In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: mass concentration, molar concentration, number concentration, and volume concentration. A concentration can be any kind of chemical mixture, but most frequently solutes and solvents in solutions. The molar (amount) concentration has variants such as normal concentration and osmotic concentration.
In chemistry, the standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. In principle, the choice of standard state is arbitrary, although the International Union of Pure and Applied Chemistry (IUPAC) recommends a conventional set of standard states for general use. IUPAC recommends using a standard pressure p⦵ = 105 Pa. Strictly speaking, temperature is not part of the definition of a standard state. For example, as discussed below, the standard state of a gas is conventionally chosen to be unit pressure (usually in bar) ideal gas, regardless of the temperature. However, most tables of thermodynamic quantities are compiled at specific temperatures, most commonly 298.15 K (25.00 °C; 77.00 °F) or, somewhat less commonly, 273.15 K (0.00 °C; 32.00 °F).
An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines.
A mass spectrum is an intensity vs. m/z (mass-to-charge ratio) plot representing a chemical analysis. Hence, the mass spectrum of a sample is a pattern representing the distribution of ions by mass (more correctly: mass-to-charge ratio) in a sample. It is a histogram usually acquired using an instrument called a mass spectrometer. Not all mass spectra of a given substance are the same. For example, some mass spectrometers break the analyte molecules into fragments; others observe the intact molecular masses with little fragmentation. A mass spectrum can represent many different types of information based on the type of mass spectrometer and the specific experiment applied; however, all plots of intensity vs. mass-to-charge are referred to as mass spectra. Common fragmentation processes for organic molecules are the McLafferty rearrangement and alpha cleavage. Straight chain alkanes and alkyl groups produce a typical series of peaks: 29 (CH3CH2+), 43 (CH3CH2CH2+), 57 (CH3CH2CH2CH2+), 71 (CH3CH2CH2CH2CH2+) etc.
In chemistry an activated complex is defined by the International Union of Pure and Applied Chemistry (IUPAC) as "that assembly of atoms which corresponds to an arbitrary infinitesimally small region at or near the col of a potential energy surface". In other words, it refers to a collection of intermediate structures in a chemical reaction that persist while bonds are breaking and new bonds are forming. It therefore represents not one defined state, but rather a range of transient configurations that a collection of atoms passes through in between clearly defined products and reactants.
In chemistry, bond energy (E) or bond enthalpy (H) is the measure of bond strength in a chemical bond. IUPAC defines bond energy as the average value of the gas-phase bond dissociation energies (usually at a temperature of 298 K) for all bonds of the same type within the same chemical species. For example, the carbon–hydrogen bond energy in methane H(C–H) is the enthalpy change involved with breaking up one molecule of methane into a carbon atom and four hydrogen radicals, divided by 4. Tabulated bond energies are generally values of bond energies averaged over a number of selected typical chemical species containing that type of bond. Bond energy (E) or bond enthalpy (H) should not be confused with bond-dissociation energy. Bond energy is the average of all the bond-dissociation energies in a molecule, and will show a different value for a given bond than the bond-dissociation energy would. This is because the energy required to break a single bond in a specific molecule differs for each bond in that molecule. For example, methane has four C–H bonds and the bond-dissociation energies are 435 kJ/mol for D(CH3–H), 444 kJ/mol for D(CH2–H), 444 kJ/mol for D(CH–H) and 339 kJ/mol for D(C–H). Their average, and hence the bond energy, is 414 kJ/mol, even though not a single bond required specifically 414 kJ/mol to be broken.
Enantiomeric excess (ee) is a measurement of purity used for chiral substances. It reflects the degree to which a sample contains one enantiomer in greater amounts than the other. A racemic mixture has an ee of 0%, while a single completely pure enantiomer has an ee of 100%. A sample with 70% of one enantiomer and 30% of the other has an ee of 40%.
In acid catalysis and base catalysis, a chemical reaction is catalyzed by an acid or a base. By Brønsted–Lowry acid–base theory, the acid is the proton (hydrogen ion, H+) donor and the base is the proton acceptor. Typical reactions catalyzed by proton transfer are esterfications and aldol reactions. In these reactions, the conjugate acid of the carbonyl group is a better electrophile than the neutral carbonyl group itself. Depending on the chemical species that act as the acid or base, catalytic mechanisms can be classified as either specific catalysis and general catalysis. Many enzymes operate by specific catalysis.
In analytical chemistry, the detection limit, lower limit of detection, or LOD, is the lowest quantity of a substance that can be distinguished from the absence of that substance with a stated confidence level. The detection limit is estimated from the mean of the blank, the standard deviation of the blank and some confidence factor. Another consideration that affects the detection limit is the accuracy of the model used to predict concentration from the raw analytical signal.
In chemistry, the volume fraction φi is defined as the volume of a constituent Vi divided by the volume of all constituents of the mixture V prior to mixing:
The distribution constant (KD) is the equilibrium constant for the distribution of an analyte in two immiscible solvents.
The method of standard addition is a type of quantitative analysis approach often used in analytical chemistry whereby the standard is added directly to the aliquots of analyzed sample. This method is used in situations where sample matrix also contributes to the analytical signal, a situation known as the matrix effect, thus making it impossible to compare the analytical signal between sample and standard using the traditional calibration curve approach.
An internal standard in analytical chemistry is a chemical substance that is added in a constant amount to samples, the blank and calibration standards in a chemical analysis. This substance can then be used for calibration by plotting the ratio of the analyte signal to the internal standard signal as a function of the analyte concentration of the standards. This is done to correct for the loss of analyte during sample preparation or sample inlet. The internal standard is a compound that is very similar, but not identical to the chemical species of interest in the samples, as the effects of sample preparation should, relative to the amount of each species, be the same for the signal from the internal standard as for the signal(s) from the species of interest in the ideal case. Adding known quantities of analyte(s) of interest is a distinct technique called standard addition, which is performed to correct for matrix effects.
A mass chromatogram is a representation of mass spectrometry data as a chromatogram, where the x-axis represents time and the y-axis represents signal intensity. The source data contains mass information; however, it is not graphically represented in a mass chromatogram in favor of visualizing signal intensity versus time. The most common use of this data representation is when mass spectrometry is used in conjunction with some form of chromatography, such as in liquid chromatography–mass spectrometry or gas chromatography–mass spectrometry. In this case, the x-axis represents retention time, analogous to any other chromatogram. The y-axis represents signal intensity or relative signal intensity. There are many different types of metrics that this intensity may represent, depending on what information is extracted from each mass spectrum.
In chromatography, the retardation factor (R) is the fraction of an analyte in the mobile phase of a chromatographic system. In planar chromatography in particular, the retardation factor Rf is defined as the ratio of the distance traveled by the center of a spot to the distance traveled by the solvent front. Ideally, the values for RF are equivalent to the R values used in column chromatography.
Sample preparation for mass spectrometry is used for the optimization of a sample for analysis in a mass spectrometer (MS). Each ionization method has certain factors that must be considered for that method to be successful, such as volume, concentration, sample phase, and composition of the analyte solution. Quite possibly the most important consideration in sample preparation is knowing what phase the sample must be in for analysis to be successful. In some cases the analyte itself must be purified before entering the ion source. In other situations, the matrix, or everything in the solution surrounding the analyte, is the most important factor to consider and adjust. Often, sample preparation itself for mass spectrometry can be avoided by coupling mass spectrometry to a chromatography method, or some other form of separation before entering the mass spectrometer. In some cases, the analyte itself must be adjusted so that analysis is possible, such as in protein mass spectrometry, where usually the protein of interest is cleaved into peptides before analysis, either by in-gel digestion or by proteolysis in solution.
In chemistry, the mass fraction of a substance within a mixture is the ratio of the mass of that substance to the total mass of the mixture. Expressed as a formula, the mass fraction is:
In electrochemistry, the diffusion layer, according to IUPAC, is defined as the "region in the vicinity of an electrode where the concentrations are different from their value in the bulk solution. The definition of the thickness of the diffusion layer is arbitrary because the concentration approaches asymptotically the value in the bulk solution". The diffusion layer thus depends on the diffusion coefficient (D) of the analyte and for voltammetric measurements on the scan rate (V/s). It is usually considered to be some multiple of (Dt)1/2. At slow scan rates, the diffusion layer is large, on the order of micrometers, whereas at fast scan rates the diffusion layer is nanometers in thickness. The relationship is described in part by the Cottrell equation.
Ion suppression in LC-MS and LC-MS/MS refers to reduced detector response, or signal:noise as a manifested effect of competition for ionisation efficiency in the ionisation source, between the analyte(s) of interest and other endogenous or exogenous species which have not been removed from the sample matrix during sample preparation. Ion suppression is not strictly a problem unless interfering compounds elute at the same time as the analyte of interest. In cases where ion suppressing species do co-elute with an analyte, the effects on the important analytical parameters including precision, accuracy and limit of detection can be extensive, severely limiting the validity of an assay's results.
In chromatography, resolution is a measure of the separation of two peaks of different retention time t in a chromatogram.
