viability for everyday use in analytical chemistry. In 1942 Hickling built the first three electrodes potentiostat.[6] The 1960s and 1970s saw many advances in the theory, instrumentation, and the introduction of computer added and controlled systems. These advancements improved sensitivity and created new analytical methods. Industry responded with the production of cheaper potentiostat, electrodes, and cells that could be effectively used in routine analytical work.

Voltammetry

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Applications
Voltammetric sensors A number of voltammetric systems are produced commercially for the determination of specific species that are of interest in industry and research. These devices are sometimes called electrodes but are, in fact, complete voltammetric cells and are better referred to as sensors. The oxygen electrode The determination of dissolved oxygen in a variety of aqueous environments, such as sea water, blood, sewage, effluents from chemical plants, and soils is of tremendous importance to industry, biomedical and environmental research, and clinical medicine. One of the most common and convenient methods for making such measurements is with the Clark oxygen sensor, which was patented by L.C. Clark, Jr. in 1956.

References
[1] Kissinger, Peter; William R. Heineman (1996-01-23). Laboratory Techniques in Electroanalytical Chemistry, Second Edition, Revised and Expanded (2 ed.). CRC. ISBN0824794451. [2] Zoski, Cynthia G. (2007-02-07). Handbook of Electrochemistry. Elsevier Science. ISBN0444519580. [3] Bard, Allen J.; Larry R. Faulkner (2000-12-18). Electrochemical Methods: Fundamentals and Applications (2 ed.). Wiley. ISBN0471043729. [4] Gritzner, G.; J. Kuta (1984). "Recommendations on reporting electrode potentials in nonaqueous solvents" (http:/ / iupac. org/ publications/ pac/ 56/ 4/ 0461/ ). Pure Appl. Chem. 56 (4): 461466. doi:10.1351/pac198456040461. . Retrieved 2009-04-17. [5] Nicholson, R. S.; Irving. Shain (1964-04-01). "Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.". Analytical Chemistry 36 (4): 706723. doi:10.1021/ac60210a007. [6] Hickling, A. (1942). "Studies in electrode polarisation. Part IV.-The automatic control of the potential of a working electrode". Transactions of the Faraday Society 38: 2733. doi:10.1039/TF9423800027.

Further reading
Reinmuth, W. H. (1961-11-01). "Theory of Stationary Electrode Polarography". Analytical Chemistry 33 (12): 17931794. doi:10.1021/ac60180a004. Skoog, Douglas A.; Donald M. West, F. James Holler (1995-08-25). Fundamentals of Analytical Chemistry (7th ed.). Harcourt Brace College Publishers. ISBN0030059380. Zanello, P. (2003-10-01). Inorganic Electrochemistry: Theory, Practice, and Application (1 ed.). Royal Society of Chemistry. ISBN0854046615.

External links
http://www.drhuang.com/science/chemistry/electrochemistry/polar.doc.htm http://new.ametek.com/content-manager/files/PAR/ App%20Note%20E-4%20-%20Electrochemical%20Analysis%20Techniques1.pdf http://www.prenhall.com/settle/chapters/ch37.pdf

Photometer

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Photometer
In its widest sense, a photometer is an instrument for measuring light intensity or optical properties of solutions or surfaces. Photometers are used to measure: Illuminance Irradiance Light absorption Scattering of light Reflection of light Fluorescence Phosphorescence Luminescence

A photometer

History
Before electronic light sensitive elements were developed, photometry was done by estimation by the eye. The relative luminous flux of a source was compared with a standard source. The photometer is placed such that the illuminance from the source being investigated is equal to that of the standard source as equal illuminance can be judged by the eye. The relative luminous fluxes can then be calculated as the illuminance decreases proportionally to the inverse square of distance. A standard example of such a photometer consists of a piece of paper with an oil spot on it that makes the paper there slightly more transparent. When the spot is not visible from either side, the illuminance from the two sides is equal.

Principle of photometers
Most photometers detect the light with photoresistors, photodiodes or photomultipliers. To analyze the light, the photometer may measure the light after it has passed through a filter or through a monochromator for determination at defined wavelengths or for analysis of the spectral distribution of the light.

Photon counting
Some photometers measure light by counting individual photons rather than incoming flux. The operating principles are the same but the results are given in units such as photons/cm2 or photonscm2sr1 rather than W/cm2 or Wcm2sr1. Due to their individual photon counting nature, these instruments are limited to observations where the irradiance is low. The irradiance is limited by the time resolution of its associated detector readout electronics. With current technology this is in the megahertz range. The maximum irradiance is also limited by the throughput and gain parameters of the detector itself. The light sensing element in photon counting devices in NIR, visible and ultrviolet wavelengths is a photomultiplier to achieve sufficient sensitivity. In airborne and space-based remote sensing such photon counters are used at the upper reaches of the electromagnetic spectrum such as the X-ray to far ultraviolet. This is usually due to the lower radiant intensity of the objects being measured as well as the difficulty of measuring light at higher energies using its particle-like nature as compared to the wavelike nature of light at lower frequencies. Conversely, radiometers are typically used for remote sensing from the visible, infrared though radio frequency range.

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Photography
Photometers are used to determine the correct exposure in photography. In modern cameras, the photometer is usually built in. As the illumination of different parts of the picture varies, advanced photometers measure the light intensity in different parts of the potential picture and use an algorithm to determine the most suitable exposure for the final picture, adapting the algorithm to the type of picture intended(see Metering mode). Historically, a photometer was separate from the camera. The advanced photometers then could be used either to measure the light from the potential picture as a whole, to measure from elements of the picture to ascertain that the most important parts of the picture are optimally exposed, or to measure the incident light to the scene with an integrating adapter.

Visible light reflectance photometry

A reflectance photometer measures the reflectance of a surface as a function of wavelength. The surface is illuminated with white light, and the reflected light is measured after passing through a monochromator. This type of measurement has mainly practical applications, for instance in the paint industry to characterize the colour of a surface objectively.

UV and visible light transmission photometry

These are optical instruments for measurement of the absorption of light of a given wavelength (or a given range of wavelengths) of coloured substances in solution. From the light absorption, Beer's law makes it possible to calculate the concentration of the coloured substance in the solution. Due to its wide range of application and its reliability and robustness, the photometer has become one of the principal instruments in biochemistry and analytical chemistry. Absorption photometers for work in aqueous solution work in the ultraviolet and visible ranges, from wavelength around 240nm up to 750nm. The principle of spectrophotometers and filter photometers is that (as far as possible) monochromatic light is allowed to pass through a container (cell) with optically flat windows containing the solution. It then reaches a light detector, that measures the intensity of the light compared to the intensity after passing through an identical cell with the same solvent but without the coloured substance. From the ratio between the light intensities, knowing the capacity of the coloured substance to absorb light (the absorbancy of the coloured substance, or the photon cross section area of the molecules of the coloured substance at a given wavelength), it is possible to calculate the concentration of the substance using Beer's law. Two types of photometers are used: spectrophotometer and filter photometer. In spectrophotometers a monochromator (with prism or with grating) is used to obtain monochromatic light of one defined wavelength. In filter photometers, optical filters are used to give the monochromatic light. Spectrophotometers can thus easily be set to measure the absorbance at different wavelengths, and they can also be used to scan the spectrum of the absorbing substance. They are in this way more flexible than filter photometers, also give a higher optical purity of the analyzing light, and therefore they are preferably used for research purposes. Filter photometers are cheaper, robuster and easier to use and therefore they are used for routine analysis. Photometers for microtiter plates are filter photometers.

Infrared light transmission photometry

Spectrophotometry in infrared light is mainly used to study structure of substances, as given groups give absorption at defined wavelengths. Measurement in aqueous solution is generally not possible, as water absorbs infrared light strongly in some wavelength ranges. Therefore, infrared spectroscopy is either performed in the gaseous phase (for volatile substances) or with the substances pressed into tablets together with salts that are transparent in the infrared range. Potassium bromide (KBr) is commonly used for this purpose. The substance to be tested is thoroughly mixed with specially purified KBr and pressed into a transparent tablet, that is placed in the beam of light. The analysis of

Photometer the wavelength dependence is generally not done using a monochromator as it is in UV-Vis, but with the use of an interferometer. The interference pattern can be analyzed using a Fourier transform algorithm. In this way, the whole wavelength range can be analyzed simultaneously, saving time, and an interferometer is also less expensive than a monochromator. The light absorbed in the infrared region does not correspond to electronic excitation of the substance studied, but rather to different kinds of vibrational excitation. The vibrational excitations are characteristic of different groups in a molecule, that can in this way be identified. The infrared spectrum typically has very narrow absorption lines, which makes them unsuited for quantitative analysis but gives very detailed information about the molecules. The frequencies of the different modes of vibration varies with isotope, and therefore different isotopes give different peaks. This makes it possible also to study the isotopic composition of a sample with infrared spectrophotometry.

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Atomic absorption photometry

Atomic absorption photometers are photometers that measure the light from a very hot flame. The solution to be analyzed is injected into the flame at a constant, known rate. Metals in the solution are present in atomic form in the flame. The monochromatic light in this type of photometer is generated by a discharge lamp where the discharge takes place in a gas with the metal to be determined. The discharge then emits light with wavelengths corresponding to the spectral lines of the metal. A filter may be used to isolate one of the main spectral lines of the metal to be analyzed. The light is absorbed by the metal in the flame, and the absorption is used to determine the concentration of the metal in the original solution.

pH meter
A pH meter is an electronic instrument used for measuring the pH (acidity or alkalinity) of a liquid (though special probes are sometimes used to measure the pH of semi-solid substances). A typical pH meter consists of a special measuring probe (a glass electrode) connected to an electronic meter that measures and displays the pH reading.

The probe
The pH probe measures pH as the activity of hydrogen cations surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06volt per pH unit) that is measured and displayed as pH units by the meter. For more information about pH probes, see glass electrode.

A pH meter

The meter
The meter circuit is no more than a voltmeter that displays measurements in pH units instead of volts. The input impedance of the meter must be very high because of the high resistance approximately 20 to 1000M of the glass electrode probes typically used with pH meters. The circuit of a simple pH meter usually consists of operational amplifiers in an inverting configuration, with a total voltage gain of about 17. The inverting amplifier converts the small voltage produced by the probe (+0.059volt/pH) into pH units, which are then offset by seven volts to give a reading on the pH scale. For example: At neutral pH (pH7) the voltage at the probe's output is 0volts. 0*17 + 7 = 7.

pH meter At basic pH, the voltage at the probe's output ranges from +0 to +0.41volts (7*0.059 = 0.41). So for a sample of pH10 (3 pH units above neutral), 3*0.059 = 0.18volts), the output of the meter's amplifier is 0.18*17 + 7 = 10. At acid pH, the voltage at the probe's output ranges from 0.41volts to 0. So for a sample of pH4 (3 pH units below neutral), 3*0.059 = 0.18volts, the output of the meter's amplifier is 0.18*17 + 7 = 3.94. The two basic adjustments performed at calibration (see below) set the gain and offset of the inverting amplifier.

17

Calibration and use

For very precise work the pH meter should be calibrated before each measurement. For normal use calibration should be performed at the beginning of each day. The reason for this is that the glass electrode does not give a reproducible e.m.f. over longer periods of time. Calibration should be performed with at least two standard buffer solutions that span the range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are acceptable. The pH meter has one control (calibrate) to set the meter reading equal to the value of the first standard buffer and a second control (slope) which is used to adjust the meter reading to the value of the second buffer. A third control allows the temperature to be set. Standard buffer sachets, which can be obtained from a variety of suppliers, usually state how the buffer value changes with temperature. For more precise measurements, a three buffer solution calibration is preferred. As pH 7 is essentially, a "zero point" calibration (akin to zeroing or taring a scale or balance), calibrating at pH 7 first, calibrating at the pH closest to the point of interest ( e.g. either 4 or 10) second and checking the third point will provide a more linear accuracy to what is essentially a non-linear problem. Some meters will allow a three point calibration and that is the preferred scheme for the most accurate work. Higher quality meters will have a provision to account for temperature coefficient correction, and high-end pH probes have temperature probes built in. The calibration process correlates the voltage produced by the probe (approximately 0.06volts per pH unit) with the pH scale. After each single measurement, the probe is rinsed with distilled water or deionized water to remove any traces of the solution being measured, blotted with a scientific wipe to absorb any remaining water which could dilute the sample and thus alter the reading, and then quickly immersed in another solution.

Storage conditions of the glass probes

When not in use, the glass probe tip must be kept wet at all times to avoid the pH sensing membrane dehydration and the subsequent dysfunction of the electrode. A glass electrode alone (i.e., without combined reference electrode) is typically stored immersed in an acidic solution of around pH 3.0. In an emergency, acidified tap water can be used, but distilled or deionised water must never be used for longer-term probe storage as the relatively ionless water "sucks" ions out of the probe membrane through diffusion, which degrades it. Combined electrodes (glass membrane + reference electrode) are better stored immersed in the bridge electrolyte (often KCl 3M) to avoid the diffusion of the electrolyte (KCl) out of the liquid junction.

Cleaning and troubleshooting of the glass probes

Occasionally (about once a month), the probe may be cleaned using pH-electrode cleaning solution; generally a 0.1M solution of hydrochloric acid (HCl) is used,[1] having a pH of about one. In case of strong degradation of the glass membrane performance due to membrane poisoning, diluted hydrofluoric acid (HF<2%) can be used to quickly etch (<1minute) a thin damaged film of glass. Alternatively a dilute solution of ammonium fluoride (NH4F) can be used. To avoid unexpected problems, the best practice is however to always refer to the electrode manufacturer recommendations or to a classical textbook of analytical chemistry.

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Types of pH meters
pH meters range from simple and inexpensive pen-like devices to complex and expensive laboratory instruments with computer interfaces and several inputs for indicator and temperature measurements to be entered to adjust for the slight variation in pH caused by temperature. Specialty meters and probes are available for use in special applications, harsh environments, etc.

History

A simple pH meter

The first commercial pH meters were built around 1936 by Radiometer in Denmark and by Arnold Orville Beckman in the United States. While Beckman was an assistant professor of chemistry at the California Institute of Technology, he was asked to devise a quick and accurate method for measuring the acidity of lemon juice for the California Fruit Growers Exchange (Sunkist). Beckman's invention helped him to launch the Beckman Instruments company (now Beckman Coulter). In 2004 the Beckman pH meter was designated an ACS National Historical Chemical Landmark in recognition of its significance as the first commercially successful electronic pH meter.[2] In the 1970s Jenco Electronics of Taiwan designed and manufactured the first portable digital pH meter. This meter was sold under Cole-Parmer's label.

Building a pH meter
Because the circuitry of a basic pH meter is quite simple, it is possible to build a serviceable pH meter or pH controller with parts available at a neighborhood electronics retailer. (pH probes, however, are not so easily acquired and must usually be ordered from a scientific instrument supplier.) For a walkthrough of how to build the simplest possible pH meter [3] or a detailed description of how to build a pH meter/pH controller [4], see The pH Pages [5]. The application note for the LM6001 [6] chip at the National Semiconductor web site also has a very simple demonstration circuit. Although the application note is for a specialty IC, serviceable pH meters can be built from any operational amplifier with a high input impedance, such as the common and inexpensive National Semiconductor TL082 [7] or its equivalent.

References
[1] [2] [3] [4] [5] [6] [7] Cleaning electrodes (http:/ / www. ph-meter. info/ pH-electrode-cleaning) The Beckman pH Meter (http:/ / acswebcontent. acs. org/ landmarks/ landmarks/ phmeter/ phmeter. html) http:/ / www. 66pacific. com/ ph/ simplest_ph. aspx http:/ / www. 66pacific. com/ ph/ ph_1. htm http:/ / www. 66pacific. com/ ph/ ph. aspx http:/ / www. national. com/ ds/ LM/ LMC6001. pdf http:/ / www. national. com/ pf/ TL/ TL082. html

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External links
Introduction to pH (http://www.omega.com/techref/ph.html) Excellent overview of pH and pH measurement at the Omega Engineering website The Beckman pH Meter (http://acswebcontent.acs.org/landmarks/landmarks/phmeter/phmeter.html) National Historic Chemical Landmark of the American Chemical Society

Electrometer
An electrometer is an electrical instrument for measuring electric charge or electrical potential difference. There are many different types, ranging from historical hand-made mechanical instruments to high-precision electronic devices. Modern electrometers based on vacuum tube or solid-state technology can be used to make voltage and charge measurements with very low leakage currents, down to 1 femtoampere. A simpler but related instrument, the electroscope, works on similar principles but only indicates the relative magnitudes of voltages or charges.

Volta Electrometers

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Older electrometers and charge indicating devices

Gold-leaf electroscopes
The gold-leaf electroscope was one of the first sensitive instruments used to indicate electric charge. It is still used for science demonstrations but has been superseded in most applications by electronic measuring instruments. The instrument consists of two thin leaves of gold foil suspended from an electrode. When the electrode is charged by induction or by contact, the leaves acquire similar electric charges and repel each other due to the Coulomb force. Their separation is a direct indication of the net charge stored on them. The leaves may be enclosed in a glass envelope to protect them from draughts, and the envelope may be evacuated to minimize charge leakage. A further cause of charge leakage is ionizing radiation, so to prevent this, the electrometer must be surrounded by lead shielding. This type of electroscope usually acts as an indicator and not a measuring device, although it can be calibrated. The Braun electroscope replaced the gold-leaf electroscope for more accurate measurements. For many years a common radiation measurement device, which was widely used in the nuclear industry, was the Quartz Fibre Electrometer (or QFE) personal dosimeter, which is actually a ruggedized, calibrated electroscope. It uses the leakage effect mentioned above to detect ionizing radiation. Though still in limited use, the QFE has been superseded by much more accurate radiation measurement devices. The Kearny Fallout Meter works the same way, though it uses aluminum foil rather than gold. The instrument was developed in the 18th century by several researchers, among them Abraham Bennet and Alessandro Volta.

Gold-leaf electroscope

Repulsion electrometers
Based on the same principle as the gold-leaf electroscope, repulsion electrometers are more sensitive indicating devices using a form of torsion balance. The most well-known designs are named after their inventors: Dellmann, Peltier, Bohenberger and others. The Peltier electrometer, developed by Jean Charles Peltier, uses a form of magnetic compass to measure deflection by balancing the electrostatic force with a magnetic needle.
Lord Kelvin's Quadrant Electrometer

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Attraction electrometers
Also known as Attracted Disk Electrometers, attraction electrometers are sensitive balances measuring the attraction between charged disks. William Snow Harris is credited with the invention of this instrument, which was further improved by Lord Kelvin.

Quadrant electrometers
Developed by Lord Kelvin, this is the most sensitive and accurate of all the mechanical electrometers. The original design uses a light aluminum sector suspended inside a drum cut into four segments. The segments are insulated and connected diagonally in pairs. The charged aluminum sector is attracted to one pair of segments and repelled from the other. The deflection is observed by a beam of light reflected from a small mirror attached to the sector, just as in a galvanometer. The engraving on the right shows a slightly different form of this electrometer, using four flat plates rather than closed segments. The plates can be connected externally in the conventional diagonal way (as shown), or in a different order for specific applications. A more sensitive form of quadrant electrometer was developed by Frederick Lindemann. It employs a metal-coated quartz fiber instead of an aluminum sector. The deflection is measured by observing the movement of the fiber under a microscope. Initially used for measuring star light, it was employed for the infrared detection of airplanes in the early stages of World War II. Some mechanic electrometers were housed inside a cage often referred to as a bird cage. This is a form of Faraday Cage that protected the instrument from external electrostatic charges.

Modern electrometers
In modern parlance, an electrometer is a highly sensitive electronic voltmeter whose input impedance is so high that the current flowing into it can be considered, for most practical purposes, to be zero. The actual value of input resistance for modern electronic electrometers is around 1014, compared to around 1010 for nanovoltmeters.[1][2] Among other applications, electrometers are of use in nuclear physics as they are able to measure the tiny charges left in matter by the passage of ionizing radiation. The most common use for modern electrometers is the measurement of radiation with ionization chambers, in instruments such as geiger counters.

Vibrating reed electrometers

Vibrating reed electrometers use a variable capacitor formed between a moving electrode (in the form of a vibrating reed) and a fixed input electrode. As the distance between the two electrodes varies, the capacitance also varies and electric charge is forced in and out of the capacitor. The alternating current signal produced by the flow of this charge is amplified and used as an analogue for the DC voltage applied to the capacitor. The input resistance of the electrometer is determined solely by the leakage resistance of the capacitor (although its AC input impedance is clearly somewhat larger). For convenience of use, the vibrating reed assembly is often attached by a cable to the rest of the electrometer. This allows for a relatively small unit to be located near the charge to be measured while the much larger reed-driver and amplifier unit can be located wherever it is convenient for the operator.

Valve electrometers
Valve electrometers use a specialized vacuum tube (thermionic valve) with a very high gain (transconductance) and input resistance. The input current is allowed to flow into the high impedance grid, and the voltage so generated is vastly amplified in the anode (plate) circuit. Valves designed for electrometer use have leakage currents as low as a few femtoamperes (1015 amperes). Such valves must be handled with gloved hands as the salts left on the glass envelope can provide leakage paths for these tiny currents.

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Solid-state electrometers
The most modern electrometers consist of a solid state amplifier using one or more field-effect transistors, connections for external measurement devices, and usually a display and/or data-logging connections. The amplifier amplifies small currents so that they are more easily measured. The external connections are usually of a co-axial or tri-axial design, and allow attachment of diodes or ionization chambers for radiation measurement. The display or data-logging connections allow the user to see the data or record it for later analysis. Electrometers designed for use with ionization chambers may include a high-voltage power supply, which is used to power the ionization chamber. Solid-state electrometers are often multipurpose devices that can measure voltage, charge, resistance and current. They measure voltage by means of "voltage balancing", in which the input voltage is compared with an internal reference voltage source using an electronic circuit with a very high input impedance (of the order of 1014 ohms). A similar circuit modified to act as a current-to-voltage converter enables the instrument to measure currents as small as a few femtoamperes. Combined with an internal voltage source, the current measuring mode can be adapted to measure very high resistances, of the order of 1017 ohms. Finally, by calculation from the known capacitance of the electrometer's input terminal, the instrument can measure very small electric charges, down to a small fraction of a picocoulomb. [3]

References
Dr. J. Frick, Physical Technics; Or Practical Instructions for Making Experiments in Physics Translated By John D. Easter, Ph.D. - J. B. Lippincott & Co., Philadelphia 1862 Robert Mfurgeson Ph.D. Electricity - William and Robert Chambers, London and Edinburgh 1866 Silvanus P. Thompson, Elementary Lessons in electricity and Magnetism. - Macmillan and Co. Limited, London 1905 Jones, R. V., Instruments and Experiences - John Wiley and Sons, London 1988
[1] Keithley, Making precision low current and high resistance measurements, "A greater measure of confidence" brochure, 2011, page 8 [2] Keithley, Nanovoltmeter 2182A, Datasheet, page 5 (http:/ / www. keithley. com/ data?asset=15912) [3] http:/ / www. keithley. com/ data?asset=11894

External links
Build this FET electrometer (http://www.amasci.com/emotor/chargdet.html) - A very simple circuit - 2 components Simple FET electrometer (http://www.vk2zay.net/article.php/9) - A simple bridged circuit An op-amp electrometer (http://amasci.com/electrom/sas51p1.html#Electro) Early electrometers (http://www.orau.org/ptp/collection/electrometers/electrometers.htm) Charging an Electroscope by Induction Using a Negatively-Charged Balloon (http://www.glenbrook.k12.il. us/gbssci/phys/mmedia/estatics/esn.html) from Multimedia Physics Studios 30 Years of Test & Measurement (http://www.techbriefs.com/component/content/article/148) Taking the Measure: Whats an electrometer? (http://www.tmworld.com/blog/640000064/post/1280008928. html)

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Calorimeter
A calorimeter (from Latin calor, meaning heat) is a device used for calorimetry, the science of measuring the heat of chemical reactions or physical changes as well as heat capacity. Differential scanning calorimeters, isothermal microcalorimeters, titration calorimeters and accelerated rate calorimeters are among the most common types. A simple calorimeter just consists of a thermometer attached to a metal container full of water suspended above a combustion chamber. To find the enthalpy change per mole of a substance A in a reaction between two substances A and B, the substances are added to a calorimeter and the initial and final temperatures (before the reaction started and after it has finished) are noted. Multiplying the temperature change by the mass and specific heat capacities of the substances gives a value for the energy given off or absorbed during the reaction. Dividing the energy change by how many moles of A were present gives its enthalpy change of reaction. This method is used primarily in academic teaching as it describes the theory of calorimetry. It does not account for the heat loss through the container or the heat capacity of the thermometer and container itself. In addition, the object placed inside the calorimeter show that the objects transferred their heat to the calorimeter and into the liquid, and the heat absorbed by the calorimeter and the liquid is equal to the heat given off by the metals.

Adiabatic calorimeters

The worlds first ice-calorimeter, used in the winter of 1782-83, by Antoine Lavoisier and Pierre-Simon Laplace, to determine the heat evolved in various chemical changes; calculations which were based on Joseph Blacks prior discovery of latent heat. These experiments mark the foundation of thermochemistry.

An adiabatic calorimeter is a calorimeter used to examine a runaway reaction. Since the calorimeter runs in an adiabatic environment, any heat generated by the material sample under test causes the sample to increase in temperature, thus fuelling the reaction. No adiabatic calorimeter is truly adiabatic - some heat will be lost by the sample to the sample holder. A mathematical correction factor, known as the phi-factor, can be used to adjust the calorimetric result to account for these heat losses. The phi-factor is the ratio of the thermal mass of the sample and sample holder to the thermal mass of the sample alone. Examples of adiabatic calorimeters are: THT EV-Accelerating Rate Calorimeter[1] HEL Phi-Tec[2] A simple Dewar flask Systag FlexyTSC[3] a successor of their SIKAREX unit - the electronics of which could be used to apply a feedback system to heat the sample holder to give a result closer to true adiabaticy, however as the sample holder is an open ended glass tube, one soon loses the sample as a great deal of smoke.

Reaction calorimeters
A reaction calorimeter is a calorimeter in which a chemical reaction is initiated within a closed insulated container. Reaction heats are measured and the total heat is obtained by integrating heatflow versus time. This is the standard used in industry to measure heats since industrial processes are engineered to run at constant temperatures. Reaction calorimetry can also be used to determine maximum heat release rate for chemical process engineering and for tracking the global kinetics of reactions. There are four main methods for measuring the heat in reaction calorimeter:

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Heat flow calorimetry

The cooling/heating jacket controls either the temperature of the process or the temperature of the jacket. Heat is measured by monitoring the temperature difference between heat transfer fluid and the process fluid. In addition fill volumes (i.e. wetted area), specific heat, heat transfer coefficient have to be determined to arrive at a correct value. It is possible with this type of calorimeter to do reactions at reflux, although the accuracy is not as good.

Heat balance calorimeter

The cooling/heating jacket controls the temperature of the process. Heat is measured by monitoring the heat gained or lost by the heat transfer fluid.

Power compensation
Power compensation uses a heater placed within the vessel to maintain a constant temperature. The energy supplied to this heater can be varied as reactions require and the calorimetry signal is purely derived from this electrical power.

Constant flux
Constant flux calorimetry (or COFLUX as it is often termed) is derived from heat balance calorimetry and uses specialized control mechanisms to maintain a constant heat flow (or flux) across the vessel wall.

Bomb calorimeters
A bomb calorimeter is a type of constant-volume calorimeter used in measuring the heat of combustion of a particular reaction. Bomb calorimeters have to withstand the large pressure within the calorimeter as the reaction is being measured. Electrical energy is used to ignite the fuel; as the fuel is burning, it will heat up the surrounding air, which expands and escapes through a tube that leads the air out of the calorimeter. When the air is escaping through the copper tube it will also heat up the water outside the tube. The temperature of the water allows for calculating calorie content of the fuel. In more recent calorimeter designs, the whole bomb, pressurized with excess pure oxygen (typically at 30atm) and containing a weighed mass of a sample (typically 1-1.5 g) and a small fixed amount of water Bomb calorimeter (to absorb produced acid gases), is submerged under a known volume of water (ca.2000 ml) before the charge is electrically ignited. The bomb, with the known mass of the sample and oxygen, form a closed system - no air escapes during the reaction. The weighted reactant put inside the steel container is then ignited. Energy is released by the combustion and heat flow from this crosses the stainless steel wall, thus raising the temperature of the steel bomb, its contents, and the surrounding water jacket. The temperature change in the water is then accurately measured with a thermometer. This reading, along with a bomb factor (which is dependent on the heat capacity of the metal bomb parts), is used to calculate the energy given out by the sample burn. A small correction is made to account for the electrical energy input, the burning fuse, and acid production (by titration of the residual liquid). After the temperature rise has been measured, the excess pressure in the bomb is released. Basically, a bomb calorimeter consists of a small cup to contain the sample, oxygen, a stainless steel bomb, water, a stirrer, a thermometer, the dewar or insulating container (to prevent heat flow from the calorimeter to the surroundings) and ignition circuit connected to the bomb. By using stainless steel for the bomb, the reaction will

Calorimeter occur with no volume change observed. Since there is no heat exchange between the calorimeter and surroundings Q = 0 (adiabatic) ; no work performed W = 0 Thus, the total internal energy change U(total) = Q + W = 0 Also, total internal energy change U(total) = U(system) + U(surroundings) = 0 U(system) = U(surroundings) = -Cv T (constant volume dV = 0) where Cv = heat capacity of the bomb Before the bomb can be used to determine heat of combustion of any compound, it must be calibrated. The value of Cv can be estimated by Cv (calorimeter) = m (water). Cv (water) + m (steel). Cv (steel) m (water) and m (steel) can be measured; Cv(water)= 1 cal/g.K Cv(steel)= 0.1 cal/g.K In laboratory, Cv is determined by running a compound with known heat of combustion value: Cv = Hc/T Common compounds are benzoic acid (Hc = 6318 cal/g) or p-methyl benzoic acid (Hc = 6957 cal/g). Temperature (T) is recorded every minute and T = T(final) - T(initial) A small factor contributes to the correction of the total heat of combustion is the fuse wire. Nickel fuse wire is often used and has heat of combustion = 981.3 cal/g In order to calibrate the bomb, a small amount (~ 1 g) of benzoic acid, or p-methyl benzoic acid is weighed. A length of Nickel fuse wire (~10cm) is weighed both before and after the combustion process. Mass of fuse wire burned m = m(before) - m(after) The combustion of sample (benzoic acid) inside the bomb Hc = Hc (benzoic acid) x m (benzoic acid) + Hc (Ni fuse wire) x m (Ni fuse wire) Hc = Cv. T Cv = Hc/T Once Cv value of the bomb is determined, the bomb is ready to use to calculate heat of combustion of any compounds by Hc = Cv. T
[4] [5]

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Calvet-type calorimeters
The detection is based on a three-dimensional fluxmeter sensor. The fluxmeter element consists of a ring of several thermocouples in series. The corresponding thermopile of high thermal conductivity surrounds the experimental space within the calorimetric block. The radial arrangement of the thermopiles guarantees an almost complete integration of the heat. This is verified by the calculation of the efficiency ratio that indicates that an average value of 94 % +/- 1 % of heat is transmitted through the sensor on the full range of temperature of the Calvet-type calorimeter. In this setup, the sensitivity of the calorimeter is not affected by the crucible, the type of purgegas, or the flow rate. The main advantage of the setup is the increase of the experimental vessel's size and consequently the size of the sample, without affecting the accuracy of the calorimetric measurement. The calibration of the calorimetric detectors is a key parameter and has to be performed very carefully. For Calvet-type calorimeters, a specific calibration, so called Joule effect or electrical calibration, has been developed to overcome all the problems encountered by a calibration done with standard materials. The main advantages of this type of calibration are as follows: It is an absolute calibration. The use of standard materials for calibration is not necessary. The calibration can be performed at a constant temperature, in the heating mode and in the cooling mode. It can be applied to any experimental vessel volume.

Calorimeter It is a very accurate calibration. An example of Calvet-type calorimeter is the C80 Calorimeter (reaction, isothermal and scanning calorimeter).[6]

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Constant-pressure calorimeter
A constant-pressure calorimeter measures the change in enthalpy of a reaction occurring in solution during which the atmospheric pressure remains constant. An example is a coffee-cup calorimeter, which is constructed from two nested Styrofoam cups and a lid with two holes, allowing insertion of a thermometer and a stirring rod. The inner cup holds a known amount of a solute, usually water, that absorbs the heat from the reaction. When the reaction occurs, the outer cup provides insulation. Then

where = Specific heat at constant pressure = Enthalpy of solution = Change in temperature = mass of solute = molecular mass of solute The measurement of heat using a simple calorimeter, like the coffee cup calorimeter, is an example of constant-pressure calorimetry, since the pressure (atmospheric pressure) remains constant during the process. Constant-pressure calorimetry is used in determining the changes in enthalpy occurring in solution. Under these conditions the change in enthalpy equals the heat.

Differential scanning calorimeter

In a differential scanning calorimeter (DSC), heat flow into a sampleusually contained in a small aluminium capsule or 'pan'is measured differentially, i.e., by comparing it to the flow into an empty reference pan. In a heat flux DSC, both pans sit on a small slab of material with a known (calibrated) heat resistance K. The temperature of the calorimeter is raised linearly with time (scanned), i.e., the heating rate dT/dt = is kept constant. This time linearity requires good design and good (computerized) temperature control. Of course, controlled cooling and isothermal experiments are also possible. Heat flows into the two pans by conduction. The flow of heat into the sample is larger because of its heat capacity Cp. The difference in flow dq/dt induces a small temperature difference T across the slab. This temperature difference is measured using a thermocouple. The heat capacity can in principle be determined from this signal:

Note that this formula (equivalent to Newton's law of heat flow) is analogous to, and much older than, Ohm's law of electric flow: V = R dQ/dt = R I. When suddenly heat is absorbed by the sample (e.g., when the sample melts), the signal will respond and exhibit a peak.

From the integral of this peak the enthalpy of melting can be determined, and from its onset the melting temperature. Differential scanning calorimetry is a workhorse technique in many fields, particularly in polymer characterization.

Calorimeter A modulated temperature differential scanning calorimeter (MTDSC) is a type of DSC in which a small oscillation is imposed upon the otherwise linear heating rate. This has a number of advantages. It facilitates the direct measurement of the heat capacity in one measurement, even in (quasi-)isothermal conditions. It permits the simultaneous measurement of heat effects that are reversible and not reversible at the timescale of the oscillation (reversing and non-reversing heat flow, respectively). It increases the sensitivity of the heat capacity measurement, allowing for scans at a slow underlying heating rate. Safety Screening:- DSC may also be used as an initial safety screening tool. In this mode the sample will be housed in a non-reactive crucible (often Gold, or Gold plated steel), and which will be able to withstand pressure (typically up to 100 bar). The presence of an exothermic event can then be used to assess the stability of a substance to heat. However, due to a combination of relatively poor sensitivity, slower than normal scan rates (typically 2-3/min - due to much heavier crucible) and unknonwn activation energy, it is necessary to deduct about 75-100C from the initial start of the observed exotherm to suggest a maximum temperature for the material. A much more accurate data set can be obtained from an adiabatic calorimeter, but such a test may take 23 days from ambient at a rate of 3C increment per half hour.

27

Isothermal titration calorimeter

In an isothermal titration calorimeter, the heat of reaction is used to follow a titration experiment. This permits determination of the mid point (stoichiometry) (N) of a reaction as well as its enthalpy (delta H), entropy (delta S) and of primary concern the binding affinity (Ka) The technique is gaining in importance particularly in the field of biochemistry, because it facilitates determination of substrate binding to enzymes. The technique is commonly used in the pharmaceutical industry to characterize potential drug candidates.

References
[1] [2] [3] [4] THT EV-ARC (http:/ / www. thermalhazardtechnology. com/ products/ ev-accelerating+ rate+ calorimeter) HEL Phi-Tec (http:/ / www. helgroup. com/ home/ reactor-systems/ safety. html?subpage=5) Systag FlexyTSC (http:/ / www. systag. ch/ E_400_TA. html) Polik, W. (1997). Bomb Calorimetery. Retrieved from http:/ / www. chem. hope. edu/ ~polik/Chem345-1997/calorimetry/bombcalorimetry1.html [5] Bozzelli, J. (2010). Heat of Combustion via Calorimetry: Detailed Procedures. Chem 339-Physical Chemistry Lab for Chemical Engineers Lab Manual. [6] C80 Calorimeter from Setaram Instrumentation (http:/ / www. setaram. com/ C80. htm)

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Spectrometer
A spectrometer (spectrophotometer, spectrograph or spectroscope) is an instrument used to measure properties of light over a specific portion of the electromagnetic spectrum, typically used in spectroscopic analysis to identify [1] materials. The variable measured is most often the light's intensity but could also, for instance, be the polarization state. The Grating spectrometer schematic independent variable is usually the wavelength of the light or a unit directly proportional to the photon energy, such as wavenumber or electron volts, which has a reciprocal relationship to wavelength. A spectrometer is used in spectroscopy for producing spectral lines and measuring their wavelengths and intensities. Spectrometer is a term that is applied to instruments that operate over a very wide range of wavelengths, from gamma rays and X-rays into the far infrared. If the instrument is designed to measure the spectrum in absolute units rather than relative units, then it is typically called a spectrophotometer. The majority of spectrophotomers are used in spectral regions near the visible spectrum. In general, any particular instrument will operate over a small portion of this total range because of the different techniques used to measure different portions of the spectrum. Below optical frequencies (that is, at microwave and radio frequencies), the spectrum analyzer is a closely related electronic device.

Spectroscopes
Spectroscope

Other names Related items

Spectrograph Mass spectrograph

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Spectroscopes are often used in astronomy and some branches of chemistry. Early spectroscopes were simply prisms with graduations marking wavelengths of light. Modern spectroscopes generally use a diffraction grating, a movable slit, and some kind of photodetector, all automated and controlled by a computer. The spectroscope was invented in 1819 by Joseph von Fraunhofer. Gustav Robert Kirchhoff and Robert Bunsen invented a spectroscope in 1859 that enabled the discovery of caesium and rubidium.[2][3] Kirchoff and Bunsen also explained the origin of Fraunhofer lines. When a material is heated to incandescence it emits light that is characteristic of the atomic makeup of the material. Particular light frequencies give rise to sharply defined bands on the scale which can be thought of as fingerprints. For example, the element sodium has a very characteristic double yellow band known as the Sodium D-lines at 588.9950 and 589.5924 nanometers, the color of which will be familiar to anyone who has seen a low pressure sodium vapor lamp. In the original spectroscope design in the early 19th century, light entered a slit and a collimating lens transformed the light into a thin Comparison of different diffraction based beam of parallel rays. The light then passed through a prism (in spectrometers: Reflection optics, refraction hand-held spectroscopes, usually an Amici prism) that refracted the optics, fiber optics beam into a spectrum because different wavelengths were refracted different amounts due to dispersion. This image was then viewed through a tube with a scale that was transposed upon the spectral image, enabling its direct measurement. With the development of photographic film, the more accurate spectrograph was created. It was based on the same principle as the spectroscope, but it had a camera in place of the viewing tube. In recent years the electronic circuits built around the photomultiplier tube have replaced the camera, allowing real-time spectrographic analysis with far greater accuracy. Arrays of photosensors are also used in place of film in spectrographic systems. Such spectral analysis, or spectroscopy, has become an important scientific tool for analyzing the composition of unknown material and for studying astronomical phenomena and testing astronomical theories. In modern spectrographs in the UV, visible, and near-IR spectral ranges, the spectrum is generally given in the form of photon number per unit wavelength (nm or m), wavenumber (m1, cm1), frequency (THz), or energy (eV), with the units indicated by the abscissa. In the mid- to far-IR, spectra are typically expressed in units of Watts per unit wavelength (m) or wavenumber (cm1). In many cases, the spectrum is displayed with the units left implied (such as "digital counts" per spectral channel).

A comparison of the four abscissa types typically used for visible spectrometers.

A comparison of the four abscissa types typically used for infrared spectrometers.

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A spectrograph is an instrument that separates an incoming wave into a frequency spectrum. There are several kinds of machines referred to as spectrographs, depending on the precise nature of the waves. The first spectrographs used photographic paper as the detector. The star spectral classification and discovery of the main sequence, Hubble's law and the Hubble sequence were all made with spectrographs that used photographic paper. The plant pigment phytochrome was discovered using a spectrograph that used living plants as the detector. More recent spectrographs use electronic detectors, such as CCDs which can be used for both visible and UV light. The exact choice of detector depends on the wavelengths of light to be recorded. An echelle spectrograph uses two diffraction gratings, rotated 90 degrees with respect to each other and placed close to one another. Therefore an entrance point and not a slit is used and a 2d CCD-chip records the spectrum. Usually one would guess to retrieve a spectrum on the diagonal, but when both gratings have a wide spacing and one is blazed so that only the first order is visible and the other is blazed that a lot of higher orders are visible, one gets a very fine spectrum nicely folded onto a small common A very simple spectroscope based on a prism CCD-chip. The small chip also means that the collimating optics need not to be optimized for coma or astigmatism, but the spherical aberration can be set to zero. A spectrograph is sometimes called polychromator, as an analogy to monochromator.

References
[1] L. R. P. Butler and K. Laqua (1995). "Nomenclature, symbols, units and their usage in spectrochemical analysis-IX. Instrumentation for the spectral dispersion and isolation of optical radiation (IUPAC Recommendations 1995)" (http:/ / iupac. org/ publications/ pac/ 67/ 10/ 1725/ ). Pure Appl. Chem. (IUPAC) 67 (10): 17251744. doi:10.1351/pac199567101725. . "A spectrometer is the general term for describing a combination of spectral apparatus with one or more detectors to measure the intensity of one or more spectral bands." [2] Weeks, Mary Elvira (1932). "The discovery of the elements. XIII. Some spectroscopic discoveries" (http:/ / pubs. acs. org/ doi/ abs/ 10. 1021/ ed009p1413). Journal of Chemical Education 9 (8): 14131434. Bibcode1932JChEd...9.1413W. doi:10.1021/ed009p1413. . Retrieved 2011-11-21. [3] "Robert Bunsen" (http:/ / www. infoplease. com/ biography/ var/ robertbunsen. html). infoplease. Pearson Education. 2007. . Retrieved 2011-11-21.

Bibliography
J. F. James and R. S. Sternberg (1969), The Design of Optical Spectrometers (Chapman and Hall Ltd) James, John (2007), Spectrograph Design Fundamentals (Cambridge University Press) ISBN 0521864631 Browning, John (1882), How to work with the spectroscope : a manual of practical manipulation with spectroscopes of all kinds (http://www.archive.org/details/howtoworkwithspe00browrich) Palmer, Christopher, Diffraction Grating Handbook, 6th edition, Newport Corporation (2005). (http://gratings. newport.com/library/handbook/cover.asp)

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External links
Spectrometer (http://www.dmoz.org/Science/Instruments_and_Supplies/Laboratory_Equipment/Spectroscopy/) at the Open Directory Project

Spectrophotometry
In chemistry, spectrophotometry is the quantitative measurement of the reflection or transmission properties of a material as a function of wavelength.[1] It is more specific than the general term electromagnetic spectroscopy in that spectrophotometry deals with visible light, near-ultraviolet, and near-infrared, but does not cover time-resolved spectroscopic techniques. Spectrophotometry involves the use of a spectrophotometer. A spectrophotometer is a photometer (a device for measuring light intensity) that can measure intensity as a function of the light source wavelength. Spectrophotometer Important features of spectrophotometers are spectral bandwidth and linear range of absorption or reflectance measurement. A spectrophotometer is commonly used for the measurement of transmittance or reflectance of solutions, transparent or opaque solids, such as polished glass, or gases. However they can also be designed to measure the diffusivity on any of the listed light ranges that usually cover around 200nm - 2500nm using different controls and calibrations.[2] Within these ranges of light, calibrations are needed on the machine using standards that vary in type depending on the wavelength of the photometric determination.[3] An example of an experiment in which spectrophotometry is used is the determination of the equilibrium constant of a solution. A certain chemical reaction within a solution may occur in a forward and reverse direction where reactants form products and products break down into reactants. At some point, this chemical reaction will reach a point of balance called an equilibrium point. In order to determine the respective concentrations of reactants and products at this point, the light transmittance of the solution can be tested using spectrophotometry. The amount of light that passes through the solution is indicative of the concentration of certain chemicals that do not allow light to pass through. The use of spectrophotometers spans various scientific fields, such as physics, materials science, chemistry, biochemistry, and molecular biology.[4] They are widely used in many industries including semiconductors, laser and optical manufacturing, printing and forensic examination, as well in laboratories for the study of chemical substances. Ultimately, a spectrophotometer is able to determine, depending on the control or calibration, what substances are present in a target and exactly how much through calculations of observed wavelengths.

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Design
There are two major classes of devices: single beam and double beam. A double beam spectrophotometer compares the light intensity between two light paths, one path containing a reference sample and the other the test sample. A single beam spectrophotometer measures the Single beam spectrophotometer relative light intensity of the beam before and after a test sample is inserted. Although comparison measurements from double beam instruments are easier and more stable, single beam instruments can have a larger dynamic range and are optically simpler and more compact. Additionally, some specialized instruments, such as spectrophotometer built onto microscopes or telescopes, are single beam instruments due to practicality. Historically, spectrophotometers use a monochromator containing a diffraction grating to produce the analytical spectrum. The grating can either be movable or fixed. If a single detector, such as a photomultiplier tube or photodiode is used, the grating can be scanned stepwise so that the detector can measure the light intensity at each wavelength (which will correspond to each "step"). Arrays of detectors, such as charge coupled devices (CCD) or photodiode arrays (PDA) can also be used. In such systems, the grating is fixed and the intensity of each wavelength of light is measured by a different detector in the array. Additionally, most modern mid-infrared spectrophotometers use a Fourier transform technique to acquire the spectral information. The technique is called Fourier Transform Infrared. When making transmission measurements, the spectrophotometer quantitatively compares the fraction of light that passes through a reference solution and a test solution. For reflectance measurements, the spectrophotometer quantitatively compares the fraction of light that reflects from the reference and test samples. Light from the source lamp is passed through a monochromator, which diffracts the light into a "rainbow" of wavelengths and outputs narrow bandwidths of this diffracted spectrum. Discrete frequencies are transmitted through the test sample. Then the photon flux density (watts per metre squared usually) of the transmitted or reflected light is measured with a photodiode, charge coupled device or other light sensor. The transmittance or reflectance value for each wavelength of the test sample is then compared with the transmission (or reflectance) values from the reference sample. In short, the sequence of events in a modern spectrophotometer is as follows: 1. 2. 3. 4. The light source is imaged upon the sample A fraction of the light is transmitted or reflected from the sample The light from the sample is imaged upon the entrance slit of the monochromator The monochromator separates the wavelengths of light and focuses each of them onto the photodetector sequentially

Many older spectrophotometers must be calibrated by a procedure known as "zeroing." The absorbancy of a reference substance is set as a baseline value, so the absorbancies of all other substances are recorded relative to the initial "zeroed" substance. The spectrophotometer then displays % absorbancy (the amount of light absorbed relative to the initial substance).[4]

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UV-visible spectrophotometry
The most common spectrophotometers are used in the UV and visible regions of the spectrum, and some of these instruments also operate into the near-infrared region as well. Visible region 400700nm spectrophotometry is used extensively in colorimetry science. Ink manufacturers, printing companies, textiles vendors, and many more, need the data provided through colorimetry. They take readings in the region of every 520 nanometers along the visible region, and produce a spectral reflectance curve or a data stream for alternative presentations. These curves can be used to test a new batch of colorant to check if it makes a match to specifications e.g., ISO printing standards. Traditional visible region spectrophotometers cannot detect if a colorant or the base material has fluorescence. This can make it difficult to manage color issues if for example one or more of the printing inks is fluorescent. Where a colorant contains fluorescence, a bi-spectral fluorescent spectrophotometer is used. There are two major setups for visual spectrum spectrophotometers, d/8 (spherical) and 0/45. The names are due to the geometry of the light source, observer and interior of the measurement chamber. Scientists use this instrument to measure the amount of compounds in a sample. If the compound is more concentrated more light will be absorbed by the sample; within small ranges, the Beer-Lambert law holds and the absorbance between samples vary with concentration linearly. In the case of printing measurements two alternative settings are commonly used- without/with uv filter to control better the effect of uv brighteners within the paper stock. Samples are usually prepared in cuvettes; depending on the region of interest, they may be constructed of glass, plastic, or quartz. Small sample amounts (starting with 0.3 l) of biological samples (DNA, RNA, Protein) can be quantified cuvetteless by pipetting the sample directly on the measuring window of a specialized NanoPhotometer.[5]

Nano UV-visible spectrophotometry

Multiple biological applications (e.g. DNA microarray experiment, array CGH, qPCR, Nucleic acid and protein labelling) imply quantitative and qualitative nucleic acid and protein quantification with minimal sample volumes. Specialized nano-volume photometer offer the possibility to determine sample concentrations cuvetteless with submicroliter volumes. A drop of sample (0.03 l to 5 l) is pipetted directly onto the measuring window of the photometer. In the measuring chamber the sample is squeezed to defined path lengths ranging from 0.04 mm up to 2 mm. Due to this reduction of the optical pathlength samples are diluted automatically (virtual dilution factor: 1/250 to 1/5) in comparison to standard cuvette measurements (path length 1 cm). Because the measurements are processed with undiluted samples, the samples can be retrieved after the measurement for further processing.

IR spectrophotometry
Spectrophotometers designed for the main infrared region are quite different because of the technical requirements of measurement in that region. One major factor is the type of photosensors that are available for different spectral regions, but infrared measurement is also challenging because virtually everything emits IR light as thermal radiation, especially at wavelengths beyond about 5m. Another complication is that quite a few materials such as glass and plastic absorb infrared light, making it incompatible as an optical medium. Ideal optical materials are salts, which do not absorb strongly. Samples for IR spectrophotometry may be smeared between two discs of potassium bromide or ground with potassium bromide and pressed into a pellet. Where aqueous solutions are to be measured, insoluble silver chloride is used to construct the cell.

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Spectroradiometers
Spectroradiometers, which operate almost like the visible region spectrophotometers, are designed to measure the spectral density of illuminants in order to evaluate and categorize lighting for sales by the manufacturer, or for the customers to confirm the lamp they decided to purchase is within their specifications. Components: 1. 2. 3. 4. The light source shines onto or through the sample. The sample transmits or reflects light. The detector detects how much light was reflected from or transmitted through the sample. The detector then converts how much light the sample transmitted or reflected into a number.

References
[1] Allen, D., Cooksey, C., & Tsai, B. (2010, October 5). Spectrophotometry. Retrieved from http:/ / www. nist. gov/ pml/ div685/ grp03/ spectrophotometry. cfm [2] Allen, D., Cooksey, C., & Tsai, B. (2010, October 5). Spectrophotometry. Retrieved from http:/ / www. nist. gov/ pml/ div685/ grp03/ spectrophotometry. cfm [3] Schwedt, Georg. (1997). The Essential Guide to Analytical Chemistry. (Brooks Haderlie, trans.). Chichester, NY: Wiley. (Original Work Published 1943). pp. 16-17 [4] Rendina, George. Experimental Methods in Modern Biochemistry W. B. Saunders Company: Philadelphia, PA. 1976. pp. 46-55 [5] Kartha, R. Spectrophotometric Quantification of Nano- and Standard-Volume Samples, (2008, October 7), American Biotechnology Laboratory, http:/ / www. iscpubs. com/ Media/ PublishingTitles/ b0608kar. pdf

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Article Sources and Contributors

Gas chromatography Source: http://en.wikipedia.org/w/index.php?oldid=469790704 Contributors: .:Ajvol:., 95j, AAMiller, AZidell, Achem, Agilent Life, Ahmed Eltahhan, Alash, Allentchang, Auntof6, Babbles, Barneca, Belovedfreak, Bensaccount, Billymac00, Bishop249, Blake-, Bobblewik, BusterIrby, CWenger, Cadillac, Carboxen, Cedonia, Charles Matthews, Choi1021, Christopherlin, Cielmort, Closedmouth, Cobaltbluetony, Crazynas, Crofters1, DMacks, Dan100, Danski14, DaveChem, Dealsmahoney, Death&Taxes, Docboat, Drobbere, Drrahulkulkarni, Dtgriscom, El C, Elvim, Eman502, Epbr123, Eric685, Fconaway, Flapitrr, Frankvangeel, Frumphammer, Fuzzform, GGenov, Geert Alkema, Glhann17, Graeme Bartlett, Hemanshu, Hjs521, Hols0089, Human.v2.0, IW.HG, Icseaturtles, Ike9898, IloveIUPAC, ItsZippy, JLaTondre, Jaeger5432, Jaysweet, Jcwf, Jeffrey Smith, JettWIlderbeast, Jlin, John of Reading, JohnnyMrNinja, Josep M. Gibert, Jossi, Jtillotson3, Juliancolton, Jvraba, Kakofonous, Keimzelle, Kesal, KingTT, Kkmurray, Kmontani, Kristof vt, Ksfu, Kukini, Lahiru k, Laslovarga, Lauciusa, Lavigne, Lexor, Light current, Lindigo, Lkinkade, Macrakis, Materialscientist, Mattj63, Mboverload, Mion, Moocha, MrOllie, Mullet, Nick1nildram, Niel Malan, Nono64, Oliverdl, PDH, Pearle, Phgao, Pi3832, Picofluidicist, Possum, Puffin, Qtea, RexNL, Rich Farmbrough, Rifleman 82, Rune.welsh, Saxbryn, Seaphoto, Sebastiankessel, Shakiestone, Shawnhath, Shweta Chakraborty, Signalhead, Skier Dude, Someguy1221, Sp33dyphil, SpaceFlight89, Specious, Spellmaster, Stechpalme, Stephen Harrison, Tangaloomaflyer, Techman224, The Thing That Should Not Be, Thingg, TimVickers, Tom, Tony1, Twas Now, UWChemist, Ucucha, Unmitigated Success, Veinor, Vwatts, Walkerma, Walkingmelways, WaysToEscape, Williamy, Windharp, Winnyec, ZayZayEM, Zhou Yu, , 386 anonymous edits Voltammetry Source: http://en.wikipedia.org/w/index.php?oldid=467586123 Contributors: Aransil, Aushulz, Bblackburn, Bunnyhop11, Dcirovic, Ency, Erbrumar, Erodium, Gaius Cornelius, Gene Nygaard, Goldenman82, IByte, JPBoyd, Jaeger5432, JanSuchy, Jannikkappel, Japo, Jcwf, Joe Schmedley, John of Reading, Karol Langner, Kkmurray, LabFox, Lcolson, Livetowin06, Michael Devore, Msrasnw, OMCV, Pdcook, Rhodopsin, Rjwilmsi, Siddhant, Skier Dude, Stan J Klimas, Stassats, Synchronism, Woohookitty, Yogesh9ic, ~K, 37 anonymous edits Photometer Source: http://en.wikipedia.org/w/index.php?oldid=466877952 Contributors: Amada44, Bluemoose, Bryan Derksen, Conscious, Falcon8765, Gaius Cornelius, Hooperbloob, Jacobolus, Jamelan, Lave, M-le-mot-dit, Manuel Anastcio, N2e, Nathan Johnson, Nixdorf, Oz1sej, Rjstott, Sowelilitokiemu, Srleffler, Tranh Nguyen, UNV, WillAndrews, 33 anonymous edits pH meter Source: http://en.wikipedia.org/w/index.php?oldid=472976246 Contributors: 32paul52, ABF, AJim, Alansohn, Animeronin, Arvindk.bareilly, BarretB, Bovineone, Carstensen, Cbgiunta, CesarB, Chuender, Coneslayer, Courcelles, Cpeditorial, DARTH SIDIOUS 2, Dareny, Darthpotatothe7th, Datamax, David Shay, Dead3y3, Decoder24, Devon Fyson, Edgar181, Elockid, Epbr123, Erodium, Extransit, Femto, Filll, F, Gaius Cornelius, Georgia guy, Glenn, Hongthay, I B Wright, Incnis Mrsi, Ixfd64, JHunterJ, Jeremiah, Jmabel, John254, Jsanders78, KFP, Kaverin, Keenan Pepper, Kenton Rod, Kkmurray, L Kensington, Lilly granger, Lowercase Sigma, Lpgeffen, LuigiManiac, LuisAceituno, M stone, Materialscientist, Mathias-S, Mikelantis, Mikespedia, Mlewis000, Mm instruments, Mondebleu, Morgankevinj huggle, MrOllie, Nmnogueira, Ocaasi, Pavel Vozenilek, Pengo, Petergans, PhilKnight, Philip Trueman, Physchim62, Plr4ever, ProlixDog, Rich Farmbrough, Rich257, Rmhermen, Rsrikanth05, Ruhrfisch, Rumping, ST47, Sam Hayes, Shinkolobwe, Silverxxx, Simon12, Skarebo, Souad27, Specious, The Thing That Should Not Be, Themfromspace, ThinkEnemies, Topbanana, Tristanb, Uthbrian, Vicenarian, Vignaux, Yahia.barie, Zero1328, ,42.. , 197 anonymous edits Electrometer Source: http://en.wikipedia.org/w/index.php?oldid=472701823 Contributors: Alexius08, Atlant, Bah2222, Bctwriter, BillC, Bryan Derksen, CMD Beaker, CharlesC, Chetvorno, Christophe.Finot, Ck lostsword, Cyberman, Darklilac, Dual Freq, Elm, Heron, Hmains, IvanLanin, Ixfd64, JorisvS, KnightRider, Krysith, LeeHunter, Light current, Loupeter, Lus Felipe Braga, Mav, Mintleaf, Mlewis000, Omegatron, Phe, Reddi, RexNL, Seejyb, Stikonas, Stw, SunCreator, Tom harrison, Trurle, WillMak050389, Williamgelbart, Wtshymanski, Zoohouse, Zureks, 001 ,anonymous edits Calorimeter Source: http://en.wikipedia.org/w/index.php?oldid=470795265 Contributors: A Softer Answer, AC+79 3888, Acroterion, Acsmith7, AgentPeppermint, Ahoerstemeier, Aillema, Alan Liefting, Alphachimp, Andre.holzner, Andy Dingley, Andymc, Antonin, Arkenflame, AwamerT, Babychimp16, Beligaronia, BenFrantzDale, Bennetto, Bensaccount, BillFlis, Bobblewik, Bones999, Brumon, Bryan Derksen, Calorimetrist, Capricorn42, Cassiewoofer, Citicat, Colonies Chris, Cometstyles, CommonsDelinker, Courcelles, Cwshea, Dagimar, Dalanos1976, Darth Chyrsaor, David Chouinard, DavidCary, Deeptrivia, Deli nk, Diaboli, Dysprosia, Echis, Eequor, Eikm2, Eloy, Epbr123, Ewlyahoocom, Fanyavizuri, Femto, Filou, FreplySpang, F, Gene Nygaard, Gentgeen, Gerry Ashton, Gilligan mark, GlennH2004, Gnj, Guyd, Habbit, HappyApple, Henitsirk, Heron, Hertz1888, Hoeksas, IceUnshattered, Igoldste, IronLance532, J.delanoy, J04n, JDHeinzmann, Jeffrey Smith, Jefw83, Jesielt, Jimp, Jkabay, JoeMK, Johann Wolfgang, John, JohnCD, Johnny C. Morse, Julesd, Jusjih, Keenan Pepper, KingTT, Kkmurray, Lamro, Liangren3, Linas, M1ss1ontomars2k4, MER-C, Machadwi, MarkS, Miborovsky, Mike4ty4, Myanw, Novangelis, Obadiah Withanoh, Olga Vovk, OneWeirdDude, Orangutan, OwenX, Passport90, Patricksears, Peterlewis, Phils, Pinethicket, Plrk, PopUpPirate, Poslamp, Puppy8800, Quadell, Qwerty Binary, Qxz, Rabbiz, RevRagnarok, Ronhjones, SCZenz, Sardanaphalus, Shanes, Shkedi, Sietse Snel, Silverweed, Slambo, Sodium, Stephenb, TUAN-NJITWILL, Tagishsimon, Talon Artaine, Teles, Teratornis, The Thing That Should Not Be, Toonitw, Uopchem253, Uopchem25a, User A1, Versus22, Vsmith, Waffenkartoffel, Wasell, West.andrew.g, WhisperToMe, Whosyourjudas, Widawski, Wikibofh, Wikipelli, WinterSpw, Wlodzimierz, Woohookitty, Xiaxei, Xtifr, 493 ,anonymous edits Spectrometer Source: http://en.wikipedia.org/w/index.php?oldid=471577600 Contributors: A.R., A8UDI, ABeelut, AJim, Acroterion, Adb65ss, Adoniscik, Afrine, Ahoerstemeier, Ancheta Wis, Andrewa, Antandrus, Anton Gutsunaev, Ardonik, Arnero, Arshdeep 3519, Asteron, Atlant, Bensaccount, Blackbaud, Bobet, Breezertree4599, BrianWelsch, Brion VIBBER, Bykgardner, C.Bluck, Camboxer, Can't sleep, clown will eat me, Capricorn42, CesarB, Cfn137, Christopherlin, Chuck Sirloin, Conversion script, Cybercobra, DH85868993, DOSGuy, DVdm, Dculberson, DerHexer, Dina, Dodiad, Dolovis, Dpeinador, DrBob, Dzubint, E Wing, Eclecticology, Eedderyi, Elvim, Erkan Yilmaz, Fastolfe00, Foogod, Fotaun, Frap, Glenn, Glrx, Grocceni, Groovenstein, Haham hanuka, Hankwang, HappyBunny12, HiDrNick, Ilyaroz, Ish ishwar, Itub, JNW, Jam225, Jeff Root, JeremyA, John254, JohnFlux, Johnster08, Jopparn, Katalaveno, Kazubon, Kelsey wagner, Kerotan, KevWasHere, Kkmurray, Kormoran, Kraftlos, LimoWreck, Lion Info, Looxix, Ma'ame Michu, Martinez-Shaw, Matthudson, Mav, Metric, Metthe, Mnmngb, Moshe Constantine Hassan Al-Silverburg, Mygerardromance, Naddy, NathanHagen, Ncu s0cc3r, Neko-chan, Ng.j, Nickj, Nnh, Noah Salzman, Nuno Tavares, Obradovic Goran, OlavN, Orange Suede Sofa, OrgasGirl, PV=nRT, Pearle, Phe, Phydend, Pi zza314159, Pjacobi, Porqin, Postmortemjapan, Professor marginalia, Quantumobserver, RJHall, Radon210, Rbeas, Rjstott, Rnt20, Rossgk, RoyBoy, Rvoorhees, RyanGerbil10, Sardanaphalus, Sceptre, SchfiftyThree, Seleonov, Skew-t, Smack, Ste4k, Stemperm, Steve Quinn, Stwalkerster, The Anome, The Ronin, Timwether, Tkma, Tldcollins, TomPreuss, Tyguy007, Useight, Vanakaris, Vniizht, Vsmith, Wapcaplet, Wavehunter, William Ackerman, WilliamKF, Wtshymanski, ZachPruckowski, 193 anonymous edits Spectrophotometry Source: http://en.wikipedia.org/w/index.php?oldid=464984119 Contributors: 20Lukianto, AAMiller, AJim, AS, Aboalbiss, Adenosine, Adoniscik, Afrine, Almit39, Antandrus, Astroinst, Atlant, BSDLab, Bensaccount, Bryan Derksen, Can't sleep, clown will eat me, Chilifrenzy, Christopherlin, Chrumps, Cian584, Cmdrjameson, Cpeditorial, Cs1987, Dawgspound, Dayyanb, Dbeatty, Dcirovic, Delta G, Diannaa, Dkroll2, Dmartin25, Doulos Christos, Duncan.france, El C, Garett Long, Gurch, H Padleckas, Hankwang, Heaven4uni, Heron, Ishuta, J.delanoy, Jackol, Jimp, Johnuniq, Katrobideau, Kkmurray, Krisirk, Leahrunner123, LeaveSleaves, Llamabread, MAvino-NJITWILL, Michael Hardy, Mindmatrix, Monty845, MrOllie, NawlinWiki, NewEnglandYankee, Orchidee3, Pdeitiker, Plastikspork, Ragstoriches919, Rifleman 82, Saintrain, Sardanaphalus, Slmader, Smack, Solitude, Squidonius, Steve Quinn, Stillnotelf, The Rambling Man, Tom, Twas Now, Ultramandk, Unyoyega, Vijay1403, Virusunknown, WODUP, West London Dweller, Whosyourjudas, WinterSpw, YassineMrabet, Yerpo, Zaphraud, 198 anonymous edits

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Image Sources, Licenses and Contributors

file:gaschromatograph.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Gaschromatograph.jpg License: Public Domain Contributors: Mcbort Image:Gas chromatograph.png Source: http://en.wikipedia.org/w/index.php?title=File:Gas_chromatograph.png License: GNU Free Documentation License Contributors: Eddideigel, Gauravjuvekar, Herbythyme, Karelj, Laslovarga, TommyBee, 1 anonymous edits Image:GeoStrataEclipse.jpg Source: http://en.wikipedia.org/w/index.php?title=File:GeoStrataEclipse.jpg License: Creative Commons Attribution-Sharealike 3.0 Contributors: BusterIrby Image:GCruleof10.jpg Source: http://en.wikipedia.org/w/index.php?title=File:GCruleof10.jpg License: Public Domain Contributors: Original uploader was UWChemist at en.wikipedia Image:GC Oven inside.jpg Source: http://en.wikipedia.org/w/index.php?title=File:GC_Oven_inside.jpg License: Creative Commons Attribution-Share Alike Contributors: Polimerek Image:Linear Potential Sweep.JPG Source: http://en.wikipedia.org/w/index.php?title=File:Linear_Potential_Sweep.JPG License: Public Domain Contributors: Lcolson Image:Linear Potential Sweep Anodic Stripping Voltammetry.JPG Source: http://en.wikipedia.org/w/index.php?title=File:Linear_Potential_Sweep_Anodic_Stripping_Voltammetry.JPG License: Public Domain Contributors: Lcolson Image:Three electrode setup.png Source: http://en.wikipedia.org/w/index.php?title=File:Three_electrode_setup.png License: Creative Commons Attribution 3.0 Contributors: Stan J Klimas File:Fotometer.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Fotometer.jpg License: Creative Commons Attribution-Sharealike 3.0 Germany Contributors: Thomas Wydra. Original uploader was Mr.checker at de.wikipedia Image:PH Meter.jpg Source: http://en.wikipedia.org/w/index.php?title=File:PH_Meter.jpg License: Public Domain Contributors: Datamax Image:2009-03-30 Red pH meter reads 4.96.jpg Source: http://en.wikipedia.org/w/index.php?title=File:2009-03-30_Red_pH_meter_reads_4.96.jpg License: Creative Commons Attribution-Share Alike Contributors: Ildar Sagdejev (Specious) File:Exposition Hautes Tensions - Electroscopes de type Volta.JPG Source: http://en.wikipedia.org/w/index.php?title=File:Exposition_Hautes_Tensions_-_Electroscopes_de_type_Volta.JPG License: Creative Commons Attribution-Sharealike 3.0 Contributors: photography taken by Christophe.Finot Image:Electroscope.png Source: http://en.wikipedia.org/w/index.php?title=File:Electroscope.png License: Creative Commons Attribution-ShareAlike 3.0 Unported Contributors: User:Stw Image:Lord Kelvin quadrant electrometer engraving.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Lord_Kelvin_quadrant_electrometer_engraving.jpg License: Public Domain Contributors: Williamgelbart Image:Ice-calorimeter.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Ice-calorimeter.jpg License: Public Domain Contributors: Originally en:User:Sadi Carnot File:Bombenkalorimeter mit bombe.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Bombenkalorimeter_mit_bombe.jpg License: Creative Commons Attribution 3.0 Contributors: Harbor1 Image:Spectrometer schematic.gif Source: http://en.wikipedia.org/w/index.php?title=File:Spectrometer_schematic.gif License: Creative Commons Attribution-Sharealike 3.0 Contributors: Kkmurray Image:Spektrometr.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Spektrometr.jpg License: Public Domain Contributors: Murg Image:Optical spectrometers.png Source: http://en.wikipedia.org/w/index.php?title=File:Optical_spectrometers.png License: Public Domain Contributors: Myself Image:Units visible spectrum.png Source: http://en.wikipedia.org/w/index.php?title=File:Units_visible_spectrum.png License: Public Domain Contributors: NathanHagen Image:Units IR spectrum.png Source: http://en.wikipedia.org/w/index.php?title=File:Units_IR_spectrum.png License: Public Domain Contributors: NathanHagen Image:simple spectroscope.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Simple_spectroscope.jpg License: Creative Commons Attribution-Sharealike 3.0 Contributors: Timwether Image:Spektrofotometri.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Spektrofotometri.jpg License: Public Domain Contributors: Karelj, Skorpion87, TimVickers, 1 anonymous edits File:Spetrophotometer-en.svg Source: http://en.wikipedia.org/w/index.php?title=File:Spetrophotometer-en.svg License: Creative Commons Attribution-Share Alike Contributors: Pieter Kuiper, YassineMrabet

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License
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