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for interactions (xy, xz, yz, xyz). All terms require hypothesis tests. The proliferation of interaction terms increases the risk that some hypothesis test will produce a false positive by chance. Fortunately, experience says that high order interactions are rare. The ability to detect interactions is a major advantage of multiple factor ANOVA. Testing one factor at a time hides interactions, but produces apparently inconsistent experimental results. Caution is advised when encountering interactions; Test interaction terms first and expand the analysis beyond ANOVA if interactions are found. Texts vary in their recommendations regarding the continuation of the ANOVA procedure after encountering an interaction. Interactions complicate the interpretation of experimental data. Neither the calculations of significance nor the estimated treatment effects can be taken at face value. "A significant interaction will often mask the significance of main effects." Graphical methods are recommended to enhance understanding. Regression is often useful. A lengthy discussion of interactions is available in Cox (1958). Some interactions can be removed (by transformations) while others cannot. A variety of techniques are used with multiple factor ANOVA to reduce expense. One technique used in factorial designs is to minimize replication (possibly no replication with support of analytical trickery) and to combine groups when effects are found to be statistically (or practically) insignificant. An experiment with many insignificant factors may collapse into one with a few factors supported by many replications. Associated analysis Some analysis is required in support of the design of the experiment while other analysis is performed after changes in the factors are formally found to produce statistically significant changes in the responses. Because experimentation is iterative, the results of one experiment alter plans for following experiments. Preparatory analysis The number of experimental units In the design of an experiment, the number of experimental units is planned to satisfy the goals of the experiment. Experimentation is often sequential. Early experiments are often designed to provide mean-unbiased estimates of treatment effects and of experimental error. Later experiments are often designed to test a hypothesis that a treatment effect has an important magnitude; in this case, the number of experimental units is chosen so that the experiment is within budget and has adequate power, among other goals. Reporting sample size analysis is generally required in psychology. "Provide information on sample size and the process that led to sample size decisions." The analysis, which is written in the experimental protocol before

the experiment is conducted, is examined in grant applications and administrative review boards. Besides the power analysis, there are less formal methods for selecting the number of experimental units. These include graphical methods based on limiting the probability of false negative errors, graphical methods based on an expected variation increase (above the residuals) and methods based on achieving a desired confidence interval. Power analysis Power analysis is often applied in the context of ANOVA in order to assess the probability of successfully rejecting the null hypothesis if we assume a certain ANOVA design, effect size in the population, sample size and significance level. Power analysis can assist in study design by determining what sample size would be required in order to have a reasonable chance of rejecting the null hypothesis when the alternative hypothesis is true. Effect size Several standardized measures of effect have been proposed for ANOVA to summarize the strength of the association between a predictor(s) and the dependent variable or the overall standardized difference of the complete model. Standardized effect-size estimates facilitate comparison of findings across studies and disciplines. However, while standardized effect sizes are commonly used in much of the professional literature, a non-standardized measure of effect size that has immediately "meaningful" units may be preferable for reporting purposes. Model confirmation Sometimes tests are conducted to determine whether the assumptions of ANOVA appear to be violated. Residuals are examined or analyzed to confirm homoscedasticity and gross normality. Residuals should have the appearance of (zero mean normal distribution) noise when plotted as a function of anything including time and modeled data values. Trends hint at interactions among factors or among observations. Follow-up tests A statistically significant effect in ANOVA is often followed by additional tests. This can be done in order to assess which groups are different from which other groups or to test various other focused hypotheses. Follow-up tests are often distinguished in terms of whether they are "planned" (a priori) or "post hoc." Planned tests are determined before looking at the data, and post hoc tests are conceived only after looking at the data (though the term "post hoc" is inconsistently used). The follow-up tests may be "simple" pairwise comparisons of individual group means or may be "compound" comparisons (e.g., comparing the mean pooling across groups A, B and C to the mean of group D). Comparisons can also look at tests of trend, such

as linear and quadratic relationships, when the independent variable involves ordered levels. Often the follow-up tests incorporate a method of adjusting for the multiple comparisons problem. Follow-up tests to identify which specific groups, variables, or factors have statistically different means include the Tukey's range test, and Duncan's new multiple range test. In turn, these tests are often followed with a Compact Letter Display (CLD) methodology in order to render the output of the mentioned tests more transparent to a non-statistician audience. Study designs There are several types of ANOVA. Many statisticians base ANOVA on the design of the experiment, especially on the protocol that specifies the random assignment of treatments to subjects; the protocol's description of the assignment mechanism should include a specification of the structure of the treatments and of any blocking. It is also common to apply ANOVA to observational data using an appropriate statistical model. Some popular designs use the following types of ANOVA: One-way ANOVA is used to test for differences among two or more independent groups (means), e.g. different levels of urea application in a crop, or different levels of antibiotic action on several different bacterial species, or different levels of effect of some medicine on groups of patients. However, should these groups not be independent, and there is an order in the groups (such as mild, moderate and severe disease), or in the dose of a drug (such as 5 mg/mL, 10 mg/mL, 20 mg/mL) given to the same group of patients, then a linear trend estimation should be used. Typically, however, the one-way ANOVA is used to test for differences among at least three groups, since the two-group case can be covered by a t-test. When there are only two means to compare, the t-test and the ANOVA F-test are equivalent; the relation between ANOVA and t is given by . Factorial ANOVA is used when there is more than one factor. Repeated measures ANOVA is used when the same subjects are used for each factor (e.g., in a longitudinal study). Multivariate analysis of variance (MANOVA) is used when there is more than one response variable. Cautions Balanced experiments (those with an equal sample size for each treatment) are relatively easy to interpret; unbalanced experiments offer more complexity. For single-factor (one-way) ANOVA, the adjustment for unbalanced data is easy, but the unbalanced analysis lacks both robustness and power. For more complex designs the

lack of balance leads to further complications. "The orthogonality property of main effects and interactions present in balanced data does not carry over to the unbalanced case. This means that the usual analysis of variance techniques do not apply. Consequently, the analysis of unbalanced factorials is much more difficult than that for balanced designs." In the general case, "The analysis of variance can also be applied to unbalanced data, but then the sums of squares, mean squares, and F-ratios will depend on the order in which the sources of variation are considered." ANOVA is (in part) a test of statistical significance. The American Psychological Association (and many other organisations) holds the view that simply reporting statistical significance is insufficient and that reporting confidence bounds is preferred. Generalizations ANOVA is considered to be a special case of linear regression which in turn is a special case of the general linear model. All consider the observations to be the sum of a model (fit) and a residual (error) to be minimized. The Kruskal–Wallis test and the Friedman test are nonparametric tests, which do not rely on an assumption of normality. Connection to linear regression Below we make clear the connection between multi-way ANOVA and linear regression. Linearly re-order the data so that -th observation is associated with a response and factors where denotes the different factors and is the total number of factors. In one-way ANOVA and in two-way ANOVA . Furthermore, we assume the -th factor has levels, namely . Now, we can one-hot encode the factors into the dimensional vector . The one-hot encoding function is defined such that the -th entry of is The vector is the concatenation of all of the above vectors for all . Thus, . In order to obtain a fully general -way interaction ANOVA we must also concatenate every additional interaction term in the vector and then add an intercept term. Let that vector be . With this notation in place, we now have the exact connection with linear regression. We simply regress response against the vector . However, there is a concern about identifiability. In order to overcome such issues we assume that the sum of the parameters within each set of interactions is equal to zero. From here, one can use F-statistics or other methods to determine the relevance of the individual factors. Example We can consider the 2-way interaction example where

we assume that the first factor has 2 levels and the second factor has 3 levels. Define if and if , i.e. is the one-hot encoding of the first factor and is the one-hot encoding of the second factor. With that, where the last term is an intercept term. For a more concrete example suppose that Then, See also ANOVA on ranks ANOVA-simultaneous component analysis Analysis of covariance (ANCOVA) Analysis of molecular variance (AMOVA) Analysis of rhythmic variance (ANORVA) Expected mean squares Explained variation Linear trend estimation Mixed-design analysis of variance Multivariate analysis of covariance (MANCOVA) Permutational analysis of variance Variance decomposition Footnotes Notes References Pre-publication chapters are available on-line. Cohen, Jacob (1988). Statistical power analysis for the behavior sciences (2nd ed.). Routledge Cox, David R. (1958). Planning of experiments. Reprinted as Freedman, David A.(2005). Statistical Models: Theory and Practice, Cambridge University Press. Lehmann, E.L. (1959) Testing Statistical Hypotheses. John Wiley & Sons. Moore, David S. & McCabe, George P. (2003). Introduction to the Practice of Statistics (4e). W H Freeman & Co. Rosenbaum, Paul R. (2002). Observational Studies (2nd ed.). New York: Springer-Verlag. Further reading Cox, David R. & Reid, Nancy M. (2000). The theory of design of experiments. (Chapman & Hall/CRC). Freedman, David A.; Pisani, Robert; Purves, Roger (2007) Statistics, 4th edition. W.W. Norton & Company Tabachnick, Barbara G. & Fidell, Linda S. (2007). Using Multivariate Statistics (5th ed.). Boston: Pearson International Edition. External links SOCR: ANOVA Activity Examples of all ANOVA and ANCOVA models with up to three treatment factors, including randomized block, split plot, repeated measures, and Latin squares, and their analysis in R (University of Southampton) NIST/SEMATECH e-Handbook of Statistical Methods, section 7.4.3: "Are the means equal?" Analysis of variance: Introduction Design of experiments Statistical tests Parametric statistics

In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in which all the carbon–carbon bonds are single. Alkanes have the general chemical formula . The alkanes range in complexity from the simplest case of methane (), where n = 1 (sometimes called the parent molecule), to arbitrarily large and complex molecules, like pentacontane () or 6-ethyl-2-methyl-5-(1-methylethyl) octane, an isomer of tetradecane (). The International Union of Pure and Applied Chemistry (IUPAC) defines alkanes as "acyclic branched or unbranched hydrocarbons having the general formula , and therefore consisting entirely of hydrogen atoms and saturated carbon atoms". However, some sources use the term to denote any saturated hydrocarbon, including those that are either monocyclic (i.e. the cycloalkanes) or polycyclic, despite their having a distinct general formula (i.e. cycloalkanes are ). In an alkane, each carbon atom is sp3-hybridized with 4 sigma bonds (either C–C or C–H), and each hydrogen atom is joined to one of the carbon atoms (in a C–H bond). The longest series of linked carbon atoms in a molecule is known as its carbon skeleton or carbon backbone. The number of carbon atoms may be considered as the size of the alkane. One group of the higher alkanes are waxes, solids at standard ambient temperature and pressure (SATP), for which the number of carbon atoms in the carbon backbone is greater than about 17. With their repeated – units, the alkanes constitute a homologous series of organic compounds in which the members differ in molecular mass by multiples of 14.03 u (the total mass of each such methylene-bridge unit, which comprises a single carbon atom of mass 12.01 u and two hydrogen atoms of mass ~1.01 u each). Methane is produced by methanogenic bacteria and some long-chain alkanes function as pheromones in certain animal species or as protective waxes in plants and fungi. Nevertheless, most alkanes do not have much biological activity. They can be viewed as molecular trees upon which can be hung the more active/reactive functional groups of biological molecules. The alkanes have two main commercial sources: petroleum (crude oil) and natural gas. An alkyl group is an alkane-based molecular fragment that bears one open valence for bonding. They are generally abbreviated with the symbol for any organyl group,

R, although Alk is sometimes used to specifically symbolize an alkyl group (as opposed to an alkenyl group or aryl group). Structure and classification Ordinarily the C-C single bond distance is . Saturated hydrocarbons can be linear, branched, or cyclic. The third group is sometimes called cycloalkanes. Very complicated structures are possible by combining linear, branch, cyclic alkanes. Isomerism Alkanes with more than three carbon atoms can be arranged in various ways, forming structural isomers. The simplest isomer of an alkane is the one in which the carbon atoms are arranged in a single chain with no branches. This isomer is sometimes called the n-isomer (n for "normal", although it is not necessarily the most common). However, the chain of carbon atoms may also be branched at one or more points. The number of possible isomers increases rapidly with the number of carbon atoms. For example, for acyclic alkanes: C1: methane only C2: ethane only C3: propane only C4: 2 isomers: butane and isobutane C5: 3 isomers: pentane, isopentane, and neopentane C6: 5 isomers: hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane C7: 9 isomers: heptane, methylhexane (2 isomers), dimethylpentane (4 isomers), 3-ethylpentane, 2,2,3-trimethylbutane C8: 18 isomers: octane, 2-methylheptane, 3-methylheptane, 2,3-dimethylhexane, 3,4-dimethylhexane, 2,3,4-trimethylpentane, 3,3-dimethylhexane, 2,2-trimethylpentane, 2,4-dimethylhexane, 2,2,4-trimethylpentane, 2,3,3-Trimethylpentane, 3,3,4-trimethyl-pentane, 3,4,4-trimethylpentane, 2,4,4-trimethylpentane, (5 isomers) C9: 35 isomers C10: 75 isomers C12: 355 isomers C32: 27,711,253,769 isomers C60: 22,158,734,535,770,411,074,184 isomers, many of which are not stable Branched alkanes can be chiral. For example, 3-methylhexane and its higher homologues are chiral due to their stereogenic center at carbon atom number 3. The above list only includes differences of connectivity, not stereochemistry. In addition to the alkane isomers, the chain of carbon atoms may form one or more rings. Such compounds are called cycloalkanes, and are also excluded from the above list because changing the number of rings changes the molecular formula. For example, cyclobutane and methylcyclopropane are isomers of each other (C4H8), but are not isomers of butane (C4H10). Nomenclature The IUPAC nomenclature (systematic way of naming compounds) for alkanes is based on identifying hydrocarbon chains. Unbranched, saturated hydrocarbon chains are named systematically with a Greek numerical prefix denoting the number of carbons and the suffix "-ane". In 1866, August Wilhelm von Hofmann suggested systematizing nomenclature by using the whole sequence of vowels a, e, i, o and u to create suffixes -ane, -ene, -ine (or -yne), -one, -une, for the hydrocarbons CnH2n+2, CnH2n, CnH2n−2,

CnH2n−4, CnH2n−6. In modern nomenclature, the first three specifically name hydrocarbons with single, double and triple bonds; while "-one" now represents a ketone. Linear alkanes Straight-chain alkanes are sometimes indicated by the prefix "n-" or "n-"(for "normal") where a non-linear isomer exists. Although this is not strictly necessary and is not part of the IUPAC naming system, the usage is still common in cases where one wishes to emphasize or distinguish between the straight-chain and branched-chain isomers, e.g., "n-butane" rather than simply "butane" to differentiate it from isobutane. Alternative names for this group used in the petroleum industry are linear paraffins or n-paraffins. The first six members of the series (in terms of number of carbon atoms) are named as follows: methane CH4 – one carbon and 4 hydrogen ethane C2H6 – two carbon and 6 hydrogen propane C3H8 – three carbon and 8 hydrogen butane C4H10 – four carbon and 10 hydrogen pentane C5H12 – five carbon and 12 hydrogen hexane C6H14 – six carbon and 14 hydrogen The first four names were derived from methanol, ether, propionic acid and butyric acid. Alkanes with five or more carbon atoms are named by adding the suffix -ane to the appropriate numerical multiplier prefix with elision of any terminal vowel (-a or -o) from the basic numerical term. Hence, pentane, C5H12; hexane, C6H14; heptane, C7H16; octane, C8H18; etc. The numeral prefix is generally Greek; however, alkanes with a carbon atom count ending in nine, for example nonane, use the Latin prefix non-. For a more complete list, see list of straight-chain alkanes. Branched alkanes Simple branched alkanes often have a common name using a prefix to distinguish them from linear alkanes, for example n-pentane, isopentane, and neopentane. IUPAC naming conventions can be used to produce a systematic name. The key steps in the naming of more complicated branched alkanes are as follows: Identify the longest continuous chain of carbon atoms Name this longest root chain using standard naming rules Name each side chain by changing the suffix of the name of the alkane from "-ane" to "-yl" Number the longest continuous chain in order to give the lowest possible numbers for the side-chains Number and name the side chains before the name of the root chain If there are multiple side chains of the same type, use prefixes such as "di-" and "tri-" to indicate it as such, and number each

one. Add side chain names in alphabetical (disregarding "di-" etc. prefixes) order in front of the name of the root chain Saturated cyclic hydrocarbons Though technically distinct from the alkanes, this class of hydrocarbons is referred to by some as the "cyclic alkanes." As their description implies, they contain one or more rings. Simple cycloalkanes have a prefix "cyclo-" to distinguish them from alkanes. Cycloalkanes are named as per their acyclic counterparts with respect to the number of carbon atoms in their backbones, e.g., cyclopentane (C5H10) is a cycloalkane with 5 carbon atoms just like pentane (C5H12), but they are joined up in a five-membered ring. In a similar manner, propane and cyclopropane, butane and cyclobutane, etc. Substituted cycloalkanes are named similarly to substituted alkanes – the cycloalkane ring is stated, and the substituents are according to their position on the ring, with the numbering decided by the Cahn–Ingold–Prelog priority rules. Trivial/common names The trivial (non-systematic) name for alkanes is 'paraffins'. Together, alkanes are known as the 'paraffin series'. Trivial names for compounds are usually historical artifacts. They were coined before the development of systematic names, and have been retained due to familiar usage in industry. Cycloalkanes are also called naphthenes. Branched-chain alkanes are called isoparaffins. "Paraffin" is a general term and often does not distinguish between pure compounds and mixtures of isomers, i.e., compounds of the same chemical formula, e.g., pentane and isopentane. In IUPAC The following trivial names are retained in the IUPAC system: isobutane for 2-methylpropane isopentane for 2-methylbutane neopentane for 2,2-dimethylpropane. Non-IUPAC Some non-IUPAC trivial names are occasionally used: cetane, for hexadecane cerane, for hexacosane Physical properties All alkanes are colorless. Alkanes with the lowest molecular weights are gases, those of intermediate molecular weight are liquids, and the heaviest are waxy solids. Table of alkanes Boiling point Alkanes experience intermolecular van der Waals forces. Stronger intermolecular van der Waals forces give rise to greater boiling points of alkanes. There are two determinants for the strength of the van der Waals forces: the number of electrons surrounding the molecule, which increases with the alkane's molecular weight the surface area of the molecule Under standard conditions, from CH4 to C4H10 alkanes are gaseous; from C5H12 to C17H36 they are liquids; and after C18H38 they are solids. As the boiling point of alkanes is primarily determined by weight, it should not be a surprise that the boiling point has

an almost linear relationship with the size (molecular weight) of the molecule. As a rule of thumb, the boiling point rises 20–30 °C for each carbon added to the chain; this rule applies to other homologous series. A straight-chain alkane will have a boiling point higher than a branched-chain alkane due to the greater surface area in contact, and thus greater van der Waals forces, between adjacent molecules. For example, compare isobutane (2-methylpropane) and n-butane (butane), which boil at −12 and 0 °C, and 2,2-dimethylbutane and 2,3-dimethylbutane which boil at 50 and 58 °C, respectively. On the other hand, cycloalkanes tend to have higher boiling points than their linear counterparts due to the locked conformations of the molecules, which give a plane of intermolecular contact. Melting points The melting points of the alkanes follow a similar trend to boiling points for the same reason as outlined above. That is, (all other things being equal) the larger the molecule the higher the melting point. There is one significant difference between boiling points and melting points. Solids have a more rigid and fixed structure than liquids. This rigid structure requires energy to break down. Thus the better put together solid structures will require more energy to break apart. For alkanes, this can be seen from the graph above (i.e., the blue line). The odd-numbered alkanes have a lower trend in melting points than even-numbered alkanes. This is because even-numbered alkanes pack well in the solid phase, forming a well-organized structure which requires more energy to break apart. The odd-numbered alkanes pack less well and so the "looser"-organized solid packing structure requires less energy to break apart. For a visualization of the crystal structures see. The melting points of branched-chain alkanes can be either higher or lower than those of the corresponding straight-chain alkanes, again depending on the ability of the alkane in question to pack well in the solid phase. Conductivity and solubility Alkanes do not conduct electricity in any way, nor are they substantially polarized by an electric field. For this reason, they do not form hydrogen bonds and are insoluble in polar solvents such as water. Since the hydrogen bonds between individual water molecules are aligned away from an alkane molecule, the coexistence of an alkane and water leads to an increase in molecular order (a reduction in entropy). As there is no significant bonding between water molecules and alkane

molecules, the second law of thermodynamics suggests that this reduction in entropy should be minimized by minimizing the contact between alkane and water: Alkanes are said to be hydrophobic as they are insoluble in water. Their solubility in nonpolar solvents is relatively high, a property that is called lipophilicity. Alkanes are, for example, miscible in all proportions among themselves. The density of the alkanes usually increases with the number of carbon atoms but remains less than that of water. Hence, alkanes form the upper layer in an alkane–water mixture. Molecular geometry The molecular structure of the alkanes directly affects their physical and chemical characteristics. It is derived from the electron configuration of carbon, which has four valence electrons. The carbon atoms in alkanes are described as sp3 hybrids; that is to say that, to a good approximation, the valence electrons are in orbitals directed towards the corners of a tetrahedron which are derived from the combination of the 2s orbital and the three 2p orbitals. Geometrically, the angle between the bonds are cos−1(−) ≈ 109.47°. This is exact for the case of methane, while larger alkanes containing a combination of C–H and C–C bonds generally have bonds that are within several degrees of this idealized value. Bond lengths and bond angles An alkane has only C–H and C–C single bonds. The former result from the overlap of an sp3 orbital of carbon with the 1s orbital of a hydrogen; the latter by the overlap of two sp3 orbitals on adjacent carbon atoms. The bond lengths amount to 1.09 × 10−10 m for a C–H bond and 1.54 × 10−10 m for a C–C bond. The spatial arrangement of the bonds is similar to that of the four sp3 orbitals—they are tetrahedrally arranged, with an angle of 109.47° between them. Structural formulae that represent the bonds as being at right angles to one another, while both common and useful, do not accurately depict the geometry. Conformation The structural formula and the bond angles are not usually sufficient to completely describe the geometry of a molecule. There is a further degree of freedom for each carbon–carbon bond: the torsion angle between the atoms or groups bound to the atoms at each end of the bond. The spatial arrangement described by the torsion angles of the molecule is known as its conformation. Ethane forms the simplest case for studying the conformation of alkanes,

as there is only one C–C bond. If one looks down the axis of the C–C bond, one will see the so-called Newman projection. The hydrogen atoms on both the front and rear carbon atoms have an angle of 120° between them, resulting from the projection of the base of the tetrahedron onto a flat plane. However, the torsion angle between a given hydrogen atom attached to the front carbon and a given hydrogen atom attached to the rear carbon can vary freely between 0° and 360°. This is a consequence of the free rotation about a carbon–carbon single bond. Despite this apparent freedom, only two limiting conformations are important: eclipsed conformation and staggered conformation. The two conformations differ in energy: the staggered conformation is 12.6 kJ/mol (3.0 kcal/mol) lower in energy (more stable) than the eclipsed conformation (the least stable). This difference in energy between the two conformations, known as the torsion energy, is low compared to the thermal energy of an ethane molecule at ambient temperature. There is constant rotation about the C–C bond. The time taken for an ethane molecule to pass from one staggered conformation to the next, equivalent to the rotation of one CH3 group by 120° relative to the other, is of the order of 10−11 seconds. The case of higher alkanes is more complex but based on similar principles, with the antiperiplanar conformation always being the most favored around each carbon–carbon bond. For this reason, alkanes are usually shown in a zigzag arrangement in diagrams or in models. The actual structure will always differ somewhat from these idealized forms, as the differences in energy between the conformations are small compared to the thermal energy of the molecules: Alkane molecules have no fixed structural form, whatever the models may suggest. Spectroscopic properties Virtually all organic compounds contain carbon–carbon and carbon–hydrogen bonds, and so show some of the features of alkanes in their spectra. Alkanes are notable for having no other groups, and therefore for the absence of other characteristic spectroscopic features of a functional group like –OH, –CHO, –COOH, etc. Infrared spectroscopy The carbon–hydrogen stretching mode gives a strong absorption between 2850 and 2960 cm−1, while the carbon–carbon stretching mode absorbs between 800 and 1300 cm−1. The carbon–hydrogen bending modes depend on the nature of the group: methyl groups show bands at 1450 cm−1 and 1375 cm−1, while methylene groups show bands at 1465

cm−1 and 1450 cm−1. Carbon chains with more than four carbon atoms show a weak absorption at around 725 cm−1. NMR spectroscopy The proton resonances of alkanes are usually found at δH = 0.5–1.5. The carbon-13 resonances depend on the number of hydrogen atoms attached to the carbon: δC = 8–30 (primary, methyl, –CH3), 15–55 (secondary, methylene, –CH2–), 20–60 (tertiary, methyne, C–H) and quaternary. The carbon-13 resonance of quaternary carbon atoms is characteristically weak, due to the lack of nuclear Overhauser effect and the long relaxation time, and can be missed in weak samples, or samples that have not been run for a sufficiently long time. Mass spectrometry Alkanes have a high ionization energy, and the molecular ion is usually weak. The fragmentation pattern can be difficult to interpret, but in the case of branched chain alkanes, the carbon chain is preferentially cleaved at tertiary or quaternary carbons due to the relative stability of the resulting free radicals. The fragment resulting from the loss of a single methyl group (M − 15) is often absent, and other fragments are often spaced by intervals of fourteen mass units, corresponding to sequential loss of CH2 groups. Chemical properties Alkanes are only weakly reactive with most chemical compounds. The acid dissociation constant (pKa) values of all alkanes are estimated to range from 50 to 70, depending on the extrapolation method, hence they are extremely weak acids that are practically inert to bases (see: carbon acids). They are also extremely weak bases, undergoing no observable protonation in pure sulfuric acid (H0 ~ −12), although superacids that are at least millions of times stronger have been known to protonate them to give hypercoordinate alkanium ions (see: methanium ion). Similarly, they only show reactivity with the strongest of electrophilic reagents (e.g., dioxiranes and salts containing the NF4+ cation). By virtue of their strong C–H bonds (~100 kcal/mol) and C–C bonds (~90 kcal/mol, but usually less sterically accessible), they are also relatively unreactive toward free radicals, although many electron-deficient radicals will react with alkanes in the absence of other electron-rich bonds (see below). This inertness is the source of the term paraffins (with the meaning here of "lacking affinity"). In crude oil the alkane molecules have remained chemically unchanged for millions of years. Free radicals, molecules with unpaired electrons, play a large role in most reactions of alkanes, such as cracking and reformation where long-chain alkanes are

converted into shorter-chain alkanes and straight-chain alkanes into branched-chain isomers. Moreover, redox reactions of alkanes involving free radical intermediates, in particular with oxygen and the halogens, are possible as the carbon atoms are in a strongly reduced state; in the case of methane, carbon is in its lowest possible oxidation state (−4). Reaction with oxygen (if present in sufficient quantity to satisfy the reaction stoichiometry) leads to combustion without any smoke, producing carbon dioxide and water. Free radical halogenation reactions occur with halogens, leading to the production of haloalkanes. In addition, alkanes have been shown to interact with, and bind to, certain transition metal complexes in C–H bond activation reactions. In highly branched alkanes, the bond angle may differ significantly from the optimal value (109.5°) to accommodate bulky groups. Such distortions introduce a tension in the molecule, known as steric hindrance or strain. Strain substantially increases reactivity. However, in general and perhaps surprisingly, when branching is not extensive enough to make highly disfavorable 1,2- and 1,3-alkyl–alkyl steric interactions (worth ~3.1 kcal/mol and ~3.7 kcal/mol in the case of the eclipsing conformations of butane and pentane, respectively) unavoidable, the branched alkanes are actually more thermodynamically stable than their linear (or less branched) isomers. For example, the highly branched 2,2,3,3-tetramethylbutane is about 1.9 kcal/mol more stable than its linear isomer, n-octane. Due to the subtlety of this effect, the exact reasons for this rule have been vigorously debated in the chemical literature and is yet unsettled. Several explanations, including stabilization of branched alkanes by electron correlation, destabilization of linear alkanes by steric repulsion, stabilization by neutral hyperconjugation, and/or electrostatic effects have been advanced as possibilities. The controversy is related to the question of whether the traditional explanation of hyperconjugation is the primary factor governing the stability of alkyl radicals. Reactions with oxygen (combustion reaction) All alkanes react with oxygen in a combustion reaction, although they become increasingly difficult to ignite as the number of carbon atoms increases. The general equation for complete combustion is: CnH2n+2 + (n + ) O2 → (n + 1) H2O + n CO2 or CnH2n+2 + () O2 → (n + 1) H2O + n CO2 In the absence of sufficient oxygen, carbon monoxide or even soot can be formed, as shown below: CnH2n+2 + (n + ) O2 → (n + 1) H2O + n CO CnH2n+2 + (n + ) O2 → (n + 1)

H2O + n C For example, methane: 2 CH4 + 3 O2 → 4 H2O + 2 CO CH4 + O2 → 2 H2O + C See the alkane heat of formation table for detailed data. The standard enthalpy change of combustion, ΔcH⊖, for alkanes increases by about 650 kJ/mol per CH2 group. Branched-chain alkanes have lower values of ΔcH⊖ than straight-chain alkanes of the same number of carbon atoms, and so can be seen to be somewhat more stable. Reactions with halogens Alkanes react with halogens in a so-called free radical halogenation reaction. The hydrogen atoms of the alkane are progressively replaced by halogen atoms. Free radicals are the reactive species that participate in the reaction, which usually leads to a mixture of products. The reaction is highly exothermic with halogen fluorine and can lead to an explosion. These reactions are an important industrial route to halogenated hydrocarbons. There are three steps: Initiation the halogen radicals form by homolysis. Usually, energy in the form of heat or light is required. Chain reaction or Propagation then takes place—the halogen radical abstracts a hydrogen from the alkane to give an alkyl radical. This reacts further. Chain termination where the radicals recombine. Experiments have shown that all halogenation produces a mixture of all possible isomers, indicating that all hydrogen atoms are susceptible to reaction. The mixture produced, however, is not a statistical mixture: Secondary and tertiary hydrogen atoms are preferentially replaced due to the greater stability of secondary and tertiary free-radicals. An example can be seen in the monobromination of propane: Cracking Cracking breaks larger molecules into smaller ones. This can be done with a thermal or catalytic method. The thermal cracking process follows a homolytic mechanism with formation of free radicals. The catalytic cracking process involves the presence of acid catalysts (usually solid acids such as silica-alumina and zeolites), which promote a heterolytic (asymmetric) breakage of bonds yielding pairs of ions of opposite charges, usually a carbocation and the very unstable hydride anion. Carbon-localized free radicals and cations are both highly unstable and undergo processes of chain rearrangement, C–C scission in position beta (i.e., cracking) and intra- and intermolecular hydrogen transfer or hydride transfer. In both types of processes, the corresponding reactive intermediates (radicals, ions) are permanently regenerated, and thus they proceed by a self-propagating chain mechanism. The chain of reactions is eventually terminated by radical or ion recombination. Isomerization and

reformation Dragan and his colleague were the first to report about isomerization in alkanes. Isomerization and reformation are processes in which straight-chain alkanes are heated in the presence of a platinum catalyst. In isomerization, the alkanes become branched-chain isomers. In other words, it does not lose any carbons or hydrogens, keeping the same molecular weight. In reformation, the alkanes become cycloalkanes or aromatic hydrocarbons, giving off hydrogen as a by-product. Both of these processes raise the octane number of the substance. Butane is the most common alkane that is put under the process of isomerization, as it makes many branched alkanes with high octane numbers. Other reactions Alkanes will react with steam in the presence of a nickel catalyst to give hydrogen. Alkanes can be chlorosulfonated and nitrated, although both reactions require special conditions. The fermentation of alkanes to carboxylic acids is of some technical importance. In the Reed reaction, sulfur dioxide, chlorine and light convert hydrocarbons to sulfonyl chlorides. Nucleophilic abstraction can be used to separate an alkane from a metal. Alkyl groups can be transferred from one compound to another by transmetalation reactions. A mixture of antimony pentafluoride (SbF5) and fluorosulfonic acid (HSO3F), called magic acid, can protonate alkanes. Occurrence Occurrence of alkanes in the Universe Alkanes form a small portion of the atmospheres of the outer gas planets such as Jupiter (0.1% methane, 2 ppm ethane), Saturn (0.2% methane, 5 ppm ethane), Uranus (1.99% methane, 2.5 ppm ethane) and Neptune (1.5% methane, 1.5 ppm ethane). Titan (1.6% methane), a satellite of Saturn, was examined by the Huygens probe, which indicated that Titan's atmosphere periodically rains liquid methane onto the moon's surface. Also on Titan, the Cassini mission has imaged seasonal methane/ethane lakes near the polar regions of Titan. Methane and ethane have also been detected in the tail of the comet Hyakutake. Chemical analysis showed that the abundances of ethane and methane were roughly equal, which is thought to imply that its ices formed in interstellar space, away from the Sun, which would have evaporated these volatile molecules. Alkanes have also been detected in meteorites such as carbonaceous chondrites. Occurrence of alkanes on Earth Traces of methane gas (about 0.0002% or 1745 ppb) occur in the Earth's atmosphere, produced primarily by methanogenic microorganisms, such as Archaea in the gut of ruminants. The most important commercial sources for alkanes are natural gas and oil. Natural gas contains primarily

methane and ethane, with some propane and butane: oil is a mixture of liquid alkanes and other hydrocarbons. These hydrocarbons were formed when marine animals and plants (zooplankton and phytoplankton) died and sank to the bottom of ancient seas and were covered with sediments in an anoxic environment and converted over many millions of years at high temperatures and high pressure to their current form. Natural gas resulted thereby for example from the following reaction: C6H12O6 → 3 CH4 + 3 CO2 These hydrocarbon deposits, collected in porous rocks trapped beneath impermeable cap rocks, comprise commercial oil fields. They have formed over millions of years and once exhausted cannot be readily replaced. The depletion of these hydrocarbons reserves is the basis for what is known as the energy crisis. Alkanes have a low solubility in water, so the content in the oceans is negligible; however, at high pressures and low temperatures (such as at the bottom of the oceans), methane can co-crystallize with water to form a solid methane clathrate (methane hydrate). Although this cannot be commercially exploited at the present time, the amount of combustible energy of the known methane clathrate fields exceeds the energy content of all the natural gas and oil deposits put together. Methane extracted from methane clathrate is, therefore, a candidate for future fuels. Biological occurrence Acyclic alkanes occur in nature in various ways. Methane is present in what is called biogas, produced by animals and decaying matter, which is a possible renewable energy source. Bacteria and archaea Certain types of bacteria can metabolize alkanes: they prefer even-numbered carbon chains as they are easier to degrade than odd-numbered chains. On the other hand, certain archaea, the methanogens, produce large quantities of methane by the metabolism of carbon dioxide or other oxidized organic compounds. The energy is released by the oxidation of hydrogen: CO2 + 4 H2 → CH4 + 2 H2O Methanogens are also the producers of marsh gas in wetlands. The methane output of cattle and other herbivores, which can release 30 to 50 gallons per day, and of termites, is also due to methanogens. They also produce this simplest of all alkanes in the intestines of humans. Methanogenic archaea are, hence, at the end of the carbon cycle, with carbon being released back into the atmosphere after having been fixed by photosynthesis. It is probable that our current deposits of natural gas were

formed in a similar way. Fungi and plants Alkanes also play a role, if a minor role, in the biology of the three eukaryotic groups of organisms: fungi, plants, and animals. Some specialized yeasts, e.g., Candida tropicale, Pichia sp., Rhodotorula sp., can use alkanes as a source of carbon or energy. The fungus Amorphotheca resinae prefers the longer-chain alkanes in aviation fuel, and can cause serious problems for aircraft in tropical regions. In plants, the solid long-chain alkanes are found in the plant cuticle and epicuticular wax of many species, but are only rarely major constituents. They protect the plant against water loss, prevent the leaching of important minerals by the rain, and protect against bacteria, fungi, and harmful insects. The carbon chains in plant alkanes are usually odd-numbered, between 27 and 33 carbon atoms in length, and are made by the plants by decarboxylation of even-numbered fatty acids. The exact composition of the layer of wax is not only species-dependent but also changes with the season and such environmental factors as lighting conditions, temperature or humidity. More volatile short-chain alkanes are also produced by and found in plant tissues. The Jeffrey pine is noted for producing exceptionally high levels of n-heptane in its resin, for which reason its distillate was designated as the zero point for one octane rating. Floral scents have also long been known to contain volatile alkane components, and n-nonane is a significant component in the scent of some roses. Emission of gaseous and volatile alkanes such as ethane, pentane, and hexane by plants has also been documented at low levels, though they are not generally considered to be a major component of biogenic air pollution. Edible vegetable oils also typically contain small fractions of biogenic alkanes with a wide spectrum of carbon numbers, mainly 8 to 35, usually peaking in the low to upper 20s, with concentrations up to dozens of milligrams per kilogram (parts per million by weight) and sometimes over a hundred for the total alkane fraction. Animals Alkanes are found in animal products, although they are less important than unsaturated hydrocarbons. One example is the shark liver oil, which is approximately 14% pristane (2,6,10,14-tetramethylpentadecane, C19H40). They are important as pheromones, chemical messenger materials, on which insects depend for communication. In some species, e.g. the support beetle Xylotrechus colonus, pentacosane (C25H52), 3-methylpentaicosane (C26H54) and 9-methylpentaicosane (C26H54) are transferred by body contact. With others

like the tsetse fly Glossina morsitans morsitans, the pheromone contains the four alkanes 2-methylheptadecane (C18H38), 17,21-dimethylheptatriacontane (C39H80), 15,19-dimethylheptatriacontane (C39H80) and 15,19,23-trimethylheptatriacontane (C40H82), and acts by smell over longer distances. Waggle-dancing honey bees produce and release two alkanes, tricosane and pentacosane. Ecological relations One example, in which both plant and animal alkanes play a role, is the ecological relationship between the sand bee (Andrena nigroaenea) and the early spider orchid (Ophrys sphegodes); the latter is dependent for pollination on the former. Sand bees use pheromones in order to identify a mate; in the case of A. nigroaenea, the females emit a mixture of tricosane (C23H48), pentacosane (C25H52) and heptacosane (C27H56) in the ratio 3:3:1, and males are attracted by specifically this odor. The orchid takes advantage of this mating arrangement to get the male bee to collect and disseminate its pollen; parts of its flower not only resemble the appearance of sand bees but also produce large quantities of the three alkanes in the same ratio as female sand bees. As a result, numerous males are lured to the blooms and attempt to copulate with their imaginary partner: although this endeavor is not crowned with success for the bee, it allows the orchid to transfer its pollen, which will be dispersed after the departure of the frustrated male to other blooms. Production Petroleum refining As stated earlier, the most important source of alkanes is natural gas and crude oil. Alkanes are separated in an oil refinery by fractional distillation and processed into many products. Fischer–Tropsch The Fischer–Tropsch process is a method to synthesize liquid hydrocarbons, including alkanes, from carbon monoxide and hydrogen. This method is used to produce substitutes for petroleum distillates. Laboratory preparation There is usually little need for alkanes to be synthesized in the laboratory, since they are usually commercially available. Also, alkanes are generally unreactive chemically or biologically, and do not undergo functional group interconversions cleanly. When alkanes are produced in the laboratory, it is often a side-product of a reaction. For example, the use of n-butyllithium as a strong base gives the conjugate acid n-butane as a side-product: However, at times it may be desirable to make a section of a molecule into an alkane-like functionality (alkyl group) using the above or similar methods. For example, an ethyl group is an alkyl group; when this is attached to a hydroxy group, it gives ethanol, which is not

an alkane. To do so, the best-known methods are hydrogenation of alkenes: (R = alkyl) Alkanes or alkyl groups can also be prepared directly from alkyl halides in the Corey–House–Posner–Whitesides reaction. The Barton–McCombie deoxygenation removes hydroxyl groups from alcohols e.g. and the Clemmensen reduction removes carbonyl groups from aldehydes and ketones to form alkanes or alkyl-substituted compounds e.g.: Preparation from other organic compounds Alkanes can be prepared from a variety of organic compounds. These include alkenes, alkynes, haloalkanes, alcohols, aldehydes, ketones and carboxylic acids. From alkenes and alkynes Addition of molecular hydrogen across the π bond(s) of alkenes and alkynes gives alkanes. This hydrogenation reaction is typically performed using a powdered metal catalyst, such as palladium, platinum, or nickel. The reaction is exothermic because the product alkane is more stable. This is an important process in several fields of industrial and research chemistry. From haloalkanes Several methods produce alkanes from haloalkanes. In the Wurtz reaction, a haloalkane is treated with sodium in dry ether to yield an alkane having double the number of carbon atoms. This reaction proceeds through a free radical intermediate and has the possibility of alkene formation in case of tertiary haloalkanes and vicinal dihalides. 2 R−X + 2 Na → R−R + 2 Na+X In Corey–House synthesis, a haloalkane is treated with dialkyl lithium cuprate, a Gilman reagent, to yield a higher alkane: Li+[R–Cu–R]– + R'–X → R–R' + R–Cu + Li+X Haloalkanes can be reduced to alkanes by reaction with hydride reagents such as lithium aluminium hydride. R−X + H– → R−H + X– Applications The applications of alkanes depend on the number of carbon atoms. The first four alkanes are used mainly for heating and cooking purposes, and in some countries for electricity generation. Methane and ethane are the main components of natural gas; they are normally stored as gases under pressure. It is, however, easier to transport them as liquids: This requires both compression and cooling of the gas. Propane and butane are gases at atmospheric pressure that can be liquefied at fairly low pressures and are commonly known as liquified petroleum gas (LPG). Propane is used in propane gas burners and as a fuel for road vehicles, butane in space heaters and disposable cigarette lighters. Both are used as propellants in aerosol sprays. From pentane to octane the alkanes are highly volatile liquids. They are used as fuels in internal combustion engines,

as they vaporize easily on entry into the combustion chamber without forming droplets, which would impair the uniformity of the combustion. Branched-chain alkanes are preferred as they are much less prone to premature ignition, which causes knocking, than their straight-chain homologues. This propensity to premature ignition is measured by the octane rating of the fuel, where 2,2,4-trimethylpentane (isooctane) has an arbitrary value of 100, and heptane has a value of zero. Apart from their use as fuels, the middle alkanes are also good solvents for nonpolar substances. Alkanes from nonane to, for instance, hexadecane (an alkane with sixteen carbon atoms) are liquids of higher viscosity, less and less suitable for use in gasoline. They form instead the major part of diesel and aviation fuel. Diesel fuels are characterized by their cetane number, cetane being an old name for hexadecane. However, the higher melting points of these alkanes can cause problems at low temperatures and in polar regions, where the fuel becomes too thick to flow correctly. Alkanes from hexadecane upwards form the most important components of fuel oil and lubricating oil. In the latter function, they work at the same time as anti-corrosive agents, as their hydrophobic nature means that water cannot reach the metal surface. Many solid alkanes find use as paraffin wax, for example, in candles. This should not be confused however with true wax, which consists primarily of esters. Alkanes with a chain length of approximately 35 or more carbon atoms are found in bitumen, used, for example, in road surfacing. However, the higher alkanes have little value and are usually split into lower alkanes by cracking. Some synthetic polymers such as polyethylene and polypropylene are alkanes with chains containing hundreds or thousands of carbon atoms. These materials are used in innumerable applications, and billions of kilograms of these materials are made and used each year. Environmental transformations Alkanes are chemically very inert apolar molecules which are not very reactive as organic compounds. This inertness yields serious ecological issues if they are released into the environment. Due to their lack of functional groups and low water solubility, alkanes show poor bioavailability for microorganisms. There are, however, some microorganisms possessing the metabolic capacity to utilize n-alkanes as both carbon and energy sources. Some bacterial species are highly specialised in degrading alkanes; these are referred to as hydrocarbonoclastic bacteria. Hazards Methane is flammable, explosive and dangerous to inhale; because

it is a colorless, odorless gas, special caution must be taken around methane. Ethane is also extremely flammable, explosive, and dangerous to inhale. Both of them may cause suffocation. Propane, too, is flammable and explosive, and may cause drowsiness or unconsciousness if inhaled. Butane presents the same hazards as propane. Alkanes also pose a threat to the environment. Branched alkanes have a lower biodegradability than unbranched alkanes. Methane is considered to be the greenhouse gas that is most dangerous to the environment, although the amount of methane in the atmosphere is relatively low. As of April, 2022, atmospheric methane concentrations were around 1910 ppb. See also Alkene Alkyne Cycloalkane Higher alkanes Aliphatic compound References Further reading Virtual Textbook of Organic Chemistry A visualization of the crystal structures of alkanes up to nonan Hydrocarbons

United States appellate procedure involves the rules and regulations for filing appeals in state courts and federal courts. The nature of an appeal can vary greatly depending on the type of case and the rules of the court in the jurisdiction where the case was prosecuted. There are many types of standard of review for appeals, such as de novo and abuse of discretion. However, most appeals begin when a party files a petition for review to a higher court for the purpose of overturning the lower court's decision. An appellate court is a court that hears cases on appeal from another court. Depending on the particular legal rules that apply to each circumstance, a party to a court case who is unhappy with the result might be able to challenge that result in an appellate court on specific grounds. These grounds typically could include errors of law, fact, procedure or due process. In different jurisdictions, appellate courts are also called appeals courts, courts of appeals, superior courts, or supreme courts. The specific procedures for appealing, including even whether there is a right of appeal from a particular type of decision, can vary greatly from state to state. The right to file an appeal can also vary from state to state; for example, the New Jersey Constitution vests judicial power in a Supreme Court, a Superior Court, and other courts of limited jurisdiction, with an appellate court being part of the Superior Court. Access to appellant status A party who files an appeal is called an "appellant", "plaintiff in error", "petitioner" or "pursuer", and a party on the other side is called an "appellee". A "cross-appeal" is an appeal brought by the respondent. For example, suppose at trial the judge found for the plaintiff and ordered the defendant to pay $50,000. If the defendant files an appeal arguing that he should not have to pay any money, then the plaintiff might file a cross-appeal arguing that the defendant should have to pay $200,000 instead of $50,000. The appellant is the party who, having lost part or all their claim in a lower court decision, is appealing to a higher court to have their case reconsidered. This is usually done on the basis that the lower court judge erred in the application of law, but it may also be possible to appeal on the basis of court misconduct, or that a

finding of fact was entirely unreasonable to make on the evidence. The appellant in the new case can be either the plaintiff (or claimant), defendant, third-party intervenor, or respondent (appellee) from the lower case, depending on who was the losing party. The winning party from the lower court, however, is now the respondent. In unusual cases the appellant can be the victor in the court below, but still appeal. An appellee is the party to an appeal in which the lower court judgment was in its favor. The appellee is required to respond to the petition, oral arguments, and legal briefs of the appellant. In general, the appellee takes the procedural posture that the lower court's decision should be affirmed. Ability to appeal An appeal "as of right" is one that is guaranteed by statute or some underlying constitutional or legal principle. The appellate court cannot refuse to listen to the appeal. An appeal "by leave" or "permission" requires the appellant to obtain leave to appeal; in such a situation either or both of the lower court and the court may have the discretion to grant or refuse the appellant's demand to appeal the lower court's decision. In the Supreme Court, review in most cases is available only if the Court exercises its discretion and grants a writ of certiorari. In tort, equity, or other civil matters either party to a previous case may file an appeal. In criminal matters, however, the state or prosecution generally has no appeal "as of right". And due to the double jeopardy principle, the state or prosecution may never appeal a jury or bench verdict of acquittal. But in some jurisdictions, the state or prosecution may appeal "as of right" from a trial court's dismissal of an indictment in whole or in part or from a trial court's granting of a defendant's suppression motion. Likewise, in some jurisdictions, the state or prosecution may appeal an issue of law "by leave" from the trial court or the appellate court. The ability of the prosecution to appeal a decision in favor of a defendant varies significantly internationally. All parties must present grounds to appeal, or it will not be heard. By convention in some law reports, the appellant is named first. This can mean that where it is the defendant who appeals, the name of the case in the law reports reverses (in some cases twice)

as the appeals work their way up the court hierarchy. This is not always true, however. In the federal courts, the parties' names always stay in the same order as the lower court when an appeal is taken to the circuit courts of appeals, and are re-ordered only if the appeal reaches the Supreme Court. Direct or collateral: Appealing criminal convictions Many jurisdictions recognize two types of appeals, particularly in the criminal context. The first is the traditional "direct" appeal in which the appellant files an appeal with the next higher court of review. The second is the collateral appeal or post-conviction petition, in which the petitioner-appellant files the appeal in a court of first instance—usually the court that tried the case. The key distinguishing factor between direct and collateral appeals is that the former occurs in state courts, and the latter in federal courts. Relief in post-conviction is rare and is most often found in capital or violent felony cases. The typical scenario involves an incarcerated defendant locating DNA evidence demonstrating the defendant's actual innocence. Appellate review "Appellate review" is the general term for the process by which courts with appellate jurisdiction take jurisdiction of matters decided by lower courts. It is distinguished from judicial review, which refers to the court's overriding constitutional or statutory right to determine if a legislative act or administrative decision is defective for jurisdictional or other reasons (which may vary by jurisdiction). In most jurisdictions the normal and preferred way of seeking appellate review is by filing an appeal of the final judgment. Generally, an appeal of the judgment will also allow appeal of all other orders or rulings made by the trial court in the course of the case. This is because such orders cannot be appealed "as of right". However, certain critical interlocutory court orders, such as the denial of a request for an interim injunction, or an order holding a person in contempt of court, can be appealed immediately although the case may otherwise not have been fully disposed of. There are two distinct forms of appellate review, "direct" and "collateral". For example, a criminal defendant may be convicted in state court, and lose on "direct appeal" to higher state appellate courts, and if unsuccessful, mount a "collateral" action such as filing for a writ of habeas corpus in the federal courts. Generally speaking, "[d]irect appeal statutes afford defendants the opportunity

to challenge the merits of a judgment and allege errors of law or fact. ... [Collateral review], on the other hand, provide[s] an independent and civil inquiry into the validity of a conviction and sentence, and as such are generally limited to challenges to constitutional, jurisdictional, or other fundamental violations that occurred at trial." "Graham v. Borgen", 483 F 3d. 475 (7th Cir. 2007) (no. 04–4103) (slip op. at 7) (citation omitted). In Anglo-American common law courts, appellate review of lower court decisions may also be obtained by filing a petition for review by prerogative writ in certain cases. There is no corresponding right to a writ in any pure or continental civil law legal systems, though some mixed systems such as Quebec recognize these prerogative writs. Direct appeal After exhausting the first appeal as of right, defendants usually petition the highest state court to review the decision. This appeal is known as a direct appeal. The highest state court, generally known as the Supreme Court, exercises discretion over whether it will review the case. On direct appeal, a prisoner challenges the grounds of the conviction based on an error that occurred at trial or some other stage in the adjudicative process. Preservation issues An appellant's claim(s) must usually be preserved at trial. This means that the defendant had to object to the error when it occurred in the trial. Because constitutional claims are of great magnitude, appellate courts might be more lenient to review the claim even if it was not preserved. For example, Connecticut applies the following standard to review unpreserved claims: 1.the record is adequate to review the alleged claim of error; 2. the claim is of constitutional magnitude alleging the violation of a fundamental right; 3. the alleged constitutional violation clearly exists and clearly deprived the defendant of a fair trial; 4. if subject to harmless error analysis, the state has failed to demonstrate harmlessness of the alleged constitutional violation beyond a reasonable doubt. State post-conviction relief: collateral appeal All States have a post-conviction relief process. Similar to federal post-conviction relief, an appellant can petition the court to correct alleged fundamental errors that were not corrected on direct review. Typical claims might include ineffective assistance of counsel and actual innocence based on new evidence. These proceedings are normally separate from the direct appeal, however some states allow for collateral relief to be sought on direct appeal.

After direct appeal, the conviction is considered final. An appeal from the post conviction court proceeds just as a direct appeal. That is, it goes to the intermediate appellate court, followed by the highest court. If the petition is granted the appellant could be released from incarceration, the sentence could be modified, or a new trial could be ordered. Habeas corpus Notice of appeal A "notice of appeal" is a form or document that in many cases is required to begin an appeal. The form is completed by the appellant or by the appellant's legal representative. The nature of this form can vary greatly from country to country and from court to court within a country. The specific rules of the legal system will dictate exactly how the appeal is officially begun. For example, the appellant might have to file the notice of appeal with the appellate court, or with the court from which the appeal is taken, or both. Some courts have samples of a notice of appeal on the court's own web site. In New Jersey, for example, the Administrative Office of the Court has promulgated a form of notice of appeal for use by appellants, though using this exact form is not mandatory and the failure to use it is not a jurisdictional defect provided that all pertinent information is set forth in whatever form of notice of appeal is used. The deadline for beginning an appeal can often be very short: traditionally, it is measured in days, not months. This can vary from country to country, as well as within a country, depending on the specific rules in force. In the U.S. federal court system, criminal defendants must file a notice of appeal within 10 days of the entry of either the judgment or the order being appealed, or the right to appeal is forfeited. Appellate procedure Generally speaking the appellate court examines the record of evidence presented in the trial court and the law that the lower court applied and decides whether that decision was legally sound or not. The appellate court will typically be deferential to the lower court's findings of fact (such as whether a defendant committed a particular act), unless clearly erroneous, and so will focus on the court's application of the law to those facts (such as whether the act found by the court to have occurred fits a legal definition

at issue). If the appellate court finds no defect, it "affirms" the judgment. If the appellate court does find a legal defect in the decision "below" (i.e., in the lower court), it may "modify" the ruling to correct the defect, or it may nullify ("reverse" or "vacate") the whole decision or any part of it. It may, in addition, send the case back ("remand" or "remit") to the lower court for further proceedings to remedy the defect. In some cases, an appellate court may review a lower court decision "de novo" (or completely), challenging even the lower court's findings of fact. This might be the proper standard of review, for example, if the lower court resolved the case by granting a pre-trial motion to dismiss or motion for summary judgment which is usually based only upon written submissions to the trial court and not on any trial testimony. Another situation is where appeal is by way of "re-hearing". Certain jurisdictions permit certain appeals to cause the trial to be heard afresh in the appellate court. Sometimes, the appellate court finds a defect in the procedure the parties used in filing the appeal and dismisses the appeal without considering its merits, which has the same effect as affirming the judgment below. (This would happen, for example, if the appellant waited too long, under the appellate court's rules, to file the appeal.) Generally, there is no trial in an appellate court, only consideration of the record of the evidence presented to the trial court and all the pre-trial and trial court proceedings are reviewed—unless the appeal is by way of re-hearing, new evidence will usually only be considered on appeal in "very" rare instances, for example if that material evidence was unavailable to a party for some very significant reason such as prosecutorial misconduct. In some systems, an appellate court will only consider the written decision of the lower court, together with any written evidence that was before that court and is relevant to the appeal. In other systems, the appellate court will normally consider the record of the lower court. In those cases the record will first be certified by the lower court. The appellant has the opportunity to present arguments for the granting of the appeal and the appellee (or respondent) can present arguments against it. Arguments of the parties to the appeal are presented through their appellate lawyers, if

represented, or "pro se" if the party has not engaged legal representation. Those arguments are presented in written briefs and sometimes in oral argument to the court at a hearing. At such hearings each party is allowed a brief presentation at which the appellate judges ask questions based on their review of the record below and the submitted briefs. In an adversarial system, appellate courts do not have the power to review lower court decisions unless a party appeals it. Therefore, if a lower court has ruled in an improper manner, or against legal precedent, that judgment will stand if not appealed – even if it might have been overturned on appeal. The United States legal system generally recognizes two types of appeals: a trial "de novo" or an appeal on the record. A trial de novo is usually available for review of informal proceedings conducted by some minor judicial tribunals in proceedings that do not provide all the procedural attributes of a formal judicial trial. If unchallenged, these decisions have the power to settle more minor legal disputes once and for all. If a party is dissatisfied with the finding of such a tribunal, one generally has the power to request a trial "de novo" by a court of record. In such a proceeding, all issues and evidence may be developed newly, as though never heard before, and one is not restricted to the evidence heard in the lower proceeding. Sometimes, however, the decision of the lower proceeding is itself admissible as evidence, thus helping to curb frivolous appeals. In some cases, an application for "trial de novo" effectively erases the prior trial as if it had never taken place. The Supreme Court of Virginia has stated that '"This Court has repeatedly held that the effect of an appeal to circuit court is to "annul the judgment of the inferior tribunal as completely as if there had been no previous trial."' The only exception to this is that if a defendant appeals a conviction for a crime having multiple levels of offenses, where they are convicted on a lesser offense, the appeal is of the lesser offense; the conviction represents an acquittal of the more serious offenses. "[A] trial on the same charges in the circuit court does not violate double jeopardy principles, . . . subject only to the limitation that conviction in [the] district court for an

offense lesser included in the one charged constitutes an acquittal of the greater offense, permitting trial de novo in the circuit court only for the lesser-included offense." In an appeal on the record from a decision in a judicial proceeding, both appellant and respondent are bound to base their arguments wholly on the proceedings and body of evidence as they were presented in the lower tribunal. Each seeks to prove to the higher court that the result they desired was the just result. Precedent and case law figure prominently in the arguments. In order for the appeal to succeed, the appellant must prove that the lower court committed reversible error, that is, an impermissible action by the court acted to cause a result that was unjust, and which would not have resulted had the court acted properly. Some examples of reversible error would be erroneously instructing the jury on the law applicable to the case, permitting seriously improper argument by an attorney, admitting or excluding evidence improperly, acting outside the court's jurisdiction, injecting bias into the proceeding or appearing to do so, juror misconduct, etc. The failure to formally object at the time, to what one views as improper action in the lower court, may result in the affirmance of the lower court's judgment on the grounds that one did not "preserve the issue for appeal" by objecting. In cases where a judge rather than a jury decided issues of fact, an appellate court will apply an "abuse of discretion" standard of review. Under this standard, the appellate court gives deference to the lower court's view of the evidence, and reverses its decision only if it were a clear abuse of discretion. This is usually defined as a decision outside the bounds of reasonableness. On the other hand, the appellate court normally gives less deference to a lower court's decision on issues of law, and may reverse if it finds that the lower court applied the wrong legal standard. In some cases, an appellant may successfully argue that the law under which the lower decision was rendered was unconstitutional or otherwise invalid, or may convince the higher court to order a new trial on the basis that evidence earlier sought was concealed or only recently discovered. In the case of new evidence, there must be a high probability that its presence or absence would have made a material difference in

the trial. Another issue suitable for appeal in criminal cases is effective assistance of counsel. If a defendant has been convicted and can prove that his lawyer did not adequately handle his case and that there is a reasonable probability that the result of the trial would have been different had the lawyer given competent representation, he is entitled to a new trial. A lawyer traditionally starts an oral argument to any appellate court with the words "May it please the court." After an appeal is heard, the "mandate" is a formal notice of a decision by a court of appeal; this notice is transmitted to the trial court and, when filed by the clerk of the trial court, constitutes the final judgment on the case, unless the appeal court has directed further proceedings in the trial court. The mandate is distinguished from the appeal court's opinion, which sets out the legal reasoning for its decision. In some jurisdictions the mandate is known as the "remittitur". Results The result of an appeal can be: Affirmed: Where the reviewing court basically agrees with the result of the lower courts' ruling(s). Reversed: Where the reviewing court basically disagrees with the result of the lower courts' ruling(s), and overturns their decision. Vacated: Where the reviewing court overturns the lower courts' ruling(s) as invalid, without necessarily disagreeing with it/them, e.g. because the case was decided on the basis of a legal principle that no longer applies. Remanded: Where the reviewing court sends the case back to the lower court. There can be multiple outcomes, so that the reviewing court can affirm some rulings, reverse others and remand the case all at the same time. Remand is not required where there is nothing left to do in the case. "Generally speaking, an appellate court's judgment provides 'the final directive of the appeals courts as to the matter appealed, setting out with specificity the court's determination that the action appealed from should be affirmed, reversed, remanded or modified'". Some reviewing courts who have discretionary review may send a case back without comment other than review improvidently granted. In other words, after looking at the case, they chose not to say anything. The result for the case of review improvidently granted is effectively the same as affirmed, but without that extra higher court stamp of approval. See also Appellate court Appellee Civil procedure Court of Appeals Courts-martial

in the United States Criminal procedure Defendant En banc Interlocutory appeal List of legal topics List of wrongful convictions in the United States Petition for stay Plaintiff Pursuer Reversible error Supreme Court of the United States Writ of Certiorari Writ of habeas corpus Writ of mandamus References External links Legal procedure United States procedural law

In law, an answer was originally a solemn assertion in opposition to someone or something, and thus generally any counter-statement or defense, a reply to a question or response, or objection, or a correct solution of a problem. In the common law, an answer is the first pleading by a defendant, usually filed and served upon the plaintiff within a certain strict time limit after a civil complaint or criminal information or indictment has been served upon the defendant. It may have been preceded by an optional "pre-answer" motion to dismiss or demurrer; if such a motion is unsuccessful, the defendant must file an answer to the complaint or risk an adverse default judgment. In a criminal case, there is usually an arraignment or some other kind of appearance before the defendant comes to court. The pleading in the criminal case, which is entered on the record in open court, is usually either guilty or not guilty. Generally speaking in private, civil cases there is no plea entered of guilt or innocence. There is only a judgment that grants money damages or some other kind of equitable remedy such as restitution or a permanent injunction. Criminal cases may lead to fines or other punishment, such as imprisonment. The famous Latin Responsa Prudentium ("answers of the learned ones") were the accumulated views of many successive generations of Roman lawyers, a body of legal opinion which gradually became authoritative. During debates of a contentious nature, deflection, colloquially known as 'changing the topic', has been widely observed, and is often seen as a failure to answer a question. Notes Common law Legal documents

A court of appeals, also called a court of appeal, appellate court, appeal court, court of second instance or second instance court, is any court of law that is empowered to hear an appeal of a trial court or other lower tribunal. In much of the world, court systems are divided into at least three levels: the trial court, which initially hears cases and reviews evidence and testimony to determine the facts of the case; at least one intermediate appellate court; and a supreme court (or court of last resort) which primarily reviews the decisions of the intermediate courts, often on a discretionary basis. A particular court system's supreme court is its highest appellate court. Appellate courts nationwide can operate under varying rules. Under its standard of review, an appellate court decides the extent of the deference it would give to the lower court's decision, based on whether the appeal were one of fact or of law. In reviewing an issue of fact, an appellate court ordinarily gives deference to the trial court's findings. It is the duty of trial judges or juries to find facts, view the evidence firsthand, and observe witness testimony. When reviewing lower decisions on an issue of fact, courts of appeal generally look for clear error. The appellate court reviews issues of law (anew, no deference) and may reverse or modify the lower court's decision if the appellate court believes the lower court misapplied the facts or the law. An appellate court may also review the lower judge's discretionary decisions, such as whether the judge properly granted a new trial or disallowed evidence. The lower court's decision is only changed in cases of an "abuse of discretion". This standard tends to be even more deferential than the "clear error" standard. Before hearing any case, the court must have jurisdiction to consider the appeal. The authority of appellate courts to review the decisions of lower courts varies widely from one jurisdiction to another. In some areas, the appellate court has limited powers of review. Generally, an appellate court's judgment provides the final directive of the appeals courts as to the matter appealed, setting out with specificity the court's determination that the action appealed from should be affirmed, reversed, remanded or modified. Depending on the type of case and the decision below, appellate review primarily consists of: an entirely new hearing (a non trial de novo); a

hearing where the appellate court gives deference to factual findings of the lower court; or review of particular legal rulings made by the lower court (an appeal on the record). Bifurcation of civil and criminal appeals While many appellate courts have jurisdiction over all cases decided by lower courts, some systems have appellate courts divided by the type of jurisdiction they exercise. Some jurisdictions have specialized appellate courts, such as the Texas Court of Criminal Appeals, which only hears appeals raised in criminal cases, and the U.S. Court of Appeals for the Federal Circuit, which has general jurisdiction but derives most of its caseload from patent cases, on one hand, and appeals from the Court of Federal Claims on the other. In the United States, Alabama, Tennessee, and Oklahoma also have separate courts of criminal appeals. Texas and Oklahoma have the final determination of criminal cases vested in their respective courts of criminal appeals, while Alabama and Tennessee allow decisions of its court of criminal appeals to be finally appealed to the state supreme court. Courts of criminal appeals Civilian Court of Criminal Appeal (England and Wales), abolished 1966 Court of Criminal Appeal (Ireland), abolished 2014 U.S. States: Alabama Court of Criminal Appeals Oklahoma Court of Criminal Appeals Tennessee Court of Criminal Appeals Texas Court of Criminal Appeals Military United States Army Court of Criminal Appeals Navy-Marine Corps Court of Criminal Appeals (United States) Coast Guard Court of Criminal Appeals (United States) Air Force Court of Criminal Appeals (United States) Courts of civil appeals Alabama Court of Civil Appeals Oklahoma Court of Civil Appeals Appellate courts by country Australia The High Court has appellate jurisdiction over all other courts. Leave must be granted by the court, before the appeal matter is heard. The High Court is paramount to all federal courts. Further, it has an constitutionally entrenched general power of appeal from the Supreme Courts of the States and Territories. Appeals to the High Court are by special leave only, which is generally only granted in cases of public importance, matters involving the interpretation of the Commonwealth Constitution, or where the law has been inconsistently applied across the States and Territories.[19] Therefore, in the vast majority of cases, the appellate divisions of the Supreme Courts of each State and Territory and the Federal Court are the final courts of appeal. New Zealand The Court of Appeal of New Zealand, located

in Wellington, is New Zealand's principal intermediate appellate court. In practice, most appeals are resolved at this intermediate appellate level, rather than in the Supreme Court. Philippines The Court of Appeals of the Philippines is the principal intermediate appellate court of that country. The Court of Appeals is primarily found in Manila, with three divisions each in Cebu City and Cagayan de Oro. Other appellate courts include the Sandiganbayan for cases involving graft and corruption, and the Court of Tax Appeals for cases involving tax. Appeals from all three appellate courts are to the Supreme Court. Sri Lanka The Court of Appeal of Sri Lanka, located in Colombo, is the second senior court in the Sri Lankan legal system. United Kingdom United States In the United States, both state and federal appellate courts are usually restricted to examining whether the lower court made the correct legal determinations, rather than hearing direct evidence and determining what the facts of the case were. Furthermore, U.S. appellate courts are usually restricted to hearing appeals based on matters that were originally brought up before the trial court. Hence, such an appellate court will not consider an appellant's argument if it is based on a theory that is raised for the first time in the appeal. In most U.S. states, and in U.S. federal courts, parties before the court are allowed one appeal as of right. This means that a party who is unsatisfied with the outcome of a trial may bring an appeal to contest that outcome. However, appeals may be costly, and the appellate court must find an error on the part of the court below that justifies upsetting the verdict. Therefore, only a small proportion of trial court decisions result in appeals. Some appellate courts, particularly supreme courts, have the power of discretionary review, meaning that they can decide whether they will hear an appeal brought in a particular case. Institutional titles Many U.S. jurisdictions title their appellate court a court of appeal or court of appeals. Historically, others have titled their appellate court a court of errors (or court of errors and appeals), on the premise that it was intended to correct errors made by lower courts. Examples of such courts include the New Jersey Court of Errors and Appeals (which existed from 1844 to 1947), the Connecticut Supreme Court of Errors (which has been renamed the Connecticut Supreme Court), the

Kentucky Court of Errors (renamed the Kentucky Supreme Court), and the Mississippi High Court of Errors and Appeals (since renamed the Supreme Court of Mississippi). In some jurisdictions, a court able to hear appeals is known as an appellate division. The phrase "court of appeals" most often refers to intermediate appellate courts. However, the New York Court of Appeals is the highest appellate court in New York. The New York Supreme Court is a trial court of general jurisdiction. The Supreme Court of Maryland was known as the Court of Appeals, and the Appellate Court of Maryland was known as the Court of Special Appeals, until a 2022 constitutional amendment changed their names. Depending on the system, certain courts may serve as both trial courts and appellate courts, hearing appeals of decisions made by courts with more limited jurisdiction. See also Court of Criminal Appeal (disambiguation) Court of Appeal (Hong Kong) High Court (Hong Kong) Court of Appeal (England and Wales) Court of cassation References Citations Sources Lax, Jeffrey R. "Constructing Legal Rules on Appellate Courts." American Political Science Review 101.3 (2007): 591–604. Sociological Abstracts; Worldwide Political Science Abstracts. Web. 29 May 2012. Courts by type Appellate courts Jurisdiction

Arraignment is a formal reading of a criminal charging document in the presence of the defendant, to inform them of the charges against them. In response to arraignment, in some jurisdictions, the accused is expected to enter a plea, in other jurisdictions no plea is required. Acceptable pleas vary among jurisdictions, but they generally include "guilty", "not guilty", and the peremptory pleas, or pleas in bar, setting out reasons why a trial cannot proceed. Pleas of nolo contendere ("no contest") and the Alford plea are allowed in some circumstances. Australia In Australia, arraignment is the first of 11 stages in a criminal trial, and involves the clerk of the court reading out the indictment. The judge will testify during the indictment process. Canada In every province in Canada, except British Columbia, defendants are arraigned on the day of their trial. In British Columbia, arraignment takes place in one of the first few court appearances by the defendant or their lawyer. The defendant is asked whether they plead guilty or not guilty to each charge. France In France, the general rule is that one cannot remain in police custody for more than 24 hours from the time of the arrest. However, police custody can last another 24 hours in specific circumstances, especially if the offence is punishable by at least one year's imprisonment, or if the investigation is deemed to require the extra time, and can last up to 96 hours in certain cases involving terrorism, drug trafficking or organised crime. The police need to have the consent of the prosecutor, the procureur. In the vast majority of cases, the prosecutor will consent. Germany In Germany, if one has been arrested and taken into custody by the police one must be brought before a judge as soon as possible and at the latest on the day after the arrest. New Zealand In New Zealand law, at the first appearance of the accused, they are read the charges and asked for a plea. The available pleas are: guilty, not guilty, and no plea. No plea allows the defendant to get legal advice on the plea, which must be made on the second appearance. South Africa In South Africa, arraignment is defined as the calling upon the accused to appear, the informing of the accused of the crime charged against them, the demanding of the accused whether they plead guilty or not guilty,

and the entering of their plea. Their plea having been entered, they are said to stand arraigned. United Kingdom In England, Wales, and Northern Ireland, arraignment is the first of 11 stages in a criminal trial, and involves the clerk of the court reading out the indictment. In England and Wales, the police cannot legally detain anyone for more than 24 hours without charging them unless an officer with the rank of superintendent (or above) authorises detention for a further 12 hours (36 hours total), or a judge (who will be a magistrate) authorises detention by the police before charge for up to a maximum of 96 hours, but for terrorism-related offences people can be held by the police for up to 28 days before charge. If they are not released after being charged, they should be brought before a court as soon as practicable. United States Under the United States Federal Rules of Criminal Procedure, "arraignment shall [...] [consist of an] open [...] reading [of] the indictment [...] to the defendant [...] and call[] on [the defendant] to plead thereto. [T]he defendant shall be given a copy of the indictment [...] before being called upon to plead." In federal courts, arraignment takes place in two stages. The first is called the "initial arraignment" and must take place within 48 hours of an individual's arrest, 72 hours if the individual was arrested on the weekend and not able to go before a judge until Monday. During this stage, the defendant is informed of the pending legal charges and is informed of his or her right to retain counsel. The presiding judge also decides at what amount, if any, to set bail. During the second stage, a post-indictment arraignment (PIA), the defendant is allowed to enter a plea. In New York, a person arrested without a warrant and kept in custody must be brought before to a local criminal court for arraignment "without unnecessary delay." A delay of more than 24 hours is rebuttably presumed to be unnecessary. In California, arraignments must be conducted without unnecessary delay and, in any event, within 48 hours of arrest, excluding weekends and holidays. Form of the arraignment The wording of the arraignment varies from jurisdiction to jurisdiction. However, it generally conforms with the following principles: The accused person (defendant) is addressed by name; The charge against the accused person is read, including the alleged

date, time, and place of offense (and sometimes the names of the state's witnesses and the range of punishment for the charge(s)); and, The accused person is asked formally how they plead. Video arraignment Video arraignment is the act of conducting the arraignment process using some form of videoconferencing technology. Use of video arraignment system allows the court to conduct the requisite arraignment process without the need to transport the defendant to the courtroom by using an audio-visual link between the location where the defendant is being held and the courtroom. Use of the video arraignment process addresses the problems associated with having to transport defendants. The transportation of defendants requires time, puts additional demands on the public safety organizations to provide for the safety of the public, court personnel and for the security of the population held in detention. It also addresses the rising costs of transportation. Guilty and not-guilty pleas If the defendant pleads guilty, an evidentiary hearing usually follows. The court is not required to accept a guilty plea. During the hearing, the judge assesses the offense, the mitigating factors, and the defendant's character, and passes sentence. If the defendant pleads not guilty, a date is set for a preliminary hearing or a trial. In the past, a defendant who refused to plead (or "stood mute") was subject to peine forte et dure (Law French for "strong and hard punishment"). Today, in common law jurisdictions, the court enters a plea of not guilty for a defendant who refuses to enter a plea. The rationale for this is the defendant's right to silence. Pre-trial release This is also often the stage at which arguments for or against pre-trial release and bail may be made, depending on the alleged crime and jurisdiction. See also Desk appearance ticket References Legal terminology Prosecution United States criminal procedure Criminal law of the United Kingdom Australian criminal law

"America the Beautiful" is a patriotic American song. Its lyrics were written by Katharine Lee Bates and its music was composed by church organist and choirmaster Samuel A. Ward at Grace Episcopal Church in Newark, New Jersey. The two never met. Bates wrote the words as a poem originally entitled "Pikes Peak". It was first published in the Fourth of July 1895 edition of the church periodical, The Congregationalist. It was at that time that the poem was first entitled "America". Ward had initially composed the song's melody in 1882 to accompany lyrics to "Materna", basis of the hymn, "O Mother dear, Jerusalem", though the hymn was not first published until 1892. The combination of Ward's melody and Bates's poem was first entitled "America the Beautiful" in 1910. The song is one of the most popular of the many U.S. patriotic songs. History In 1893, at the age of 33, Bates, an English professor at Wellesley College, had taken a train trip to Colorado Springs, Colorado, to teach at Colorado College. Several of the sights on her trip inspired her, and they found their way into her poem, including the World's Columbian Exposition in Chicago, the "White City" with its promise of the future contained within its gleaming white buildings; the wheat fields of North America's heartland Kansas, through which her train was riding on July 16; and the majestic view of the Great Plains from high atop Pikes Peak. On the pinnacle of that mountain, the words of the poem started to come to her, and she wrote them down upon returning to her hotel room at the original Antlers Hotel. The poem was initially published two years later in The Congregationalist to commemorate the Fourth of July. It quickly caught the public's fancy. An amended version was published in 1904. The first known melody written for the song was sent in by Silas Pratt when the poem was published in The Congregationalist. By 1900, at least 75 different melodies had been written. A hymn tune composed in 1882 by Samuel A. Ward, the organist and choir director at Grace Church, Newark, was generally considered the best music as early as 1910 and is still the popular tune today. Just as Bates had been inspired to write her poem, Ward, too, was inspired. The tune came to him while he was on a ferryboat trip from Coney Island back

to his home in New York City after a leisurely summer day and he immediately wrote it down. He composed the tune for the old hymn "O Mother Dear, Jerusalem", retitling the work "Materna". Ward's music combined with Bates's poem were first published together in 1910 and titled "America the Beautiful". Ward died in 1903, not knowing the national stature his music would attain. Bates was more fortunate, since the song's popularity was well established by the time of her death in 1929. It is included in songbooks in many religious congregations in the United States. At various times in the more than one hundred years that have elapsed since the song was written, particularly during the John F. Kennedy administration, there have been efforts to give "America the Beautiful" legal status either as a national hymn or as a national anthem equal to, or in place of, "The Star-Spangled Banner", but so far this has not succeeded. Proponents prefer "America the Beautiful" for various reasons, saying it is easier to sing, more melodic, and more adaptable to new orchestrations while still remaining as easily recognizable as "The Star-Spangled Banner". Some prefer "America the Beautiful" over "The Star-Spangled Banner" due to the latter's war-oriented imagery, while others object to the implicit support of slavery and racism in its third verse; others prefer "The Star-Spangled Banner" because of its war themes. While that national dichotomy has stymied any effort at changing the tradition of the national anthem, "America the Beautiful" continues to be held in high esteem by a large number of Americans, and was even being considered before 1931 as a candidate to become the national anthem of the United States. Lyrics Notable performances Elvis Presley performed it many times in concerts starting in 1976. Bing Crosby included the song in a medley on his album 101 Gang Songs (1961). Frank Sinatra recorded the song with Nelson Riddle during the sessions for The Concert Sinatra in February 1963, for a projected 45 single release. The 45 was not commercially issued however, but the song was later added as a bonus track to the enhanced 2012 CD release of The Concert Sinatra. In 1976, while the United States celebrated its bicentennial, a soulful version popularized by Ray Charles peaked at number 98 on the US R&B chart. His version was traditionally played on New Year's Eve in Times Square following the

ball drop. Barbra Streisand release an official music video footage during Norman Lear's Special in 1982. During her peak to stardom, R&B singer Mariah Carey sang the song at the 1990 NBA Finals. Whitney Houston also recorded the song, covering Ray Charles' soulful rearranged version as the b-side to her 1991 rendition of "The Star Spangled Banner". Three different renditions of the song have entered the Hot Country Songs charts. The first was by Charlie Rich, which went to number 22 in 1976. A second, by Mickey Newbury, peaked at number 82 in 1980. Aretha Franklin performed a rendition before an undisputed audience of 93,173 to open WrestleMania III, a performance meta-critic RJ City called "a lovely version". An all-star version of "America the Beautiful" performed by country singers Trace Adkins, Sherrié Austin, Billy Dean, Vince Gill, Carolyn Dawn Johnson, Toby Keith, Brenda Lee, Lonestar, Lyle Lovett, Lila McCann, Lorrie Morgan, Jamie O'Neal, The Oak Ridge Boys, Collin Raye, Kenny Rogers, Keith Urban and Phil Vassar reached number 58 in July 2001. The song re-entered the chart following the September 11 attacks. Popularity of the song increased greatly in the decades following 9/11; at some sporting events it was sung in addition to the traditional singing of the national anthem. During the first taping of the Late Show with David Letterman following the attacks, CBS newsman Dan Rather cried briefly as he quoted the fourth verse. For Super Bowl XLVIII, The Coca-Cola Company aired a multilingual version of the song, sung in several different languages. The commercial received some criticism on social media sites, such as Twitter and Facebook, and from some conservatives, such as Glenn Beck. Despite the controversies, Coca-Cola later reused the Super Bowl ad during Super Bowl LI, the opening ceremonies of the 2014 Winter Olympics and 2016 Summer Olympics and for patriotic holidays. In 2016, American five-piece girl group Fifth Harmony performed a rendition to honor the United States women's national soccer team on defeating Japan 5–2 in the Final to win the 2015 FIFA Women's World Cup last July at BC Place in Vancouver, British Columbia, Canada before an undisputed AT&T Stadium audience of 101,763 to open WrestleMania 32 in Dallas, Texas. In 2017, Jackie Evancho released Together We Stand, a disc containing three patriotic songs including "America the Beautiful". The song charted at No. 4 on Billboard's Classical Digital Song sales chart. An abbreviated

cover with the 1911 lyrics was performed by Greg Jong for the soundtrack of the 2020 video game Wasteland 3, and is played during the final hostile encounters in the Denver section. In 2021, Jennifer Lopez performed the song at the inauguration of Joe Biden, as the second half of a medley with "This Land Is Your Land" by Woody Guthrie. Idioms "From sea to shining sea", originally used in the charters of some of the English Colonies in North America, is an American idiom meaning "from the Atlantic Ocean to the Pacific Ocean" (or vice versa). Other songs that have used this phrase include the American patriotic song "God Bless the U.S.A." and Schoolhouse Rock's "Elbow Room". The phrase and the song are also the namesake of the Shining Sea Bikeway, a bike path in Bates's hometown of Falmouth, Massachusetts. The phrase is similar to the Latin phrase "" ("From sea to sea"), which is the official motto of Canada. "Purple mountain majesties" refers to the shade of Pikes Peak in Colorado Springs, Colorado, which inspired Bates to write the poem. The idiom inspired the Colorado Rockies to have purple as one of its team colors. In 2003, Tori Amos appropriated the phrase "for amber waves of grain" to create a personification for her song "Amber Waves". Amos imagines Amber Waves as an exotic dancer, like the character of the same name portrayed by Julianne Moore in Boogie Nights. Books Lynn Sherr's 2001 book America the Beautiful discusses the origins of the song and the backgrounds of its authors in depth. The book points out that the poem has the same meter as that of "Auld Lang Syne"; the songs can be sung interchangeably. Additionally, Sherr discusses the evolution of the lyrics, for instance, changes to the original third verse written by Bates. Melinda M. Ponder, in her 2017 biography Katharine Lee Bates: From Sea to Shining Sea, draws heavily on Bates's diaries and letters to trace the history of the poem and its place in American culture. See also "God Bless America" Notes References External links MP3 and RealAudio recordings available at the United States Library of Congress Words, sheet music & MIDI file at the Cyber Hymnal America the Beautiful Park in Colorado Springs named for Katharine Lee Bates' words. Archival collection of America the Beautiful lantern slides from the 1930s. Another free sheet music 1895 songs

American Christian hymns American patriotic songs Pikes Peak History of Colorado Springs, Colorado Songs based on poems Grammy Hall of Fame Award recipients Concert band pieces Ray Charles songs Whitney Houston songs

Assistive technology (AT) is a term for assistive, adaptive, and rehabilitative devices for people with disabilities and the elderly. Disabled people often have difficulty performing activities of daily living (ADLs) independently, or even with assistance. ADLs are self-care activities that include toileting, mobility (ambulation), eating, bathing, dressing, grooming, and personal device care. Assistive technology can ameliorate the effects of disabilities that limit the ability to perform ADLs. Assistive technology promotes greater independence by enabling people to perform tasks they were formerly unable to accomplish, or had great difficulty accomplishing, by providing enhancements to, or changing methods of interacting with, the technology needed to accomplish such tasks. For example, wheelchairs provide independent mobility for those who cannot walk, while assistive eating devices can enable people who cannot feed themselves to do so. Due to assistive technology, disabled people have an opportunity of a more positive and easygoing lifestyle, with an increase in "social participation," "security and control," and a greater chance to "reduce institutional costs without significantly increasing household expenses." In schools, assistive technology can be critical in allowing students with disabilities access the general education curriculum. Students who experience challenges writing or keyboarding, for example, can use voice recognition software instead. Assistive technologies assist people who are recovering from strokes and people who have abstained injuries that effect their daily tasks. Adaptive technology Adaptive technology and assistive technology are different. Assistive technology is something that is used to help disabled people, while adaptive technology covers items that are specifically designed for disabled people and would seldom be used by a non-disabled person. In other words, assistive technology is any object or system that helps people with disabilities, while adaptive technology is specifically designed for disabled people. Consequently, adaptive technology is a subset of assistive technology. Adaptive technology often refers specifically to electronic and information technology access. Occupational therapy Occupational therapy (OT) is a healthcare profession that specializes in maintaining or improving the quality of life for individuals that experience challenges when independently performing life's occupations. According to the Occupational Therapy Practice Framework: Domain and Process (3rd ed.; AOTA, 2014), occupations include areas related to all basic and instrumental activities of daily living (ADLs), rest and sleep, education, work, play, leisure and social participation. Occupational therapists have the specialized skill of employing assistive technology (AT) in the improvement and maintenance of optimal, functional participation in occupations. The application of AT enables

an individual to adapt aspects of the environment, that may otherwise be challenging, to the user in order to optimize functional participation in those occupations. As a result, occupational therapists may educate, recommend, and promote the use of AT to improve the quality of life for their clients. Mobility impairments Wheelchairs Wheelchairs are devices that can be manually propelled or electrically propelled, and that include a seating system and are designed to be a substitute for the normal mobility that most people have. Wheelchairs and other mobility devices allow people to perform mobility-related activities of daily living which include feeding, toileting, dressing, grooming, and bathing. The devices come in a number of variations where they can be propelled either by hand or by motors where the occupant uses electrical controls to manage motors and seating control actuators through a joystick, sip-and-puff control, head switches or other input devices. Often there are handles behind the seat for someone else to do the pushing or input devices for caregivers. Wheelchairs are used by people for whom walking is difficult or impossible due to illness, injury, or disability. People with both sitting and walking disability often need to use a wheelchair or walker. Newer advancements in wheelchair design enable wheelchairs to climb stairs, go off-road or propel using segway technology or additional add-ons like handbikes or power assists. Transfer devices Patient transfer devices generally allow patients with impaired mobility to be moved by caregivers between beds, wheelchairs, commodes, toilets, chairs, stretchers, shower benches, automobiles, swimming pools, and other patient support systems (i.e., radiology, surgical, or examining tables). The most common devices are transfer benches, stretcher or convertible chairs (for lateral, supine transfer), sit-to-stand lifts (for moving patients from one seated position to another i.e., from wheelchairs to commodes), air bearing inflatable mattresses (for supine transfer i.e., transfer from a gurney to an operating room table), gait belts (or transfer belt) and a slider board (or transfer board), usually used for transfer from a bed to a wheelchair or from a bed to an operating table. Highly dependent patients who cannot assist their caregiver in moving them often require a patient lift (a floor or ceiling-suspended sling lift) which though invented in 1955 and in common use since the early 1960s is still considered the state-of-the-art transfer device by OSHA and the American Nursing Association. Walkers A walker or walking frame or Rollator is

a tool for disabled people who need additional support to maintain balance or stability while walking. It consists of a frame that is about waist high, approximately twelve inches deep and slightly wider than the user. Walkers are also available in other sizes, such as for children, or for heavy people. Modern walkers are height-adjustable. The front two legs of the walker may or may not have wheels attached depending on the strength and abilities of the person using it. It is also common to see caster wheels or glides on the back legs of a walker with wheels on the front. Treadmills Bodyweight-supported treadmill training (BWSTT) are used to enhance walking ability of people with neurological injury. These machines are therapist-assisted devices that are used in the clinical setting, but is limited by the personnel and labor requirements placed on physical therapists. The BWSTT device, and many others like it, assist physical therapists by providing task-specific practice of walking in people following neurological injury. Prosthesis A prosthesis, prosthetic, or prosthetic limb is a device that replaces a missing body part. It is part of the field of biomechatronics, the science of using mechanical devices with human muscular, musculoskeletal, and nervous systems to assist or enhance motor control lost by trauma, disease, or defect. Prostheses are typically used to replace parts lost by injury (traumatic) or missing from birth (congenital) or to supplement defective body parts. Inside the body, artificial heart valves are in common use with artificial hearts and lungs seeing less common use but under active technology development. Other medical devices and aids that can be considered prosthetics include hearing aids, artificial eyes, palatal obturator, gastric bands, and dentures. Prostheses are specifically not orthoses, although given certain circumstances a prosthesis might end up performing some or all of the same functionary benefits as an orthosis. Prostheses are technically the complete finished item. For instance, a C-Leg knee alone is not a prosthesis, but only a prosthetic component. The complete prosthesis would consist of the attachment system to the residual limb — usually a "socket", and all the attachment hardware components all the way down to and including the terminal device. Despite the technical difference, the terms are often used interchangeably. The terms "prosthetic" and "orthotic" are adjectives used to describe devices such as a prosthetic knee. The terms "prosthetics" and "orthotics" are used to describe the respective allied

health fields. An Occupational Therapist's role in prosthetics include therapy, training and evaluations. Prosthetic training includes orientation to prosthetics components and terminology, donning and doffing, wearing schedule, and how to care for residual limb and the prosthesis. Exoskeletons A powered exoskeleton is a wearable mobile machine that is powered by a system of electric motors, pneumatics, levers, hydraulics, or a combination of technologies that allow for limb movement with increased strength and endurance. Its design aims to provide back support, sense the user's motion, and send a signal to motors which manage the gears. The exoskeleton supports the shoulder, waist and thigh, and assists movement for lifting and holding heavy items, while lowering back stress. Adaptive seating and positioning People with balance and motor function challenges often need specialized equipment to sit or stand safely and securely. This equipment is frequently specialized for specific settings such as in a classroom or nursing home. Positioning is often important in seating arrangements to ensure that user's body pressure is distributed equally without inhibiting movement in a desired way. Positioning devices have been developed to aid in allowing people to stand and bear weight on their legs without risk of a fall. These standers are generally grouped into two categories based on the position of the occupant. Prone standers distribute the body weight to the front of the individual and usually have a tray in front of them. This makes them good for users who are actively trying to carry out some task. Supine standers distribute the body weight to the back and are good for cases where the user has more limited mobility or is recovering from injury. For children Children with severe disabilities can develop learned helplessness, which makes them lose interest in their environment. Robotic arms are used to provide an alternative method to engage in joint play activities. These robotic arms allows children to manipulate real objects in the context of play activities. Visual impairments Many people with serious visual impairments live independently, using a wide range of tools and techniques. Examples of assistive technology for visually impairment include screen readers, screen magnifiers, Braille embossers, desktop video magnifiers, and voice recorders. Screen readers Screen readers are used to help the visually impaired to easily access electronic information. These software programs run on a computer in order to convey the displayed information through voice (text-to-speech) or braille (refreshable braille displays)

in combination with magnification for low vision users in some cases. There are a variety of platforms and applications available for a variety of costs with differing feature sets. Some example of screen readers are Apple VoiceOver, Google TalkBack and Microsoft Narrator. This software is provided free of charge on all Apple devices. Apple VoiceOver includes the option to magnify the screen, control the keyboard, and provide verbal descriptions to describe what is happening on the screen. There are thirty languages to select from. It also has the capacity to read aloud file content, as well as web pages, E-mail messages, and word processing files. As mentioned above, screen readers may rely on the assistance of text-to-speech tools. To use the text-to-speech tools, the documents must in an electronic form, that is uploaded as the digital format. However, people usually will use the hard copy documents scanned into the computer, which cannot be recognized by the text-to-speech software. To solve this issue, people always use Optical Character Recognition technology accompanied with text-to-speech software. Braille and braille technology Braille is a system of raised dots formed into units called braille cells. A full braille cell is made up of six dots, with two parallel rows of three dots, but other combinations and quantities of dots represent other letters, numbers, punctuation marks, or words. People can then use their fingers to read the code of raised dots. Assistive technology using braille is called braille technology. Braille translator A braille translator is a computer program that can translate inkprint into braille or braille into inkprint. A braille translator can be an app on a computer or be built into a website, a smartphone, or a braille device. Braille embosser A braille embosser is, simply put, a printer for braille. Instead of a standard printer adding ink onto a page, the braille embosser imprints the raised dots of braille onto a page. Some braille embossers combine both braille and ink so the documents can be read with either sight or touch. Refreshable braille display A refreshable braille display or braille terminal is an electro-mechanical device for displaying braille characters, usually by means of round-tipped pins raised through holes in a flat surface. Computer users who cannot use a computer monitor use it to read a braille output version of the displayed text. Desktop video magnifier Desktop video magnifiers are electronic devices that use a

camera and a display screen to perform digital magnification of printed materials. They enlarge printed pages for those with low vision. A camera connects to a monitor that displays real-time images, and the user can control settings such as magnification, focus, contrast, underlining, highlighting, and other screen preferences. They come in a variety of sizes and styles; some are small and portable with handheld cameras, while others are much larger and mounted on a fixed stand. Screen magnification software A screen magnifier is software that interfaces with a computer's graphical output to present enlarged screen content. It allows users to enlarge the texts and graphics on their computer screens for easier viewing. Similar to desktop video magnifiers, this technology assists people with low vision. After the user loads the software into their computer's memory, it serves as a kind of "computer magnifying glass." Wherever the computer cursor moves, it enlarges the area around it. This allows greater computer accessibility for a wide range of visual abilities. Large-print and tactile keyboards A large-print keyboard has large letters printed on the keys. On the keyboard shown, the round buttons at the top control software which can magnify the screen (zoom in), change the background color of the screen, or make the mouse cursor on the screen larger. The "bump dots" on the keys, installed in this case by the organization using the keyboards, help the user find the right keys in a tactile way. Navigation assistance Assistive technology for navigation has exploded on the IEEE Xplore database since 2000, with over 7,500 engineering articles written on assistive technologies and visual impairment in the past 25 years, and over 1,300 articles on solving the problem of navigation for people who are blind or visually impaired. As well, over 600 articles on augmented reality and visual impairment have appeared in the engineering literature since 2000. Most of these articles were published within the past 5 years, and the number of articles in this area is increasing every year. GPS, accelerometers, gyroscopes, and cameras can pinpoint the exact location of the user and provide information on what is in the immediate vicinity, and assistance in getting to a destination. Wearable technology Wearable technology are smart electronic devices that can be worn on the body as an implant or an accessory. New technologies are exploring how the visually impaired can receive visual information through wearable devices.

Some wearable devices for visual impairment include: OrCam device, eSight and Brainport. Personal emergency response systems Personal emergency response systems (PERS), or Telecare (UK term), are a particular sort of assistive technology that use electronic sensors connected to an alarm system to help caregivers manage risk and help vulnerable people stay independent at home longer. An example would be the systems being put in place for senior people such as fall detectors, thermometers (for hypothermia risk), flooding and unlit gas sensors (for people with mild dementia). Notably, these alerts can be customized to the particular person's risks. When the alert is triggered, a message is sent to a caregiver or contact center who can respond appropriately. Accessibility software In human–computer interaction, computer accessibility (also known as accessible computing) refers to the accessibility of a computer system to all people, regardless of disability or severity of impairment, examples include web accessibility guidelines. Another approach is for the user to present a token to the computer terminal, such as a smart card, that has configuration information to adjust the computer speed, text size, etc. to their particular needs. This is useful where users want to access public computer based terminals in Libraries, ATM, Information kiosks etc. The concept is encompassed by the CEN EN 1332-4 Identification Card Systems – Man-Machine Interface. This development of this standard has been supported in Europe by SNAPI and has been successfully incorporated into the Lasseo specifications, but with limited success due to the lack of interest from public computer terminal suppliers. Hearing impairments People in the d/Deaf and hard of hearing community have a more difficult time receiving auditory information as compared to hearing individuals. These individuals often rely on visual and tactile mediums for receiving and communicating information. The use of assistive technology and devices provides this community with various solutions to auditory communication needs by providing higher sound (for those who are hard of hearing), tactile feedback, visual cues and improved technology access. Individuals who are deaf or hard of hearing utilize a variety of assistive technologies that provide them with different access to information in numerous environments. Most devices either provide amplified sound or alternate ways to access information through vision and/or vibration. These technologies can be grouped into three general categories: Hearing Technology, alerting devices, and communication support. Hearing aids A hearing aid or deaf aid is an electro-acoustic device which is

designed to amplify sound for the wearer, usually with the aim of making speech more intelligible, and to correct impaired hearing as measured by audiometry. This type of assistive technology helps people with hearing loss participate more fully in their hearing communities by allowing them to hear more clearly. They amplify any and all sound waves through use of a microphone, amplifier, and speaker. There is a wide variety of hearing aids available, including digital, in-the-ear, in-the-canal, behind-the-ear, and on-the-body aids. Assistive listening devices Assistive listening devices include FM, infrared, and loop assistive listening devices. This type of technology allows people with hearing difficulties to focus on a speaker or subject by getting rid of extra background noises and distractions, making places like auditoriums, classrooms, and meetings much easier to participate in. The assistive listening device usually uses a microphone to capture an audio source near to its origin and broadcast it wirelessly over an FM (Frequency Modulation) transmission, IR (Infra Red) transmission, IL (Induction Loop) transmission, or other transmission methods. The person who is listening may use an FM/IR/IL Receiver to tune into the signal and listen at his/her preferred volume. Amplified telephone equipment This type of assistive technology allows users to amplify the volume and clarity of their phone calls so that they can easily partake in this medium of communication. There are also options to adjust the frequency and tone of a call to suit their individual hearing needs. Additionally, there is a wide variety of amplified telephones to choose from, with different degrees of amplification. For example, a phone with 26 to 40 decibel is generally sufficient for mild hearing loss, while a phone with 71 to 90 decibel is better for more severe hearing loss. Augmentative and alternative communication Augmentative and alternative communication (AAC) is an umbrella term that encompasses methods of communication for those with impairments or restrictions on the production or comprehension of spoken or written language. AAC systems are extremely diverse and depend on the capabilities of the user. They may be as basic as pictures on a board that are used to request food, drink, or other care; or they can be advanced speech generating devices, based on speech synthesis, that are capable of storing hundreds of phrases and words. Cognitive impairments Assistive Technology for Cognition (ATC) is the use of technology (usually high tech) to augment and assist cognitive processes

such as attention, memory, self-regulation, navigation, emotion recognition and management, planning, and sequencing activity. Systematic reviews of the field have found that the number of ATC are growing rapidly, but have focused on memory and planning, that there is emerging evidence for efficacy, that a lot of scope exists to develop new ATC. Examples of ATC include: NeuroPage which prompts users about meetings, Wakamaru, which provides companionship and reminds users to take medicine and calls for help if something is wrong, and telephone Reassurance systems. Memory aids Memory aids are any type of assistive technology that helps a user learn and remember certain information. Many memory aids are used for cognitive impairments such as reading, writing, or organizational difficulties. For example, a Smartpen records handwritten notes by creating both a digital copy and an audio recording of the text. Users simply tap certain parts of their notes, the pen saves it, and reads it back to them. From there, the user can also download their notes onto a computer for increased accessibility. Digital voice recorders are also used to record "in the moment" information for fast and easy recall at a later time. A 2017 Cochrane Review highlighted the current lack of high-quality evidence to determine whether assistive technology effectively supports people with dementia to manage memory issues. Thus, it is not presently sure whether or not assistive technology is beneficial for memory problems. Educational software Educational software is software that assists people with reading, learning, comprehension, and organizational difficulties. Any accommodation software such as text readers, notetakers, text enlargers, organization tools, word predictions, and talking word processors falls under the category of educational software. Eating impairments Adaptive eating devices include items commonly used by the general population like spoons and forks and plates. However they become assistive technology when they are modified to accommodate the needs of people who have difficulty using standard cutlery due to a disabling condition. Common modifications include increasing the size of the utensil handle to make it easier to grasp. Plates and bowls may have a guard on the edge that stops food being pushed off of the dish when it is being scooped. More sophisticated equipment for eating includes manual and powered feeding devices. These devices support those who have little or no hand and arm function and enable them to eat independently. In sports Assistive technology in sports is an area of

technology design that is growing. Assistive technology is the array of new devices created to enable sports enthusiasts who have disabilities to play. Assistive technology may be used in adaptive sports, where an existing sport is modified to enable players with a disability to participate; or, assistive technology may be used to invent completely new sports with athletes with disabilities exclusively in mind. An increasing number of people with disabilities are participating in sports, leading to the development of new assistive technology. Assistive technology devices can be simple, or "low-technology", or they may use highly advanced technology. "Low-tech" devices can include velcro gloves and adaptive bands and tubes. "High-tech" devices can include all-terrain wheelchairs and adaptive bicycles. Accordingly, assistive technology can be found in sports ranging from local community recreation to the elite Paralympic Games. More complex assistive technology devices have been developed over time, and as a result, sports for people with disabilities "have changed from being a clinical therapeutic tool to an increasingly competition-oriented activity". In education In the United States there are two major pieces of legislation that govern the use of assistive technology within the school system. The first is Section 504 of the Rehabilitation Act of 1973 and the second being the Individuals with Disabilities Education Act (IDEA) which was first enacted in 1975 under the name The Education for All Handicapped Children Act. In 2004, during the reauthorization period for IDEA, the National Instructional Material Access Center (NIMAC) was created which provided a repository of accessible text including publisher's textbooks to students with a qualifying disability. Files provided are in XML format and used as a starting platform for braille readers, screen readers, and other digital text software. IDEA defines assistive technology as follows: "any item, piece of equipment, or product system, whether acquired commercially off the shelf, modified, or customized, that is used to increase, maintain, or improve functional capabilities of a child with a disability. (B) Exception.--The term does not include a medical device that is surgically implanted, or the replacement of such device." Assistive technology listed is a student's IEP is not only recommended, it is required (Koch, 2017). These devices help students both with and without disabilities access the curriculum in a way they were previously unable to (Koch, 2017). Occupational therapists play an important role in educating students, parents and teachers about the assistive technology they may interact with.

Assistive technology in this area is broken down into low, mid, and high tech categories. Low tech encompasses equipment that is often low cost and does not include batteries or requires charging. Examples include adapted paper and pencil grips for writing or masks and color overlays for reading. Mid tech supports used in the school setting include the use of handheld spelling dictionaries and portable word processors used to keyboard writing. High tech supports involve the use of tablet devices and computers with accompanying software. Software supports for writing include the use of auditory feedback while keyboarding, word prediction for spelling, and speech to text. Supports for reading include the use of text to speech (TTS) software and font modification via access to digital text. Limited supports are available for math instruction and mostly consist of grid based software to allow younger students to keyboard equations and auditory feedback of more complex equations using MathML and Daisy. Computer accessibility One of the largest problems that affect disabled people is discomfort with prostheses. An experiment performed in Massachusetts utilized 20 people with various sensors attached to their arms. The subjects tried different arm exercises, and the sensors recorded their movements. All of the data helped engineers develop new engineering concepts for prosthetics. Assistive technology may attempt to improve the ergonomics of the devices themselves such as Dvorak and other alternative keyboard layouts, which offer more ergonomic layouts of the keys. Assistive technology devices have been created to enable disabled people to use modern touch screen mobile computers such as the iPad, iPhone and iPod Touch. The Pererro is a plug and play adapter for iOS devices which uses the built in Apple VoiceOver feature in combination with a basic switch. This brings touch screen technology to those who were previously unable to use it. Apple, with the release of iOS 7 had introduced the ability to navigate apps using switch control. Switch access could be activated either through an external bluetooth connected switch, single touch of the screen, or use of right and left head turns using the device's camera. Additional accessibility features include the use of Assistive Touch which allows a user to access multi-touch gestures through pre-programmed onscreen buttons. For users with physical disabilities a large variety of switches are available and customizable to the user's needs varying in size, shape, or amount of pressure required for activation. Switch

access may be placed near any area of the body which has consistent and reliable mobility and less subject to fatigue. Common sites include the hands, head, and feet. Eye gaze and head mouse systems can also be used as an alternative mouse navigation. A user may utilize single or multiple switch sites and the process often involves a scanning through items on a screen and activating the switch once the desired object is highlighted. Home automation The form of home automation called assistive domotics focuses on making it possible for elderly and disabled people to live independently. Home automation is becoming a viable option for the elderly and disabled who would prefer to stay in their own homes rather than move to a healthcare facility. This field uses much of the same technology and equipment as home automation for security, entertainment, and energy conservation but tailors it towards elderly and disabled users. For example, automated prompts and reminders utilize motion sensors and pre-recorded audio messages; an automated prompt in the kitchen may remind the resident to turn off the oven, and one by the front door may remind the resident to lock the door. Assistive technology and innovation Innovation is happening in assistive technology either through improvements to existing devices or the creation of new products. In the WIPO published 2021 report on Technology Trends, assistive products are grouped into either conventional or emerging technologies. Conventional assisting technology tracks innovation within well-established assistive products, whereas emerging assistive technology refers to more advanced products. These identified advanced assistive products are distinguished from the conventional ones by the use of one or more enabling technologies (for instance, artificial intelligence, Internet of Things, advanced sensors, new material, additive manufacturing, advanced robotics, augmented and virtual reality) or by the inclusion of implantable products/components. Such emerging assistive products are either more sophisticated or more functional versions of conventional assistive products, or completely novel assistive devices. For instance, in conventional self-care assistive technology, technologies involved typically include adaptive clothing, adaptive eating devices, incontinence products, assistive products for manicure, pedicure, hair and facial care, dental care, or assistive products for sexual activities. In comparison, emerging self-care assistive technologies include health and emotion monitoring, smart diapers, smart medication dispensing and management or feeding assistant robot. Although the distinction between conventional and emerging technologies is not always clear-cut, emerging assistive technology tends to be "smarter", using AI and

being more connected and interactive, and including body-integrated solutions or components. To a great extent this « conventional » versus « emerging » classification is based on the WHO's Priority Assistive Products List and the ISO 9999 standard for assistive products for persons with disabilities, the APL delineating the absolute minimum that countries should be offering to their citizens and ISO 9999 defining those products which are already well established in the market. This "well-established status" is reflected in the patent filings between 2013 and 2017. Patent registrations for assistive technologies identified as conventional are nearly eight times larger than the ones for emerging assistive technologies. However, patent filings related to more recent emerging assistive technologies are growing almost three times as fast as those pertaining to conventional ones. Patent filings in both conventional and emerging assistive technology are highly concentrated on mobility, hearing and vision. Investment in emerging assistive technology also focuses on environment. In the conventional sector, mobility represent 54% of all patents fillings, and is an indication of increased interest in advanced mobility assistive product categories, such as advanced prosthetics, walking aids, wheelchairs, and exoskeletons. In the past, the top patent offices for filing, and therefore perceived target markets, in assistive technology have been the U.S. and Japan. Patenting activity has, however, been declining in these two jurisdictions. At the same time, there has been a surge in patent filings in China and an increase in filings in the Republic of Korea. This pattern is observed for both conventional and emerging assistive technology, with China's annual filings surpassing those of the U.S. in 2008 for conventional and 2014 for emerging assistive technology. Patent filings related to conventional assistive technology have also declined in Europe, especially in Germany, France, the Netherlands and Norway. Patenting activity indicates the amount of interest and the investment made in respect to an invention's applicability and its commercialization potential. There is typically a lag between filing a patent application and commercialization, with a product being classified in various stages of readiness levels, research concept, proof of concept, minimum viable product and finally commercial product. According to the 2021 WIPO report, the emerging technologies closest to a fully commercial product were for example: myoelectric control of advanced prosthetics and wheelchair control (mobility), environment-controlling hearing aids (hearing), multifocal intraocular lenses and artificial retina, along with Virtual and Augmented Reality wearables (vision); smart assistants and navigation

aids (communication); smart home appliances (environment); medication management and smart diapers (self-care). The technology readiness level and the related patenting activity can also be explained through the following factors which contribute to a product's entry to market, such as the expected impact on a person's participation in different aspects of life, the ease of adoption (need for training, fitting, additional equipment for interoperability, and so on), the societal acceptance and potential ethical concerns, and the need for regulatory approval. This is mainly the case for assistive technology that qualifies as medical technology. Among these aspects, acceptability and ethical considerations are particularly relevant to those technologies that are extremely invasive (such as cortical or auditory brainstem implants), or replace the human caregiver and human interaction, or collect and use data on cloud-based services or interconnected devices (e.g., companion robots, smart nursing and health-monitoring technologies), raising privacy issues and requiring connectivity, or raise safety concerns, such as autonomous wheelchairs. Beyond the patent landscape, industrial designs have an added importance for the field of assistive technology. Assistive technology is often not adopted, or else abandoned entirely, because of issues to do with design (lack of appeal) or comfort (poor ergonomics). Design often plays a role after the patenting activity, as a product needs to be re-designed for mass production. Impacts Overall, assistive technology aims to allow disabled people to "participate more fully in all aspects of life (home, school, and community)" and increases their opportunities for "education, social interactions, and potential for meaningful employment". It creates greater independence and control for disabled individuals. For example, in one study of 1,342 infants, toddlers and preschoolers, all with some kind of developmental, physical, sensory, or cognitive disability, the use of assistive technology created improvements in child development. These included improvements in "cognitive, social, communication, literacy, motor, adaptive, and increases in engagement in learning activities". Additionally, it has been found to lighten caregiver load. Both family and professional caregivers benefit from assistive technology. Through its use, the time that a family member or friend would need to care for a patient significantly decreases. However, studies show that care time for a professional caregiver increases when assistive technology is used. Nonetheless, their work load is significantly easier as the assistive technology frees them of having to perform certain tasks. There are several platforms that use machine learning to identify the appropriate assistive device to suggest to patients,

making assistive devices more accessible. History In 1988 the National institute on disability and rehabilitation research, NIDRR, awarded Gaulladet University a grant for the project "Robotic finger spelling hand for communication and access to text by deaf-blind persons." Researchers at the university developed and tested a robotic hand. Although it was never commercialized the concept is relevant for current and future research. Since this grant, many others have been written. NIDRR funded research appears to be moving from the fabrication of robotic arms that can be used by disabled persons to perform daily activities, to developing robotics that assist with therapy in the hopes of achieving long-term performance gains. If there is success in development of robotics, these mass-marketed products could assist tomorrow's longer-living elderly individuals enough to postpone nursing home stays. "Jim Osborn, executive director of the Quality of Life Technology Center, told a 2007 gathering of long-term care providers that if such advances could delay all nursing home admissions by a month, societal savings could be $1 billion monthly." Shortage of both paid personal assistants and available family members makes artificial assistance a necessity. See also Accessibility Assisted Living Augmentative and alternative communication Braille technology Design for All (in ICT) Disability Flag Durable medical equipment Matching person and technology model OATS: Open Source Assistive Technology Software Occupational Therapy Powered exoskeleton Rehabilitation robotics Soft robotics Transgenerational design Universal access to education References Bibliography Assistive Technology in Education: A Teacher's Guide, Amy Foxwell, 15 February 2022 Educational technology Web accessibility

The abacus (plural abaci or abacuses), also called a counting frame, is a calculating tool which has been used since ancient times. It was used in the ancient Near East, Europe, China, and Russia, millennia before the adoption of the Hindu-Arabic numeral system. The exact origin of the abacus has not yet emerged. It consists of rows of movable beads, or similar objects, strung on a wire. They represent digits. One of the two numbers is set up, and the beads are manipulated to perform an operation such as addition, or even a square or cubic root. In their earliest designs, the rows of beads could be loose on a flat surface or sliding in grooves. Later the beads were made to slide on rods and built into a frame, allowing faster manipulation. Abacuses are still made, often as a bamboo frame with beads sliding on wires. In the ancient world, particularly before the introduction of positional notation, abacuses were a practical calculating tool. The abacus is still used to teach the fundamentals of mathematics to some children, for example, in Russia. Designs such as the Japanese soroban have been used for practical calculations of up to multi-digit numbers. Any particular abacus design supports multiple methods to perform calculations, including addition, subtraction, multiplication, division, and square and cube roots. Some of these methods work with non-natural numbers (numbers such as and ). Although calculators and computers are commonly used today instead of abacuses, abacuses remain in everyday use in some countries. Merchants, traders, and clerks in some parts of Eastern Europe, Russia, China, and Africa use abacuses. The abacus remains in common use as a scoring system in non-electronic table games. Others may use an abacus due to visual impairment that prevents the use of a calculator. Etymology The word abacus dates to at least AD 1387 when a Middle English work borrowed the word from Latin that described a sandboard abacus. The Latin word is derived from ancient Greek (abax) which means something without a base, and colloquially, any piece of rectangular material. Alternatively, without reference to ancient texts on etymology, it has been suggested that it means "a square tablet strewn with dust", or "drawing-board covered with dust (for the use of mathematics)" (the exact shape of the Latin perhaps reflects the genitive form of the Greek word, (abakos)). While the table strewn with dust definition is popular,

some argue evidence is insufficient for that conclusion. Greek probably borrowed from a Northwest Semitic language like Phoenician, evidenced by a cognate with the Hebrew word ʾābāq (), or "dust" (in the post-Biblical sense "sand used as a writing surface"). Both abacuses and abaci are used as plurals. The user of an abacus is called an abacist. History Mesopotamia The Sumerian abacus appeared between 2700 and 2300 BC. It held a table of successive columns which delimited the successive orders of magnitude of their sexagesimal (base 60) number system. Some scholars point to a character in Babylonian cuneiform that may have been derived from a representation of the abacus. It is the belief of Old Babylonian scholars, such as Ettore Carruccio, that Old Babylonians "seem to have used the abacus for the operations of addition and subtraction; however, this primitive device proved difficult to use for more complex calculations". Egypt Greek historian Herodotus mentioned the abacus in Ancient Egypt. He wrote that the Egyptians manipulated the pebbles from right to left, opposite in direction to the Greek left-to-right method. Archaeologists have found ancient disks of various sizes that are thought to have been used as counters. However, wall depictions of this instrument are yet to be discovered. Persia At around 600 BC, Persians first began to use the abacus, during the Achaemenid Empire. Under the Parthian, Sassanian, and Iranian empires, scholars concentrated on exchanging knowledge and inventions with the countries around them – India, China, and the Roman Empire- which is how the abacus may have been exported to other countries. Greece The earliest archaeological evidence for the use of the Greek abacus dates to the 5th century BC. Demosthenes (384 BC–322 BC) complained that the need to use pebbles for calculations was too difficult. A play by Alexis from the 4th century BC mentions an abacus and pebbles for accounting, and both Diogenes and Polybius use the abacus as a metaphor for human behavior, stating "that men that sometimes stood for more and sometimes for less" like the pebbles on an abacus. The Greek abacus was a table of wood or marble, pre-set with small counters in wood or metal for mathematical calculations. This Greek abacus was used in Achaemenid Persia, the Etruscan civilization, Ancient Rome, and the Western Christian world until the French Revolution. A tablet found on the Greek island Salamis in 1846 AD (the Salamis Tablet)

dates to 300 BC, making it the oldest counting board discovered so far. It is a slab of white marble in length, wide, and thick, on which are 5 groups of markings. In the tablet's center is a set of 5 parallel lines equally divided by a vertical line, capped with a semicircle at the intersection of the bottom-most horizontal line and the single vertical line. Below these lines is a wide space with a horizontal crack dividing it. Below this crack is another group of eleven parallel lines, again divided into two sections by a line perpendicular to them, but with the semicircle at the top of the intersection; the third, sixth and ninth of these lines are marked with a cross where they intersect with the vertical line. Also from this time frame, the Darius Vase was unearthed in 1851. It was covered with pictures, including a "treasurer" holding a wax tablet in one hand while manipulating counters on a table with the other. Rome The normal method of calculation in ancient Rome, as in Greece, was by moving counters on a smooth table. Originally pebbles (calculi) were used. Later, and in medieval Europe, jetons were manufactured. Marked lines indicated units, fives, tens, etc. as in the Roman numeral system. This system of 'counter casting' continued into the late Roman empire and in medieval Europe and persisted in limited use into the nineteenth century. Due to Pope Sylvester II's reintroduction of the abacus with modifications, it became widely used in Europe again during the 11th century It used beads on wires, unlike the traditional Roman counting boards, which meant the abacus could be used much faster and was more easily moved. Writing in the 1st century BC, Horace refers to the wax abacus, a board covered with a thin layer of black wax on which columns and figures were inscribed using a stylus. One example of archaeological evidence of the Roman abacus, shown nearby in reconstruction, dates to the 1st century AD. It has eight long grooves containing up to five beads in each and eight shorter grooves having either one or no beads in each. The groove marked I indicates units, X tens, and so on up to millions. The beads in the shorter grooves denote fives –five units, five tens, etc., essentially in a bi-quinary coded decimal system, related to the Roman numerals. The short grooves

on the right may have been used for marking Roman "ounces" (i.e. fractions). China The earliest known written documentation of the Chinese abacus dates to the 2nd century BC. The Chinese abacus, also known as the suanpan (算盤/算盘, lit. "calculating tray"), comes in various lengths and widths, depending on the operator. It usually has more than seven rods. There are two beads on each rod in the upper deck and five beads each in the bottom one. The beads are usually rounded and made of hardwood. The beads are counted by moving them up or down towards the beam; beads moved toward the beam are counted, while those moved away from it are not. One of the top beads is 5, while one of the bottom beads is 1. Each rod has a number under it, showing the place value. The suanpan can be reset to the starting position instantly by a quick movement along the horizontal axis to spin all the beads away from the horizontal beam at the center. The prototype of the Chinese abacus appeared during the Han Dynasty, and the beads are oval. The Song Dynasty and earlier used the 1:4 type or four-beads abacus similar to the modern abacus including the shape of the beads commonly known as Japanese-style abacus. In the early Ming Dynasty, the abacus began to appear in a 1:5 ratio. The upper deck had one bead and the bottom had five beads. In the late Ming Dynasty, the abacus styles appeared in a 2:5 ratio. The upper deck had two beads, and the bottom had five. Various calculation techniques were devised for Suanpan enabling efficient calculations. Some schools teach students how to use it. In the long scroll Along the River During the Qingming Festival painted by Zhang Zeduan during the Song dynasty (960–1297), a suanpan is clearly visible beside an account book and doctor's prescriptions on the counter of an apothecary's (Feibao). The similarity of the Roman abacus to the Chinese one suggests that one could have inspired the other, given evidence of a trade relationship between the Roman Empire and China. However, no direct connection has been demonstrated, and the similarity of the abacuses may be coincidental, both ultimately arising from counting with five fingers per hand. Where the Roman model (like most modern Korean and Japanese) has 4 plus 1 bead per decimal place, the standard suanpan has

5 plus 2. Incidentally, this allows use with a hexadecimal numeral system (or any base up to 18) which may have been used for traditional Chinese measures of weight. (Instead of running on wires as in the Chinese, Korean, and Japanese models, the Roman model used grooves, presumably making arithmetic calculations much slower.) Another possible source of the suanpan is Chinese counting rods, which operated with a decimal system but lacked the concept of zero as a placeholder. The zero was probably introduced to the Chinese in the Tang dynasty (618–907) when travel in the Indian Ocean and the Middle East would have provided direct contact with India, allowing them to acquire the concept of zero and the decimal point from Indian merchants and mathematicians. India The Abhidharmakośabhāṣya of Vasubandhu (316-396), a Sanskrit work on Buddhist philosophy, says that the second-century CE philosopher Vasumitra said that "placing a wick (Sanskrit vartikā) on the number one (ekāṅka) means it is a one while placing the wick on the number hundred means it is called a hundred, and on the number one thousand means it is a thousand". It is unclear exactly what this arrangement may have been. Around the 5th century, Indian clerks were already finding new ways of recording the contents of the abacus. Hindu texts used the term śūnya (zero) to indicate the empty column on the abacus. Japan In Japan, the abacus is called soroban (, lit. "counting tray"). It was imported from China in the 14th century. It was probably in use by the working class a century or more before the ruling class adopted it, as the class structure obstructed such changes. The 1:4 abacus, which removes the seldom-used second and fifth bead became popular in the 1940s. Today's Japanese abacus is a 1:4 type, four-bead abacus, introduced from China in the Muromachi era. It adopts the form of the upper deck one bead and the bottom four beads. The top bead on the upper deck was equal to five and the bottom one is similar to the Chinese or Korean abacus, and the decimal number can be expressed, so the abacus is designed as a one:four device. The beads are always in the shape of a diamond. The quotient division is generally used instead of the division method; at the same time, in order to make the multiplication and division digits consistently use the division

multiplication. Later, Japan had a 3:5 abacus called 天三算盤, which is now in the Ize Rongji collection of Shansi Village in Yamagata City. Japan also used a 2:5 type abacus. The four-bead abacus spread, and became common around the world. Improvements to the Japanese abacus arose in various places. In China an aluminium frame plastic bead abacus was used. The file is next to the four beads, and pressing the "clearing" button put the upper bead in the upper position, and the lower bead in the lower position. The abacus is still manufactured in Japan even with the proliferation, practicality, and affordability of pocket electronic calculators. The use of the soroban is still taught in Japanese primary schools as part of mathematics, primarily as an aid to faster mental calculation. Using visual imagery can complete a calculation as quickly as a physical instrument. Korea The Chinese abacus migrated from China to Korea around 1400 AD. Koreans call it jupan (주판), supan (수판) or jusan (주산). The four-beads abacus (1:4) was introduced during the Goryeo Dynasty. The 5:1 abacus was introduced to Korea from China during the Ming Dynasty. Native America Some sources mention the use of an abacus called a nepohualtzintzin in ancient Aztec culture. This Mesoamerican abacus used a 5-digit base-20 system. The word Nepōhualtzintzin comes from Nahuatl, formed by the roots; Ne – personal -; pōhual or pōhualli – the account -; and tzintzin – small similar elements. Its complete meaning was taken as: counting with small similar elements. Its use was taught in the Calmecac to the temalpouhqueh , who were students dedicated to taking the accounts of skies, from childhood. The Nepōhualtzintzin was divided into two main parts separated by a bar or intermediate cord. In the left part were four beads. Beads in the first row have unitary values (1, 2, 3, and 4), and on the right side, three beads had values of 5, 10, and 15, respectively. In order to know the value of the respective beads of the upper rows, it is enough to multiply by 20 (by each row), the value of the corresponding count in the first row. The device featured 13 rows with 7 beads, 91 in total. This was a basic number for this culture. It had a close relation to natural phenomena, the underworld, and the cycles of the heavens. One Nepōhualtzintzin (91) represented the number of

days that a season of the year lasts, two Nepōhualtzitzin (182) is the number of days of the corn's cycle, from its sowing to its harvest, three Nepōhualtzintzin (273) is the number of days of a baby's gestation, and four Nepōhualtzintzin (364) completed a cycle and approximated one year. When translated into modern computer arithmetic, the Nepōhualtzintzin amounted to the rank from 10 to 18 in floating point, which precisely calculated large and small amounts, although round off was not allowed. The rediscovery of the Nepōhualtzintzin was due to the Mexican engineer David Esparza Hidalgo, who in his travels throughout Mexico found diverse engravings and paintings of this instrument and reconstructed several of them in gold, jade, encrustations of shell, etc. Very old Nepōhualtzintzin are attributed to the Olmec culture, and some bracelets of Mayan origin, as well as a diversity of forms and materials in other cultures. Sanchez wrote in Arithmetic in Maya that another base 5, base 4 abacus had been found in the Yucatán Peninsula that also computed calendar data. This was a finger abacus, on one hand, 0, 1, 2, 3, and 4 were used; and on the other hand 0, 1, 2, and 3 were used. Note the use of zero at the beginning and end of the two cycles. The quipu of the Incas was a system of colored knotted cords used to record numerical data, like advanced tally sticks – but not used to perform calculations. Calculations were carried out using a yupana (Quechua for "counting tool"; see figure) which was still in use after the conquest of Peru. The working principle of a yupana is unknown, but in 2001 Italian mathematician De Pasquale proposed an explanation. By comparing the form of several yupanas, researchers found that calculations were based using the Fibonacci sequence 1, 1, 2, 3, 5 and powers of 10, 20, and 40 as place values for the different fields in the instrument. Using the Fibonacci sequence would keep the number of grains within any one field at a minimum. Russia The Russian abacus, the schoty (, plural from , counting), usually has a single slanted deck, with ten beads on each wire (except one wire with four beads for quarter-ruble fractions). 4-bead wire was introduced for quarter-kopeks, which were minted until 1916. The Russian abacus is used vertically, with each wire running horizontally. The wires are usually bowed upward

in the center, to keep the beads pinned to either side. It is cleared when all the beads are moved to the right. During manipulation, beads are moved to the left. For easy viewing, the middle 2 beads on each wire (the 5th and 6th bead) usually are of a different color from the other eight. Likewise, the left bead of the thousands wire (and the million wire, if present) may have a different color. The Russian abacus was in use in shops and markets throughout the former Soviet Union, and its usage was taught in most schools until the 1990s. Even the 1874 invention of mechanical calculator, Odhner arithmometer, had not replaced them in Russia; according to Yakov Perelman. Some businessmen attempting to import calculators into the Russian Empire were known to leave in despair after watching a skilled abacus operator. Likewise, the mass production of Felix arithmometers since 1924 did not significantly reduce abacus use in the Soviet Union. The Russian abacus began to lose popularity only after the mass production of domestic microcalculators in 1974. The Russian abacus was brought to France around 1820 by mathematician Jean-Victor Poncelet, who had served in Napoleon's army and had been a prisoner of war in Russia. The abacus had fallen out of use in western Europe in the 16th century with the rise of decimal notation and algorismic methods. To Poncelet's French contemporaries, it was something new. Poncelet used it, not for any applied purpose, but as a teaching and demonstration aid. The Turks and the Armenian people used abacuses similar to the Russian schoty. It was named a coulba by the Turks and a choreb by the Armenians. School abacus Around the world, abacuses have been used in pre-schools and elementary schools as an aid in teaching the numeral system and arithmetic. In Western countries, a bead frame similar to the Russian abacus but with straight wires and a vertical frame is common (see image). The wireframe may be used either with positional notation like other abacuses (thus the 10-wire version may represent numbers up to 9,999,999,999), or each bead may represent one unit (e.g. 74 can be represented by shifting all beads on 7 wires and 4 beads on the 8th wire, so numbers up to 100 may be represented). In the bead frame shown, the gap between the 5th and 6th wire, corresponding to the color change

between the 5th and the 6th bead on each wire, suggests the latter use. Teaching multiplication, e.g. 6 times 7, may be represented by shifting 7 beads on 6 wires. The red-and-white abacus is used in contemporary primary schools for a wide range of number-related lessons. The twenty bead version, referred to by its Dutch name rekenrek ("calculating frame"), is often used, either on a string of beads or on a rigid framework. Feynman vs the abacus Physicist Richard Feynman was noted for facility in mathematical calculations. He wrote about an encounter in Brazil with a Japanese abacus expert, who challenged him to speed contests between Feynman's pen and paper, and the abacus. The abacus was much faster for addition, somewhat faster for multiplication, but Feynman was faster at division. When the abacus was used for a really difficult challenge, i.e. cube roots, Feynman won easily. However, the number chosen at random was close to a number Feynman happened to know was an exact cube, allowing him to use approximate methods. Neurological analysis Learning how to calculate with the abacus may improve capacity for mental calculation. Abacus-based mental calculation (AMC), which was derived from the abacus, is the act of performing calculations, including addition, subtraction, multiplication, and division, in the mind by manipulating an imagined abacus. It is a high-level cognitive skill that runs calculations with an effective algorithm. People doing long-term AMC training show higher numerical memory capacity and experience more effectively connected neural pathways. They are able to retrieve memory to deal with complex processes. AMC involves both visuospatial and visuomotor processing that generate the visual abacus and move the imaginary beads. Since it only requires that the final position of beads be remembered, it takes less memory and less computation time. Renaissance abacuses Binary abacus The binary abacus is used to explain how computers manipulate numbers. The abacus shows how numbers, letters, and signs can be stored in a binary system on a computer, or via ASCII. The device consists of a series of beads on parallel wires arranged in three separate rows. The beads represent a switch on the computer in either an "on" or "off" position. Visually impaired users An adapted abacus, invented by Tim Cranmer, and called a Cranmer abacus is commonly used by visually impaired users. A piece of soft fabric or rubber is placed behind the beads, keeping them in place while

the users manipulate them. The device is then used to perform the mathematical functions of multiplication, division, addition, subtraction, square root, and cube root. Although blind students have benefited from talking calculators, the abacus is often taught to these students in early grades. Blind students can also complete mathematical assignments using a braille-writer and Nemeth code (a type of braille code for mathematics) but large multiplication and long division problems are tedious. The abacus gives these students a tool to compute mathematical problems that equals the speed and mathematical knowledge required by their sighted peers using pencil and paper. Many blind people find this number machine a useful tool throughout life. See also Chinese Zhusuan Chisanbop Logical abacus Mental abacus Napier's bones Sand table Slide rule Soroban Suanpan Notes Footnotes References Reading External links Tutorials Min Multimedia Abacus curiosities Abacus in Various Number Systems at cut-the-knot Java applet of Chinese, Japanese and Russian abaci An atomic-scale abacus Examples of Abaci Aztex Abacus Indian Abacus Mathematical tools Chinese mathematics Egyptian mathematics Greek mathematics Indian mathematics Japanese mathematics Korean mathematics Roman mathematics

An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid. The first category of acids are the proton donors, or Brønsted–Lowry acids. In the special case of aqueous solutions, proton donors form the hydronium ion H3O+ and are known as Arrhenius acids. Brønsted and Lowry generalized the Arrhenius theory to include non-aqueous solvents. A Brønsted or Arrhenius acid usually contains a hydrogen atom bonded to a chemical structure that is still energetically favorable after loss of H+. Aqueous Arrhenius acids have characteristic properties that provide a practical description of an acid. Acids form aqueous solutions with a sour taste, can turn blue litmus red, and react with bases and certain metals (like calcium) to form salts. The word acid is derived from the Latin , meaning 'sour'. An aqueous solution of an acid has a pH less than 7 and is colloquially also referred to as "acid" (as in "dissolved in acid"), while the strict definition refers only to the solute. A lower pH means a higher acidity, and thus a higher concentration of positive hydrogen ions in the solution. Chemicals or substances having the property of an acid are said to be acidic. Common aqueous acids include hydrochloric acid (a solution of hydrogen chloride that is found in gastric acid in the stomach and activates digestive enzymes), acetic acid (vinegar is a dilute aqueous solution of this liquid), sulfuric acid (used in car batteries), and citric acid (found in citrus fruits). As these examples show, acids (in the colloquial sense) can be solutions or pure substances, and can be derived from acids (in the strict sense) that are solids, liquids, or gases. Strong acids and some concentrated weak acids are corrosive, but there are exceptions such as carboranes and boric acid. The second category of acids are Lewis acids, which form a covalent bond with an electron pair. An example is boron trifluoride (BF3), whose boron atom has a vacant orbital that can form a covalent bond by sharing a lone pair of electrons on an atom in a base, for example the nitrogen atom in ammonia (NH3). Lewis considered this as a generalization of the Brønsted definition, so that an acid is a chemical species that accepts electron pairs either directly or

by releasing protons (H+) into the solution, which then accept electron pairs. Hydrogen chloride, acetic acid, and most other Brønsted–Lowry acids cannot form a covalent bond with an electron pair, however, and are therefore not Lewis acids. Conversely, many Lewis acids are not Arrhenius or Brønsted–Lowry acids. In modern terminology, an acid is implicitly a Brønsted acid and not a Lewis acid, since chemists almost always refer to a Lewis acid explicitly as a Lewis acid. Definitions and concepts Modern definitions are concerned with the fundamental chemical reactions common to all acids. Most acids encountered in everyday life are aqueous solutions, or can be dissolved in water, so the Arrhenius and Brønsted–Lowry definitions are the most relevant. The Brønsted–Lowry definition is the most widely used definition; unless otherwise specified, acid–base reactions are assumed to involve the transfer of a proton (H+) from an acid to a base. Hydronium ions are acids according to all three definitions. Although alcohols and amines can be Brønsted–Lowry acids, they can also function as Lewis bases due to the lone pairs of electrons on their oxygen and nitrogen atoms. Arrhenius acids In 1884, Svante Arrhenius attributed the properties of acidity to hydrogen ions (H+), later described as protons or hydrons. An Arrhenius acid is a substance that, when added to water, increases the concentration of H+ ions in the water. Note that chemists often write H+(aq) and refer to the hydrogen ion when describing acid–base reactions but the free hydrogen nucleus, a proton, does not exist alone in water, it exists as the hydronium ion (H3O+) or other forms (H5O2+, H9O4+). Thus, an Arrhenius acid can also be described as a substance that increases the concentration of hydronium ions when added to water. Examples include molecular substances such as hydrogen chloride and acetic acid. An Arrhenius base, on the other hand, is a substance that increases the concentration of hydroxide (OH−) ions when dissolved in water. This decreases the concentration of hydronium because the ions react to form H2O molecules: H3O + OH ⇌ H2O(liq) + H2O(liq) Due to this equilibrium, any increase in the concentration of hydronium is accompanied by a decrease in the concentration of hydroxide. Thus, an Arrhenius acid could also be said to be one that decreases hydroxide concentration, while an Arrhenius base increases it. In an acidic solution, the concentration of hydronium ions is greater than 10−7 moles per liter.

Since pH is defined as the negative logarithm of the concentration of hydronium ions, acidic solutions thus have a pH of less than 7. Brønsted–Lowry acids While the Arrhenius concept is useful for describing many reactions, it is also quite limited in its scope. In 1923, chemists Johannes Nicolaus Brønsted and Thomas Martin Lowry independently recognized that acid–base reactions involve the transfer of a proton. A Brønsted–Lowry acid (or simply Brønsted acid) is a species that donates a proton to a Brønsted–Lowry base. Brønsted–Lowry acid–base theory has several advantages over Arrhenius theory. Consider the following reactions of acetic acid (CH3COOH), the organic acid that gives vinegar its characteristic taste: Both theories easily describe the first reaction: CH3COOH acts as an Arrhenius acid because it acts as a source of H3O+ when dissolved in water, and it acts as a Brønsted acid by donating a proton to water. In the second example CH3COOH undergoes the same transformation, in this case donating a proton to ammonia (NH3), but does not relate to the Arrhenius definition of an acid because the reaction does not produce hydronium. Nevertheless, CH3COOH is both an Arrhenius and a Brønsted–Lowry acid. Brønsted–Lowry theory can be used to describe reactions of molecular compounds in nonaqueous solution or the gas phase. Hydrogen chloride (HCl) and ammonia combine under several different conditions to form ammonium chloride, NH4Cl. In aqueous solution HCl behaves as hydrochloric acid and exists as hydronium and chloride ions. The following reactions illustrate the limitations of Arrhenius's definition: H3O + Cl + NH3 → Cl + NH(aq) + H2O HCl(benzene) + NH3(benzene) → NH4Cl(s) HCl(g) + NH3(g) → NH4Cl(s) As with the acetic acid reactions, both definitions work for the first example, where water is the solvent and hydronium ion is formed by the HCl solute. The next two reactions do not involve the formation of ions but are still proton-transfer reactions. In the second reaction hydrogen chloride and ammonia (dissolved in benzene) react to form solid ammonium chloride in a benzene solvent and in the third gaseous HCl and NH3 combine to form the solid. Lewis acids A third, only marginally related concept was proposed in 1923 by Gilbert N. Lewis, which includes reactions with acid–base characteristics that do not involve a proton transfer. A Lewis acid is a species that accepts a pair of electrons from another species; in other words, it is an electron pair

acceptor. Brønsted acid–base reactions are proton transfer reactions while Lewis acid–base reactions are electron pair transfers. Many Lewis acids are not Brønsted–Lowry acids. Contrast how the following reactions are described in terms of acid–base chemistry: In the first reaction a fluoride ion, F−, gives up an electron pair to boron trifluoride to form the product tetrafluoroborate. Fluoride "loses" a pair of valence electrons because the electrons shared in the B—F bond are located in the region of space between the two atomic nuclei and are therefore more distant from the fluoride nucleus than they are in the lone fluoride ion. BF3 is a Lewis acid because it accepts the electron pair from fluoride. This reaction cannot be described in terms of Brønsted theory because there is no proton transfer. The second reaction can be described using either theory. A proton is transferred from an unspecified Brønsted acid to ammonia, a Brønsted base; alternatively, ammonia acts as a Lewis base and transfers a lone pair of electrons to form a bond with a hydrogen ion. The species that gains the electron pair is the Lewis acid; for example, the oxygen atom in H3O+ gains a pair of electrons when one of the H—O bonds is broken and the electrons shared in the bond become localized on oxygen. Depending on the context, a Lewis acid may also be described as an oxidizer or an electrophile. Organic Brønsted acids, such as acetic, citric, or oxalic acid, are not Lewis acids. They dissociate in water to produce a Lewis acid, H+, but at the same time also yield an equal amount of a Lewis base (acetate, citrate, or oxalate, respectively, for the acids mentioned). This article deals mostly with Brønsted acids rather than Lewis acids. Dissociation and equilibrium Reactions of acids are often generalized in the form , where HA represents the acid and A− is the conjugate base. This reaction is referred to as protolysis. The protonated form (HA) of an acid is also sometimes referred to as the free acid. Acid–base conjugate pairs differ by one proton, and can be interconverted by the addition or removal of a proton (protonation and deprotonation, respectively). Note that the acid can be the charged species and the conjugate base can be neutral in which case the generalized reaction scheme could be written as . In solution there exists an equilibrium between the acid and its

conjugate base. The equilibrium constant K is an expression of the equilibrium concentrations of the molecules or the ions in solution. Brackets indicate concentration, such that [H2O] means the concentration of H2O. The acid dissociation constant Ka is generally used in the context of acid–base reactions. The numerical value of Ka is equal to the product (multiplication) of the concentrations of the products divided by the concentration of the reactants, where the reactant is the acid (HA) and the products are the conjugate base and H+. The stronger of two acids will have a higher Ka than the weaker acid; the ratio of hydrogen ions to acid will be higher for the stronger acid as the stronger acid has a greater tendency to lose its proton. Because the range of possible values for Ka spans many orders of magnitude, a more manageable constant, pKa is more frequently used, where pKa = −log10 Ka. Stronger acids have a smaller pKa than weaker acids. Experimentally determined pKa at 25 °C in aqueous solution are often quoted in textbooks and reference material. Nomenclature Arrhenius acids are named according to their anions. In the classical naming system, the ionic suffix is dropped and replaced with a new suffix, according to the table following. The prefix "hydro-" is used when the acid is made up of just hydrogen and one other element. For example, HCl has chloride as its anion, so the hydro- prefix is used, and the -ide suffix makes the name take the form hydrochloric acid. Classical naming system: In the IUPAC naming system, "aqueous" is simply added to the name of the ionic compound. Thus, for hydrogen chloride, as an acid solution, the IUPAC name is aqueous hydrogen chloride. Acid strength The strength of an acid refers to its ability or tendency to lose a proton. A strong acid is one that completely dissociates in water; in other words, one mole of a strong acid HA dissolves in water yielding one mole of H+ and one mole of the conjugate base, A−, and none of the protonated acid HA. In contrast, a weak acid only partially dissociates and at equilibrium both the acid and the conjugate base are in solution. Examples of strong acids are hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr), perchloric acid (HClO4), nitric acid (HNO3) and sulfuric acid (H2SO4). In water each of these essentially ionizes 100%.

The stronger an acid is, the more easily it loses a proton, H+. Two key factors that contribute to the ease of deprotonation are the polarity of the H—A bond and the size of atom A, which determines the strength of the H—A bond. Acid strengths are also often discussed in terms of the stability of the conjugate base. Stronger acids have a larger acid dissociation constant, Ka and a more negative pKa than weaker acids. Sulfonic acids, which are organic oxyacids, are a class of strong acids. A common example is toluenesulfonic acid (tosylic acid). Unlike sulfuric acid itself, sulfonic acids can be solids. In fact, polystyrene functionalized into polystyrene sulfonate is a solid strongly acidic plastic that is filterable. Superacids are acids stronger than 100% sulfuric acid. Examples of superacids are fluoroantimonic acid, magic acid and perchloric acid. Superacids can permanently protonate water to give ionic, crystalline hydronium "salts". They can also quantitatively stabilize carbocations. While Ka measures the strength of an acid compound, the strength of an aqueous acid solution is measured by pH, which is an indication of the concentration of hydronium in the solution. The pH of a simple solution of an acid compound in water is determined by the dilution of the compound and the compound's Ka. Lewis acid strength in non-aqueous solutions Lewis acids have been classified in the ECW model and it has been shown that there is no one order of acid strengths. The relative acceptor strength of Lewis acids toward a series of bases, versus other Lewis acids, can be illustrated by C-B plots. It has been shown that to define the order of Lewis acid strength at least two properties must be considered. For Pearson's qualitative HSAB theory the two properties are hardness and strength while for Drago's quantitative ECW model the two properties are electrostatic and covalent. Chemical characteristics Monoprotic acids Monoprotic acids, also known as monobasic acids, are those acids that are able to donate one proton per molecule during the process of dissociation (sometimes called ionization) as shown below (symbolized by HA): Ka Common examples of monoprotic acids in mineral acids include hydrochloric acid (HCl) and nitric acid (HNO3). On the other hand, for organic acids the term mainly indicates the presence of one carboxylic acid group and sometimes these acids are known as monocarboxylic acid. Examples in organic acids include formic acid (HCOOH), acetic acid

(CH3COOH) and benzoic acid (C6H5COOH). Polyprotic acids Polyprotic acids, also known as polybasic acids, are able to donate more than one proton per acid molecule, in contrast to monoprotic acids that only donate one proton per molecule. Specific types of polyprotic acids have more specific names, such as diprotic (or dibasic) acid (two potential protons to donate), and triprotic (or tribasic) acid (three potential protons to donate). Some macromolecules such as proteins and nucleic acids can have a very large number of acidic protons. A diprotic acid (here symbolized by H2A) can undergo one or two dissociations depending on the pH. Each dissociation has its own dissociation constant, Ka1 and Ka2. Ka1 Ka2 The first dissociation constant is typically greater than the second (i.e., Ka1 > Ka2). For example, sulfuric acid (H2SO4) can donate one proton to form the bisulfate anion (HSO), for which Ka1 is very large; then it can donate a second proton to form the sulfate anion (SO), wherein the Ka2 is intermediate strength. The large Ka1 for the first dissociation makes sulfuric a strong acid. In a similar manner, the weak unstable carbonic acid can lose one proton to form bicarbonate anion and lose a second to form carbonate anion (CO). Both Ka values are small, but Ka1 > Ka2 . A triprotic acid (H3A) can undergo one, two, or three dissociations and has three dissociation constants, where Ka1 > Ka2 > Ka3. Ka1 Ka2 Ka3 An inorganic example of a triprotic acid is orthophosphoric acid (H3PO4), usually just called phosphoric acid. All three protons can be successively lost to yield H2PO, then HPO, and finally PO, the orthophosphate ion, usually just called phosphate. Even though the positions of the three protons on the original phosphoric acid molecule are equivalent, the successive Ka values differ since it is energetically less favorable to lose a proton if the conjugate base is more negatively charged. An organic example of a triprotic acid is citric acid, which can successively lose three protons to finally form the citrate ion. Although the subsequent loss of each hydrogen ion is less favorable, all of the conjugate bases are present in solution. The fractional concentration, α (alpha), for each species can be calculated. For example, a generic diprotic acid will generate 3 species in solution: H2A, HA−, and A2−. The fractional concentrations can be calculated as below when given either the pH (which

can be converted to the [H+]) or the concentrations of the acid with all its conjugate bases: A plot of these fractional concentrations against pH, for given K1 and K2, is known as a Bjerrum plot. A pattern is observed in the above equations and can be expanded to the general n -protic acid that has been deprotonated i -times: where K0 = 1 and the other K-terms are the dissociation constants for the acid. Neutralization Neutralization is the reaction between an acid and a base, producing a salt and neutralized base; for example, hydrochloric acid and sodium hydroxide form sodium chloride and water: HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq) Neutralization is the basis of titration, where a pH indicator shows equivalence point when the equivalent number of moles of a base have been added to an acid. It is often wrongly assumed that neutralization should result in a solution with pH 7.0, which is only the case with similar acid and base strengths during a reaction. Neutralization with a base weaker than the acid results in a weakly acidic salt. An example is the weakly acidic ammonium chloride, which is produced from the strong acid hydrogen chloride and the weak base ammonia. Conversely, neutralizing a weak acid with a strong base gives a weakly basic salt (e.g., sodium fluoride from hydrogen fluoride and sodium hydroxide). Weak acid–weak base equilibrium In order for a protonated acid to lose a proton, the pH of the system must rise above the pKa of the acid. The decreased concentration of H+ in that basic solution shifts the equilibrium towards the conjugate base form (the deprotonated form of the acid). In lower-pH (more acidic) solutions, there is a high enough H+ concentration in the solution to cause the acid to remain in its protonated form. Solutions of weak acids and salts of their conjugate bases form buffer solutions. Titration To determine the concentration of an acid in an aqueous solution, an acid–base titration is commonly performed. A strong base solution with a known concentration, usually NaOH or KOH, is added to neutralize the acid solution according to the color change of the indicator with the amount of base added. The titration curve of an acid titrated by a base has two axes, with the base volume on the x-axis and the solution's pH value on the y-axis. The pH of the solution always

goes up as the base is added to the solution. Example: Diprotic acid For each diprotic acid titration curve, from left to right, there are two midpoints, two equivalence points, and two buffer regions. Equivalence points Due to the successive dissociation processes, there are two equivalence points in the titration curve of a diprotic acid. The first equivalence point occurs when all first hydrogen ions from the first ionization are titrated. In other words, the amount of OH− added equals the original amount of H2A at the first equivalence point. The second equivalence point occurs when all hydrogen ions are titrated. Therefore, the amount of OH− added equals twice the amount of H2A at this time. For a weak diprotic acid titrated by a strong base, the second equivalence point must occur at pH above 7 due to the hydrolysis of the resulted salts in the solution. At either equivalence point, adding a drop of base will cause the steepest rise of the pH value in the system. Buffer regions and midpoints A titration curve for a diprotic acid contains two midpoints where pH=pKa. Since there are two different Ka values, the first midpoint occurs at pH=pKa1 and the second one occurs at pH=pKa2. Each segment of the curve that contains a midpoint at its center is called the buffer region. Because the buffer regions consist of the acid and its conjugate base, it can resist pH changes when base is added until the next equivalent points. Applications of acids In industry Acids are fundamental reagents in treating almost all processes in modern industry. Sulfuric acid, a diprotic acid, is the most widely used acid in industry, and is also the most-produced industrial chemical in the world. It is mainly used in producing fertilizer, detergent, batteries and dyes, as well as used in processing many products such like removing impurities. According to the statistics data in 2011, the annual production of sulfuric acid was around 200 million tonnes in the world. For example, phosphate minerals react with sulfuric acid to produce phosphoric acid for the production of phosphate fertilizers, and zinc is produced by dissolving zinc oxide into sulfuric acid, purifying the solution and electrowinning. In the chemical industry, acids react in neutralization reactions to produce salts. For example, nitric acid reacts with ammonia to produce ammonium nitrate, a fertilizer. Additionally, carboxylic acids can be esterified with alcohols, to produce

esters. Acids are often used to remove rust and other corrosion from metals in a process known as pickling. They may be used as an electrolyte in a wet cell battery, such as sulfuric acid in a car battery. In food Tartaric acid is an important component of some commonly used foods like unripened mangoes and tamarind. Natural fruits and vegetables also contain acids. Citric acid is present in oranges, lemon and other citrus fruits. Oxalic acid is present in tomatoes, spinach, and especially in carambola and rhubarb; rhubarb leaves and unripe carambolas are toxic because of high concentrations of oxalic acid. Ascorbic acid (Vitamin C) is an essential vitamin for the human body and is present in such foods as amla (Indian gooseberry), lemon, citrus fruits, and guava. Many acids can be found in various kinds of food as additives, as they alter their taste and serve as preservatives. Phosphoric acid, for example, is a component of cola drinks. Acetic acid is used in day-to-day life as vinegar. Citric acid is used as a preservative in sauces and pickles. Carbonic acid is one of the most common acid additives that are widely added in soft drinks. During the manufacturing process, CO2 is usually pressurized to dissolve in these drinks to generate carbonic acid. Carbonic acid is very unstable and tends to decompose into water and CO2 at room temperature and pressure. Therefore, when bottles or cans of these kinds of soft drinks are opened, the soft drinks fizz and effervesce as CO2 bubbles come out. Certain acids are used as drugs. Acetylsalicylic acid (Aspirin) is used as a pain killer and for bringing down fevers. In human bodies Acids play important roles in the human body. The hydrochloric acid present in the stomach aids digestion by breaking down large and complex food molecules. Amino acids are required for synthesis of proteins required for growth and repair of body tissues. Fatty acids are also required for growth and repair of body tissues. Nucleic acids are important for the manufacturing of DNA and RNA and transmitting of traits to offspring through genes. Carbonic acid is important for maintenance of pH equilibrium in the body. Human bodies contain a variety of organic and inorganic compounds, among those dicarboxylic acids play an essential role in many biological behaviors. Many of those acids are amino acids, which mainly serve as materials for the synthesis

of proteins. Other weak acids serve as buffers with their conjugate bases to keep the body's pH from undergoing large scale changes that would be harmful to cells. The rest of the dicarboxylic acids also participate in the synthesis of various biologically important compounds in human bodies. Acid catalysis Acids are used as catalysts in industrial and organic chemistry; for example, sulfuric acid is used in very large quantities in the alkylation process to produce gasoline. Some acids, such as sulfuric, phosphoric, and hydrochloric acids, also effect dehydration and condensation reactions. In biochemistry, many enzymes employ acid catalysis. Biological occurrence Many biologically important molecules are acids. Nucleic acids, which contain acidic phosphate groups, include DNA and RNA. Nucleic acids contain the genetic code that determines many of an organism's characteristics, and is passed from parents to offspring. DNA contains the chemical blueprint for the synthesis of proteins, which are made up of amino acid subunits. Cell membranes contain fatty acid esters such as phospholipids. An α-amino acid has a central carbon (the α or alpha carbon) that is covalently bonded to a carboxyl group (thus they are carboxylic acids), an amino group, a hydrogen atom and a variable group. The variable group, also called the R group or side chain, determines the identity and many of the properties of a specific amino acid. In glycine, the simplest amino acid, the R group is a hydrogen atom, but in all other amino acids it is contains one or more carbon atoms bonded to hydrogens, and may contain other elements such as sulfur, oxygen or nitrogen. With the exception of glycine, naturally occurring amino acids are chiral and almost invariably occur in the L-configuration. Peptidoglycan, found in some bacterial cell walls contains some D-amino acids. At physiological pH, typically around 7, free amino acids exist in a charged form, where the acidic carboxyl group (-COOH) loses a proton (-COO−) and the basic amine group (-NH2) gains a proton (-NH). The entire molecule has a net neutral charge and is a zwitterion, with the exception of amino acids with basic or acidic side chains. Aspartic acid, for example, possesses one protonated amine and two deprotonated carboxyl groups, for a net charge of −1 at physiological pH. Fatty acids and fatty acid derivatives are another group of carboxylic acids that play a significant role in biology. These contain long hydrocarbon chains and a carboxylic

acid group on one end. The cell membrane of nearly all organisms is primarily made up of a phospholipid bilayer, a micelle of hydrophobic fatty acid esters with polar, hydrophilic phosphate "head" groups. Membranes contain additional components, some of which can participate in acid–base reactions. In humans and many other animals, hydrochloric acid is a part of the gastric acid secreted within the stomach to help hydrolyze proteins and polysaccharides, as well as converting the inactive pro-enzyme, pepsinogen into the enzyme, pepsin. Some organisms produce acids for defense; for example, ants produce formic acid. Acid–base equilibrium plays a critical role in regulating mammalian breathing. Oxygen gas (O2) drives cellular respiration, the process by which animals release the chemical potential energy stored in food, producing carbon dioxide (CO2) as a byproduct. Oxygen and carbon dioxide are exchanged in the lungs, and the body responds to changing energy demands by adjusting the rate of ventilation. For example, during periods of exertion the body rapidly breaks down stored carbohydrates and fat, releasing CO2 into the blood stream. In aqueous solutions such as blood CO2 exists in equilibrium with carbonic acid and bicarbonate ion. It is the decrease in pH that signals the brain to breathe faster and deeper, expelling the excess CO2 and resupplying the cells with O2. Cell membranes are generally impermeable to charged or large, polar molecules because of the lipophilic fatty acyl chains comprising their interior. Many biologically important molecules, including a number of pharmaceutical agents, are organic weak acids that can cross the membrane in their protonated, uncharged form but not in their charged form (i.e., as the conjugate base). For this reason the activity of many drugs can be enhanced or inhibited by the use of antacids or acidic foods. The charged form, however, is often more soluble in blood and cytosol, both aqueous environments. When the extracellular environment is more acidic than the neutral pH within the cell, certain acids will exist in their neutral form and will be membrane soluble, allowing them to cross the phospholipid bilayer. Acids that lose a proton at the intracellular pH will exist in their soluble, charged form and are thus able to diffuse through the cytosol to their target. Ibuprofen, aspirin and penicillin are examples of drugs that are weak acids. Common acids Mineral acids (inorganic acids) Hydrogen halides and their solutions: hydrofluoric acid (HF), hydrochloric acid (HCl), hydrobromic acid

(HBr), hydroiodic acid (HI) Halogen oxoacids: hypochlorous acid (HClO), chlorous acid (HClO2), chloric acid (HClO3), perchloric acid (HClO4), and corresponding analogs for bromine and iodine Hypofluorous acid (HFO), the only known oxoacid for fluorine. Sulfuric acid (H2SO4) Fluorosulfuric acid (HSO3F) Nitric acid (HNO3) Phosphoric acid (H3PO4) Fluoroantimonic acid (HSbF6) Fluoroboric acid (HBF4) Hexafluorophosphoric acid (HPF6) Chromic acid (H2CrO4) Boric acid (H3BO3) Sulfonic acids A sulfonic acid has the general formula RS(=O)2–OH, where R is an organic radical. Methanesulfonic acid (or mesylic acid, CH3SO3H) Ethanesulfonic acid (or esylic acid, CH3CH2SO3H) Benzenesulfonic acid (or besylic acid, C6H5SO3H) p-Toluenesulfonic acid (or tosylic acid, CH3C6H4SO3H) Trifluoromethanesulfonic acid (or triflic acid, CF3SO3H) Polystyrene sulfonic acid (sulfonated polystyrene, [CH2CH(C6H4)SO3H]n) Carboxylic acids A carboxylic acid has the general formula R-C(O)OH, where R is an organic radical. The carboxyl group -C(O)OH contains a carbonyl group, C=O, and a hydroxyl group, O-H. Acetic acid (CH3COOH) Citric acid (C6H8O7) Formic acid (HCOOH) Gluconic acid HOCH2-(CHOH)4-COOH Lactic acid (CH3-CHOH-COOH) Oxalic acid (HOOC-COOH) Tartaric acid (HOOC-CHOH-CHOH-COOH) Halogenated carboxylic acids Halogenation at alpha position increases acid strength, so that the following acids are all stronger than acetic acid. Fluoroacetic acid Trifluoroacetic acid Chloroacetic acid Dichloroacetic acid Trichloroacetic acid Vinylogous carboxylic acids Normal carboxylic acids are the direct union of a carbonyl group and a hydroxyl group. In vinylogous carboxylic acids, a carbon-carbon double bond separates the carbonyl and hydroxyl groups. Ascorbic acid Nucleic acids Deoxyribonucleic acid (DNA) Ribonucleic acid (RNA) References Listing of strengths of common acids and bases External links Curtipot: Acid–Base equilibria diagrams, pH calculation and titration curves simulation and analysis – freeware Acid–base chemistry

Bitumen (, ) is a sticky, black, highly viscous liquid or semi-solid form of petroleum. In the U.S., it is commonly referred to as asphalt. It may be found in natural deposits or may be a refined product, and is classed as a pitch. Before the 20th century, the term asphaltum was also used. The word is derived from the Ancient Greek ἄσφαλτος ásphaltos. The largest natural deposit of bitumen in the world, estimated to contain 10 million tons, is the Pitch Lake in southwest Trinidad. The primary use (70%) of bitumen is in road construction, where it is used as the glue or binder mixed with aggregate particles to create asphalt concrete. Its other main uses are for bituminous waterproofing products, including production of roofing felt and for sealing flat roofs. In material sciences and engineering, the terms "asphalt" and "bitumen" are often used interchangeably to mean both natural and manufactured forms of the substance, although there is regional variation as to which term is most common. Worldwide, geologists tend to favor the term "bitumen" for the naturally occurring material. For the manufactured material, which is a refined residue from the distillation process of selected crude oils, "bitumen" is the prevalent term in much of the world; however, in American English, "asphalt" is more commonly used. To help avoid confusion, the phrases "liquid asphalt", "asphalt binder", or "asphalt cement" are used in the U.S. Colloquially, various forms of asphalt are sometimes referred to as "tar", as in the name of the La Brea Tar Pits, although tar is a different material. Naturally occurring bitumen is sometimes specified by the term "crude bitumen". Its viscosity is similar to that of cold molasses while the material obtained from the fractional distillation of crude oil boiling at is sometimes referred to as "refined bitumen". The Canadian province of Alberta has most of the world's reserves of natural bitumen in the Athabasca oil sands, which cover , an area larger than England. Terminology Etymology The word "bitumen" is from Latin, and passed via French into English. The Latin word traces to the Proto-Indo-European root *gʷet- "pitch"; see that link for other cognates. The word "asphalt" is derived from the late Middle English, in turn from French asphalte, based on Late Latin asphalton, asphaltum, which is the latinisation of the Greek (ásphaltos, ásphalton), a word meaning "asphalt/bitumen/pitch", which perhaps derives from , "not, without",

i.e. the alpha privative, and (sphallein), "to cause to fall, baffle, (in passive) err, (in passive) be balked of". The first use of asphalt by the ancients was in the nature of a cement for securing or joining various objects, and it thus seems likely that the name itself was expressive of this application. Specifically, Herodotus mentioned that bitumen was brought to Babylon to build its gigantic fortification wall. From the Greek, the word passed into late Latin, and thence into French (asphalte) and English ("asphaltum" and "asphalt"). In French, the term asphalte is used for naturally occurring asphalt-soaked limestone deposits, and for specialised manufactured products with fewer voids or greater bitumen content than the "asphaltic concrete" used to pave roads. Modern terminology Bitumen mixed with clay was usually called "asphaltum", but the term is less commonly used today. In American English, "asphalt" is equivalent to the British "bitumen". However, "asphalt" is also commonly used as a shortened form of "asphalt concrete" (therefore equivalent to the British "asphalt" or "tarmac"). In Canadian English, the word "bitumen" is used to refer to the vast Canadian deposits of extremely heavy crude oil, while "asphalt" is used for the oil refinery product. Diluted bitumen (diluted with naphtha to make it flow in pipelines) is known as "dilbit" in the Canadian petroleum industry, while bitumen "upgraded" to synthetic crude oil is known as "syncrude", and syncrude blended with bitumen is called "synbit". "Bitumen" is still the preferred geological term for naturally occurring deposits of the solid or semi-solid form of petroleum. "Bituminous rock" is a form of sandstone impregnated with bitumen. The oil sands of Alberta, Canada are a similar material. Neither of the terms "asphalt" or "bitumen" should be confused with tar or coal tars. Tar is the thick liquid product of the dry distillation and pyrolysis of organic hydrocarbons primarily sourced from vegetation masses, whether fossilized as with coal, or freshly harvested. The majority of bitumen, on the other hand, was formed naturally when vast quantities of organic animal materials were deposited by water and buried hundreds of metres deep at the diagenetic point, where the disorganized fatty hydrocarbon molecules joined in long chains in the absence of oxygen. Bitumen occurs as a solid or highly viscous liquid. It may even be mixed in with coal deposits. Bitumen, and coal using the Bergius process, can be refined into petrols such as gasoline,

and bitumen may be distilled into tar, not the other way around. Composition Normal composition The components of bitumen include four main classes of compounds: Naphthene aromatics (naphthalene), consisting of partially hydrogenated polycyclic aromatic compounds Polar aromatics, consisting of high molecular weight phenols and carboxylic acids produced by partial oxidation of the material Saturated hydrocarbons; the percentage of saturated compounds in asphalt correlates with its softening point Asphaltenes, consisting of high molecular weight phenols and heterocyclic compounds Bitumen typically contains, elementally 80% by weight of carbon; 10% hydrogen; up to 6% sulfur; and molecularly, between 5 and 25% by weight of asphaltenes dispersed in 90% to 65% maltenes. Most natural bitumens also contain organosulfur compounds, Nickel and vanadium are found at <10 parts per million, as is typical of some petroleum. The substance is soluble in carbon disulfide. It is commonly modelled as a colloid, with asphaltenes as the dispersed phase and maltenes as the continuous phase. "It is almost impossible to separate and identify all the different molecules of bitumen, because the number of molecules with different chemical structure is extremely large". Asphalt may be confused with coal tar, which is a visually similar black, thermoplastic material produced by the destructive distillation of coal. During the early and mid-20th century, when town gas was produced, coal tar was a readily available byproduct and extensively used as the binder for road aggregates. The addition of coal tar to macadam roads led to the word "tarmac", which is now used in common parlance to refer to road-making materials. However, since the 1970s, when natural gas succeeded town gas, bitumen has completely overtaken the use of coal tar in these applications. Other examples of this confusion include La Brea Tar Pits and the Canadian oil sands, both of which actually contain natural bitumen rather than tar. "Pitch" is another term sometimes informally used at times to refer to asphalt, as in Pitch Lake. Additives, mixtures and contaminants For economic and other reasons, bitumen is sometimes sold combined with other materials, often without being labeled as anything other than simply "bitumen". Of particular note is the use of re-refined engine oil bottoms – "REOB" or "REOBs"the residue of recycled automotive engine oil collected from the bottoms of re-refining vacuum distillation towers, in the manufacture of asphalt. REOB contains various elements and compounds found in recycled engine oil: additives to the original oil and

materials accumulating from its circulation in the engine (typically iron and copper). Some research has indicated a correlation between this adulteration of bitumen and poorer-performing pavement. Occurrence The majority of bitumen used commercially is obtained from petroleum. Nonetheless, large amounts of bitumen occur in concentrated form in nature. Naturally occurring deposits of bitumen are formed from the remains of ancient, microscopic algae (diatoms) and other once-living things. These natural deposits of bitumen have been formed during the Carboniferous period, when giant swamp forests dominated many parts of the Earth. They were deposited in the mud on the bottom of the ocean or lake where the organisms lived. Under the heat (above 50 °C) and pressure of burial deep in the earth, the remains were transformed into materials such as bitumen, kerogen, or petroleum. Natural deposits of bitumen include lakes such as the Pitch Lake in Trinidad and Tobago and Lake Bermudez in Venezuela. Natural seeps occur in the La Brea Tar Pits and the McKittrick Tar Pits in California, as well as in the Dead Sea. Bitumen also occurs in unconsolidated sandstones known as "oil sands" in Alberta, Canada, and the similar "tar sands" in Utah, US. The Canadian province of Alberta has most of the world's reserves, in three huge deposits covering , an area larger than England or New York state. These bituminous sands contain of commercially established oil reserves, giving Canada the third largest oil reserves in the world. Although historically it was used without refining to pave roads, nearly all of the output is now used as raw material for oil refineries in Canada and the United States. The world's largest deposit of natural bitumen, known as the Athabasca oil sands, is located in the McMurray Formation of Northern Alberta. This formation is from the early Cretaceous, and is composed of numerous lenses of oil-bearing sand with up to 20% oil. Isotopic studies show the oil deposits to be about 110 million years old. Two smaller but still very large formations occur in the Peace River oil sands and the Cold Lake oil sands, to the west and southeast of the Athabasca oil sands, respectively. Of the Alberta deposits, only parts of the Athabasca oil sands are shallow enough to be suitable for surface mining. The other 80% has to be produced by oil wells using enhanced oil recovery techniques like steam-assisted gravity drainage. Much smaller

heavy oil or bitumen deposits also occur in the Uinta Basin in Utah, US. The Tar Sand Triangle deposit, for example, is roughly 6% bitumen. Bitumen may occur in hydrothermal veins. An example of this is within the Uinta Basin of Utah, in the US, where there is a swarm of laterally and vertically extensive veins composed of a solid hydrocarbon termed Gilsonite. These veins formed by the polymerization and solidification of hydrocarbons that were mobilized from the deeper oil shales of the Green River Formation during burial and diagenesis. Bitumen is similar to the organic matter in carbonaceous meteorites. However, detailed studies have shown these materials to be distinct. The vast Alberta bitumen resources are considered to have started out as living material from marine plants and animals, mainly algae, that died millions of years ago when an ancient ocean covered Alberta. They were covered by mud, buried deeply over time, and gently cooked into oil by geothermal heat at a temperature of . Due to pressure from the rising of the Rocky Mountains in southwestern Alberta, 80 to 55 million years ago, the oil was driven northeast hundreds of kilometres and trapped into underground sand deposits left behind by ancient river beds and ocean beaches, thus forming the oil sands. History Ancient times The use of natural bitumen for waterproofing, and as an adhesive dates at least to the fifth millennium BC, with a crop storage basket discovered in Mehrgarh, of the Indus Valley civilization, lined with it. By the 3rd millennium BC refined rock asphalt was in use in the region, and was used to waterproof the Great Bath in Mohenjo-daro. In the ancient Middle East, the Sumerians used natural bitumen deposits for mortar between bricks and stones, to cement parts of carvings, such as eyes, into place, for ship caulking, and for waterproofing. The Greek historian Herodotus said hot bitumen was used as mortar in the walls of Babylon. The long Euphrates Tunnel beneath the river Euphrates at Babylon in the time of Queen Semiramis () was reportedly constructed of burnt bricks covered with bitumen as a waterproofing agent. Bitumen was used by ancient Egyptians to embalm mummies. The Persian word for asphalt is moom, which is related to the English word mummy. The Egyptians' primary source of bitumen was the Dead Sea, which the Romans knew as Palus Asphaltites (Asphalt Lake). In approximately 40 AD,

Dioscorides described the Dead Sea material as Judaicum bitumen, and noted other places in the region where it could be found. The Sidon bitumen is thought to refer to material found at Hasbeya in Lebanon. Pliny also refers to bitumen being found in Epirus. Bitumen was a valuable strategic resource. It was the object of the first known battle for a hydrocarbon deposit – between the Seleucids and the Nabateans in 312 BC. In the ancient Far East, natural bitumen was slowly boiled to get rid of the higher fractions, leaving a thermoplastic material of higher molecular weight that, when layered on objects, became hard upon cooling. This was used to cover objects that needed waterproofing, such as scabbards and other items. Statuettes of household deities were also cast with this type of material in Japan, and probably also in China. In North America, archaeological recovery has indicated that bitumen was sometimes used to adhere stone projectile points to wooden shafts. In Canada, aboriginal people used bitumen seeping out of the banks of the Athabasca and other rivers to waterproof birch bark canoes, and also heated it in smudge pots to ward off mosquitoes in the summer. Continental Europe In 1553, Pierre Belon described in his work Observations that pissasphalto, a mixture of pitch and bitumen, was used in the Republic of Ragusa (now Dubrovnik, Croatia) for tarring of ships. An 1838 edition of Mechanics Magazine cites an early use of asphalt in France. A pamphlet dated 1621, by "a certain Monsieur d'Eyrinys, states that he had discovered the existence (of asphaltum) in large quantities in the vicinity of Neufchatel", and that he proposed to use it in a variety of ways – "principally in the construction of air-proof granaries, and in protecting, by means of the arches, the water-courses in the city of Paris from the intrusion of dirt and filth", which at that time made the water unusable. "He expatiates also on the excellence of this material for forming level and durable terraces" in palaces, "the notion of forming such terraces in the streets not one likely to cross the brain of a Parisian of that generation". But the substance was generally neglected in France until the revolution of 1830. In the 1830s there was a surge of interest, and asphalt became widely used "for pavements, flat roofs, and the lining of cisterns, and in England, some use

of it had been made of it for similar purposes". Its rise in Europe was "a sudden phenomenon", after natural deposits were found "in France at Osbann (Bas-Rhin), the Parc (Ain) and the Puy-de-la-Poix (Puy-de-Dôme)", although it could also be made artificially. One of the earliest uses in France was the laying of about 24,000 square yards of Seyssel asphalt at the Place de la Concorde in 1835. United Kingdom Among the earlier uses of bitumen in the United Kingdom was for etching. William Salmon's Polygraphice (1673) provides a recipe for varnish used in etching, consisting of three ounces of virgin wax, two ounces of mastic, and one ounce of asphaltum. By the fifth edition in 1685, he had included more asphaltum recipes from other sources. The first British patent for the use of asphalt was "Cassell's patent asphalte or bitumen" in 1834. Then on 25 November 1837, Richard Tappin Claridge patented the use of Seyssel asphalt (patent #7849), for use in asphalte pavement, having seen it employed in France and Belgium when visiting with Frederick Walter Simms, who worked with him on the introduction of asphalt to Britain. Dr T. Lamb Phipson writes that his father, Samuel Ryland Phipson, a friend of Claridge, was also "instrumental in introducing the asphalte pavement (in 1836)". Claridge obtained a patent in Scotland on 27 March 1838, and obtained a patent in Ireland on 23 April 1838. In 1851, extensions for the 1837 patent and for both 1838 patents were sought by the trustees of a company previously formed by Claridge. Claridge's Patent Asphalte Companyformed in 1838 for the purpose of introducing to Britain "Asphalte in its natural state from the mine at Pyrimont Seysell in France","laid one of the first asphalt pavements in Whitehall". Trials were made of the pavement in 1838 on the footway in Whitehall, the stable at Knightsbridge Barracks, "and subsequently on the space at the bottom of the steps leading from Waterloo Place to St. James Park". "The formation in 1838 of Claridge's Patent Asphalte Company (with a distinguished list of aristocratic patrons, and Marc and Isambard Brunel as, respectively, a trustee and consulting engineer), gave an enormous impetus to the development of a British asphalt industry". "By the end of 1838, at least two other companies, Robinson's and the Bastenne company, were in production", with asphalt being laid as paving at Brighton, Herne Bay, Canterbury, Kensington, the

Strand, and a large floor area in Bunhill-row, while meantime Claridge's Whitehall paving "continue(d) in good order". The Bonnington Chemical Works manufactured asphalt using coal tar and by 1839 had installed it in Bonnington. In 1838, there was a flurry of entrepreneurial activity involving bitumen, which had uses beyond paving. For example, bitumen could also be used for flooring, damp proofing in buildings, and for waterproofing of various types of pools and baths, both of which were also proliferating in the 19th century. One of the earliest surviving examples of its use can be seen at Highgate Cemetery where it was used in 1839 to seal the roof of the terrace catacombs. On the London stockmarket, there were various claims as to the exclusivity of bitumen quality from France, Germany and England. And numerous patents were granted in France, with similar numbers of patent applications being denied in England due to their similarity to each other. In England, "Claridge's was the type most used in the 1840s and 50s". In 1914, Claridge's Company entered into a joint venture to produce tar-bound macadam, with materials manufactured through a subsidiary company called Clarmac Roads Ltd. Two products resulted, namely Clarmac, and Clarphalte, with the former being manufactured by Clarmac Roads and the latter by Claridge's Patent Asphalte Co., although Clarmac was more widely used. However, the First World War ruined the Clarmac Company, which entered into liquidation in 1915. The failure of Clarmac Roads Ltd had a flow-on effect to Claridge's Company, which was itself compulsorily wound up, ceasing operations in 1917, having invested a substantial amount of funds into the new venture, both at the outset and in a subsequent attempt to save the Clarmac Company. Bitumen was thought in 19th century Britain to contain chemicals with medicinal properties. Extracts from bitumen were used to treat catarrh and some forms of asthma and as a remedy against worms, especially the tapeworm. United States The first use of bitumen in the New World was by indigenous peoples. On the west coast, as early as the 13th century, the Tongva, Luiseño and Chumash peoples collected the naturally occurring bitumen that seeped to the surface above underlying petroleum deposits. All three groups used the substance as an adhesive. It is found on many different artifacts of tools and ceremonial items. For example, it was used on rattles to adhere gourds or turtle shells to

rattle handles. It was also used in decorations. Small round shell beads were often set in asphaltum to provide decorations. It was used as a sealant on baskets to make them watertight for carrying water, possibly poisoning those who drank the water. Asphalt was used also to seal the planks on ocean-going canoes. Asphalt was first used to pave streets in the 1870s. At first naturally occurring "bituminous rock" was used, such as at Ritchie Mines in Macfarlan in Ritchie County, West Virginia from 1852 to 1873. In 1876, asphalt-based paving was used to pave Pennsylvania Avenue in Washington DC, in time for the celebration of the national centennial. In the horse-drawn era, US streets were mostly unpaved and covered with dirt or gravel. Especially where mud or trenching often made streets difficult to pass, pavements were sometimes made of diverse materials including wooden planks, cobble stones or other stone blocks, or bricks. Unpaved roads produced uneven wear and hazards for pedestrians. In the late 19th century with the rise of the popular bicycle, bicycle clubs were important in pushing for more general pavement of streets. Advocacy for pavement increased in the early 20th century with the rise of the automobile. Asphalt gradually became an ever more common method of paving. St. Charles Avenue in New Orleans was paved its whole length with asphalt by 1889. In 1900, Manhattan alone had 130,000 horses, pulling streetcars, wagons, and carriages, and leaving their waste behind. They were not fast, and pedestrians could dodge and scramble their way across the crowded streets. Small towns continued to rely on dirt and gravel, but larger cities wanted much better streets. They looked to wood or granite blocks by the 1850s. In 1890, a third of Chicago's 2000 miles of streets were paved, chiefly with wooden blocks, which gave better traction than mud. Brick surfacing was a good compromise, but even better was asphalt paving, which was easy to install and to cut through to get at sewers. With London and Paris serving as models, Washington laid 400,000 square yards of asphalt paving by 1882; it became the model for Buffalo, Philadelphia and elsewhere. By the end of the century, American cities boasted 30 million square yards of asphalt paving, well ahead of brick. The streets became faster and more dangerous so electric traffic lights were installed. Electric trolleys (at 12 miles per hour) became the

main transportation service for middle class shoppers and office workers until they bought automobiles after 1945 and commuted from more distant suburbs in privacy and comfort on asphalt highways. Canada Canada has the world's largest deposit of natural bitumen in the Athabasca oil sands, and Canadian First Nations along the Athabasca River had long used it to waterproof their canoes. In 1719, a Cree named Wa-Pa-Su brought a sample for trade to Henry Kelsey of the Hudson's Bay Company, who was the first recorded European to see it. However, it wasn't until 1787 that fur trader and explorer Alexander MacKenzie saw the Athabasca oil sands and said, "At about 24 miles from the fork (of the Athabasca and Clearwater Rivers) are some bituminous fountains into which a pole of 20 feet long may be inserted without the least resistance." The value of the deposit was obvious from the start, but the means of extracting the bitumen was not. The nearest town, Fort McMurray, Alberta, was a small fur trading post, other markets were far away, and transportation costs were too high to ship the raw bituminous sand for paving. In 1915, Sidney Ells of the Federal Mines Branch experimented with separation techniques and used the product to pave 600 feet of road in Edmonton, Alberta. Other roads in Alberta were paved with material extracted from oil sands, but it was generally not economic. During the 1920s Dr. Karl A. Clark of the Alberta Research Council patented a hot water oil separation process and entrepreneur Robert C. Fitzsimmons built the Bitumount oil separation plant, which between 1925 and 1958 produced up to per day of bitumen using Dr. Clark's method. Most of the bitumen was used for waterproofing roofs, but other uses included fuels, lubrication oils, printers ink, medicines, rust- and acid-proof paints, fireproof roofing, street paving, patent leather, and fence post preservatives. Eventually Fitzsimmons ran out of money and the plant was taken over by the Alberta government. Today the Bitumount plant is a Provincial Historic Site. Photography and art Bitumen was used in early photographic technology. In 1826, or 1827, it was used by French scientist Joseph Nicéphore Niépce to make the oldest surviving photograph from nature. The bitumen was thinly coated onto a pewter plate which was then exposed in a camera. Exposure to light hardened the bitumen and made it insoluble, so that when it was subsequently

rinsed with a solvent only the sufficiently light-struck areas remained. Many hours of exposure in the camera were required, making bitumen impractical for ordinary photography, but from the 1850s to the 1920s it was in common use as a photoresist in the production of printing plates for various photomechanical printing processes. Bitumen was the nemesis of many artists during the 19th century. Although widely used for a time, it ultimately proved unstable for use in oil painting, especially when mixed with the most common diluents, such as linseed oil, varnish and turpentine. Unless thoroughly diluted, bitumen never fully solidifies and will in time corrupt the other pigments with which it comes into contact. The use of bitumen as a glaze to set in shadow or mixed with other colors to render a darker tone resulted in the eventual deterioration of many paintings, for instance those of Delacroix. Perhaps the most famous example of the destructiveness of bitumen is Théodore Géricault's Raft of the Medusa (1818–1819), where his use of bitumen caused the brilliant colors to degenerate into dark greens and blacks and the paint and canvas to buckle. Modern use Global use The vast majority of refined bitumen is used in construction: primarily as a constituent of products used in paving and roofing applications. According to the requirements of the end use, bitumen is produced to specification. This is achieved either by refining or blending. It is estimated that the current world use of bitumen is approximately 102 million tonnes per year. Approximately 85% of all the bitumen produced is used as the binder in asphalt concrete for roads. It is also used in other paved areas such as airport runways, car parks and footways. Typically, the production of asphalt concrete involves mixing fine and coarse aggregates such as sand, gravel and crushed rock with asphalt, which acts as the binding agent. Other materials, such as recycled polymers (e.g., rubber tyres), may be added to the bitumen to modify its properties according to the application for which the bitumen is ultimately intended. A further 10% of global bitumen production is used in roofing applications, where its waterproofing qualities are invaluable. The remaining 5% of bitumen is used mainly for sealing and insulating purposes in a variety of building materials, such as pipe coatings, carpet tile backing and paint. Bitumen is applied in the construction and maintenance of many structures, systems,

and components, such as the following: Highways Airport runways Footways and pedestrian ways Car parks Racetracks Tennis courts Roofing Damp proofing Dams Reservoir and pool linings Soundproofing Pipe coatings Cable coatings Paints Building water proofing Tile underlying waterproofing Newspaper ink production and many other applications Rolled asphalt concrete The largest use of bitumen is for making asphalt concrete for road surfaces; this accounts for approximately 85% of the bitumen consumed in the United States. There are about 4,000 asphalt concrete mixing plants in the US, and a similar number in Europe. Asphalt concrete pavement mixes are typically composed of 5% bitumen (known as asphalt cement in the US) and 95% aggregates (stone, sand, and gravel). Due to its highly viscous nature, bitumen must be heated so it can be mixed with the aggregates at the asphalt mixing facility. The temperature required varies depending upon characteristics of the bitumen and the aggregates, but warm-mix asphalt technologies allow producers to reduce the temperature required. The weight of an asphalt pavement depends upon the aggregate type, the bitumen, and the air void content. An average example in the United States is about 112 pounds per square yard, per inch of pavement thickness. When maintenance is performed on asphalt pavements, such as milling to remove a worn or damaged surface, the removed material can be returned to a facility for processing into new pavement mixtures. The bitumen in the removed material can be reactivated and put back to use in new pavement mixes. With some 95% of paved roads being constructed of or surfaced with asphalt, a substantial amount of asphalt pavement material is reclaimed each year. According to industry surveys conducted annually by the Federal Highway Administration and the National Asphalt Pavement Association, more than 99% of the bitumen removed each year from road surfaces during widening and resurfacing projects is reused as part of new pavements, roadbeds, shoulders and embankments or stockpiled for future use. Asphalt concrete paving is widely used in airports around the world. Due to the sturdiness and ability to be repaired quickly, it is widely used for runways. Mastic asphalt Mastic asphalt is a type of asphalt that differs from dense graded asphalt (asphalt concrete) in that it has a higher bitumen (binder) content, usually around 7–10% of the whole aggregate mix, as opposed to rolled asphalt concrete, which has only around 5% asphalt. This thermoplastic substance is

widely used in the building industry for waterproofing flat roofs and tanking underground. Mastic asphalt is heated to a temperature of and is spread in layers to form an impervious barrier about thick. Bitumen emulsion Bitumen emulsions are colloidal mixtures of bitumen and water. Due to the different surface tensions of the two liquids, stable emulsions cannot be created simply by mixing. Therefore, various emulsifiers and stabilizers are added. Emulsifiers are amphiphilic molecules that differ in the charge of their polar head group. They reduce the surface tension of the emulsion and thus prevent bitumen particles from fusing. The emulsifier charge defines the type of emulsion: anionic (negatively charged) and cationic (positively charged). The concentration of an emulsifier is a critical parameter affecting the size of the bitumen particles - higher concentrations lead to smaller bitumen particles. Thus, emulsifiers have a great impact on the stability, viscosity, breaking strength, and adhesion of the bitumen emulsion. The size of bitumen particles is usually between 0.1 and 50 µm with a main fraction between 1 µm and 10 µm. Laser diffraction techniques can be used to determine the particle size distribution quickly and easily. Cationic emulsifiers primarily include long-chain amines such as imidazolines, amido-amines, and diamines, which acquire a positive charge when an acid is added. Anionic emulsifiers are often fatty acids extracted from lignin, tall oil, or tree resin saponified with bases such as NaOH, which creates a negative charge. During the storage of bitumen emulsions, bitumen particles sediment, agglomerate (flocculation), or fuse (coagulation), which leads to a certain instability of the bitumen emulsion. How fast this process occurs depends on the formulation of the bitumen emulsion but also storage conditions such as temperature and humidity. When emulsified bitumen gets into contact with aggregates, emulsifiers lose their effectiveness, the emulsion breaks down, and an adhering bitumen film is formed referred to as 'breaking'. Bitumen particles almost instantly create a continuous bitumen film by coagulating and separating from water which evaporates. Not each asphalt emulsion reacts as fast as the other when it gets into contact with aggregates. That enables a classification into Rapid-setting (R), Slow-setting (SS), and Medium-setting (MS) emulsions, but also an individual, application-specific optimization of the formulation and a wide field of application (1). For example, Slow-breaking emulsions ensure a longer processing time which is particularly advantageous for fine aggregates (1). Adhesion problems are reported for anionic emulsions in

contact with quartz-rich aggregates. They are substituted by cationic emulsions achieving better adhesion. The extensive range of bitumen emulsions is covered insufficiently by standardization. DIN EN 13808 for cationic asphalt emulsions has been existing since July 2005. Here, a classification of bitumen emulsions based on letters and numbers is described, considering charges, viscosities, and the type of bitumen. The production process of bitumen emulsions is very complex. Two methods are commonly used, the "Colloid mill" method and the "High Internal Phase Ratio (HIPR)" method. In the "Colloid mill" method, a rotor moves at high speed within a stator by adding bitumen and a water-emulsifier mixture. The resulting shear forces generate bitumen particles between 5 µm and 10 µm coated with emulsifiers. The "High Internal Phase Ratio (HIPR)" method is used for creating smaller bitumen particles, monomodal, narrow particle size distributions, and very high bitumen concentrations. Here, a highly concentrated bitumen emulsion is produced first by moderate stirring and diluted afterward. In contrast to the "Colloid-Mill" method, the aqueous phase is introduced into hot bitumen, enabling very high bitumen concentrations. T The "High Internal Phase Ratio (HIPR)" method is used for creating smaller bitumen particles, monomodal, narrow particle size distributions, and very high bitumen concentrations. Here, a highly concentrated bitumen emulsion is produced first by moderate stirring and diluted afterward. In contrast to the "Colloid-Mill" method, the aqueous phase is introduced into hot bitumen, enabling very high bitumen concentrations (1).he "High Internal Phase Ratio (HIPR)" method is used for creating smaller bitumen particles, monomodal, narrow particle size distributions, and very high bitumen concentrations. Here, a highly concentrated bitumen emulsion is produced first by moderate stirring and diluted afterward. In contrast to the "Colloid-Mill" method, the aqueous phase is introduced into hot bitumen, enabling very high bitumen concentrations (1). Bitumen emulsions are used in a wide variety of applications. They are used in road construction and building protection and primarily include the application in cold recycling mixtures, adhesive coating, and surface treatment (1). Due to the lower viscosity in comparison to hot bitumen, processing requires less energy and is associated with significantly less risk of fire and burns. Chipseal involves spraying the road surface with bitumen emulsion followed by a layer of crushed rock, gravel or crushed slag. Slurry seal is a mixture of bitumen emulsion and fine crushed aggregate that is spread on the surface of a road. Cold-mixed asphalt can

also be made from bitumen emulsion to create pavements similar to hot-mixed asphalt, several inches in depth, and bitumen emulsions are also blended into recycled hot-mix asphalt to create low-cost pavements. Bitumen emulsion based techniques are known to be useful for all classes of roads, their use may also be possible in the following applications: 1. Asphalts for heavily trafficked roads (based on the use of polymer modified emulsions) 2. Warm emulsion based mixtures, to improve both their maturation time and mechanical properties 3. Half-warm technology, in which aggregates are heated up to 100 degrees, producing mixtures with similar properties to those of hot asphalts 4. High performance surface dressing. Synthetic crude oil Synthetic crude oil, also known as syncrude, is the output from a bitumen upgrader facility used in connection with oil sand production in Canada. Bituminous sands are mined using enormous (100-ton capacity) power shovels and loaded into even larger (400-ton capacity) dump trucks for movement to an upgrading facility. The process used to extract the bitumen from the sand is a hot water process originally developed by Dr. Karl Clark of the University of Alberta during the 1920s. After extraction from the sand, the bitumen is fed into a bitumen upgrader which converts it into a light crude oil equivalent. This synthetic substance is fluid enough to be transferred through conventional oil pipelines and can be fed into conventional oil refineries without any further treatment. By 2015 Canadian bitumen upgraders were producing over per day of synthetic crude oil, of which 75% was exported to oil refineries in the United States. In Alberta, five bitumen upgraders produce synthetic crude oil and a variety of other products: The Suncor Energy upgrader near Fort McMurray, Alberta produces synthetic crude oil plus diesel fuel; the Syncrude Canada, Canadian Natural Resources, and Nexen upgraders near Fort McMurray produce synthetic crude oil; and the Shell Scotford Upgrader near Edmonton produces synthetic crude oil plus an intermediate feedstock for the nearby Shell Oil Refinery. A sixth upgrader, under construction in 2015 near Redwater, Alberta, will upgrade half of its crude bitumen directly to diesel fuel, with the remainder of the output being sold as feedstock to nearby oil refineries and petrochemical plants. Non-upgraded crude bitumen Canadian bitumen does not differ substantially from oils such as Venezuelan extra-heavy and Mexican heavy oil in chemical composition, and the real difficulty is moving the extremely viscous

bitumen through oil pipelines to the refinery. Many modern oil refineries are extremely sophisticated and can process non-upgraded bitumen directly into products such as gasoline, diesel fuel, and refined asphalt without any preprocessing. This is particularly common in areas such as the US Gulf coast, where refineries were designed to process Venezuelan and Mexican oil, and in areas such as the US Midwest where refineries were rebuilt to process heavy oil as domestic light oil production declined. Given the choice, such heavy oil refineries usually prefer to buy bitumen rather than synthetic oil because the cost is lower, and in some cases because they prefer to produce more diesel fuel and less gasoline. By 2015 Canadian production and exports of non-upgraded bitumen exceeded that of synthetic crude oil at over per day, of which about 65% was exported to the United States. Because of the difficulty of moving crude bitumen through pipelines, non-upgraded bitumen is usually diluted with natural-gas condensate in a form called dilbit or with synthetic crude oil, called synbit. However, to meet international competition, much non-upgraded bitumen is now sold as a blend of multiple grades of bitumen, conventional crude oil, synthetic crude oil, and condensate in a standardized benchmark product such as Western Canadian Select. This sour, heavy crude oil blend is designed to have uniform refining characteristics to compete with internationally marketed heavy oils such as Mexican Mayan or Arabian Dubai Crude. Radioactive waste encapsulation matrix Bitumen was used starting in the 1960s as a hydrophobic matrix aiming to encapsulate radioactive waste such as medium-activity salts (mainly soluble sodium nitrate and sodium sulfate) produced by the reprocessing of spent nuclear fuels or radioactive sludges from sedimentation ponds. Bituminised radioactive waste containing highly radiotoxic alpha-emitting transuranic elements from nuclear reprocessing plants have been produced at industrial scale in France, Belgium and Japan, but this type of waste conditioning has been abandoned because operational safety issues (risks of fire, as occurred in a bituminisation plant at Tokai Works in Japan) and long-term stability problems related to their geological disposal in deep rock formations. One of the main problems is the swelling of bitumen exposed to radiation and to water. Bitumen swelling is first induced by radiation because of the presence of hydrogen gas bubbles generated by alpha and gamma radiolysis. A second mechanism is the matrix swelling when the encapsulated hygroscopic salts exposed to water or moisture

start to rehydrate and to dissolve. The high concentration of salt in the pore solution inside the bituminised matrix is then responsible for osmotic effects inside the bituminised matrix. The water moves in the direction of the concentrated salts, the bitumen acting as a semi-permeable membrane. This also causes the matrix to swell. The swelling pressure due to osmotic effect under constant volume can be as high as 200 bar. If not properly managed, this high pressure can cause fractures in the near field of a disposal gallery of bituminised medium-level waste. When the bituminised matrix has been altered by swelling, encapsulated radionuclides are easily leached by the contact of ground water and released in the geosphere. The high ionic strength of the concentrated saline solution also favours the migration of radionuclides in clay host rocks. The presence of chemically reactive nitrate can also affect the redox conditions prevailing in the host rock by establishing oxidizing conditions, preventing the reduction of redox-sensitive radionuclides. Under their higher valences, radionuclides of elements such as selenium, technetium, uranium, neptunium and plutonium have a higher solubility and are also often present in water as non-retarded anions. This makes the disposal of medium-level bituminised waste very challenging. Different types of bitumen have been used: blown bitumen (partly oxidized with air oxygen at high temperature after distillation, and harder) and direct distillation bitumen (softer). Blown bitumens like Mexphalte, with a high content of saturated hydrocarbons, are more easily biodegraded by microorganisms than direct distillation bitumen, with a low content of saturated hydrocarbons and a high content of aromatic hydrocarbons. Concrete encapsulation of radwaste is presently considered a safer alternative by the nuclear industry and the waste management organisations. Other uses Roofing shingles and roll roofing account for most of the remaining bitumen consumption. Other uses include cattle sprays, fence-post treatments, and waterproofing for fabrics. Bitumen is used to make Japan black, a lacquer known especially for its use on iron and steel, and it is also used in paint and marker inks by some exterior paint supply companies to increase the weather resistance and permanence of the paint or ink, and to make the color darker. Bitumen is also used to seal some alkaline batteries during the manufacturing process. Production About 40,000,000 tons were produced in 1984. It is obtained as the "heavy" (i.e., difficult to distill) fraction. Material with a boiling point greater than around