Stoichiometry rests upon the law of conservation of mass, the law of definite proportions (i.e., the law of constant composition) and the law of multiple proportions. In general, chemical reactions combine in definite ratios of chemicals. Since chemical reactions can neither create nor destroy matter, nor transmute one element into another, the amount of each element must be the same throughout the overall reaction. For example, the amount of element X on the reactant side must equal the amount of element X on the product side.
Stoichiometry is often used to balance chemical equations. For example, the two diatomic gases, hydrogen and oxygen, can combine to form a liquid, water, in an exothermic reaction, as described by the following equation:
The term stoichiometry is also often used for the molar proportions of elements in stoichiometric compounds. For example, the stoichiometry of hydrogen and oxygen in H2O is 2:1. In stoichiometric compounds, the molar proportions are whole numbers (that is what the law of multiple proportions is about).
Compounds for which the molar proportions are not whole numbers are called non-stoichiometric compounds.
Stoichiometry is used not only to balance chemical equations but also is used in conversions — i.e. converting from grams to moles, or from grams to millilitres. For example, if there were 2.00 g of NaCl, to find the number of moles, one would do the following,
In the above example, when written out in fraction form, the units of grams form a multiplicative identity, which is equivalent to one (g/g=1), with the resulting amount of moles (the unit that was needed), as shown in the following equation,
Stoichiometry is also used to find the right amount of reactants to use in a chemical reaction. An example is shown below using the thermite reaction,
So, to completely react with 85.0 grams of iron (III) oxide, 28.7 grams of aluminum are needed.
[edit] Different stoichiometries in competing reactions
Often, more than one reaction is possible given the same starting materials. The reactions may differ in their stoichiometry. For example, the methylation of benzene (C6H6) may produce singly-methylated (C6H5CH3), doubly-methylated (C6H4(CH3)2), or still more highly-methylated (C6H6 − n(CH3)n) products, as shown in the following example,
In this example, which reaction takes place is controlled in part by the relative concentrations of the reactants.
[edit] Stoichiometric coefficient
The stoichiometric coefficient in a chemical reaction system of the i–th component is defined as
or
where Ni is the number of molecules of i, and ξ is the progress variable or extent of reaction (Prigogine & Defay, p. 18; Prigogine, pp. 4–7; Guggenheim, p. 37 & 62). The extent of reaction can be regarded as a real (or hypothetical) product, one molecule of which is produced each time the reaction event occurs.
The stoichiometric coefficient νi represents the degree to which a chemical species participates in a reaction. The convention is to assign negative coefficients to "reactants" (which are consumed) and positive ones to "products". However, any reaction may be viewed as "going" in the reverse direction, and all the coefficients then change sign (as does the free energy). Whether a reaction actually will go in the arbitrarily selected forward direction or not depends on the amounts of the substances present at any given time, which determines the kinetics and thermodynamics; i.e. whether equilibrium lies to the "right" or the "left".
If one contemplates actual reaction mechanisms, stoichiometric coefficients will always be integers, since elementary reactions always involve whole molecules. If one uses a composite representation of an "overall" reaction, some may be rational fractions. There are often chemical species present which do not participate in a reaction; their stoichiometric coefficients are therefore zero. Any chemical species which is regenerated, such as a catalyst, also has a stoichiometric coefficient of zero.
The simplest possible case is an isomerism
in which νB = 1 since one molecule of B is produced each time the reaction occurs, while νA = −1 since one molecule of A is necessarily consumed. In any chemical reaction, not only is the total mass conserved, but also the numbers of atoms of each kind, and this imposes a corresponding number of constraints on possible values for the stoichiometric coefficients. Of course, only a small subset of the possible atomic rearrangements will occur.
There are usually multiple reactions proceeding simultaneously in any natural reaction system, including those in biology. Since any chemical component can participate in several reactions simultaneously, the stoichiometric coefficient of the i–th component in the k–th reaction is defined as
so that the total (differential) change in the amount of the i–th component is
.
Extents of reaction provide the clearest and most explicit way of representing compositional change, although they are not yet widely used.
With complex reaction systems, it is often useful to consider both the representation of a reaction system in terms of the amounts of the chemicals present { Ni } (state variables), and the representation in terms of the actual compositional degrees of freedom, as expressed by the extents of reaction { ξk }. The transformation from a vector expressing the extents to a vector expressing the amounts uses a rectangular matrix whose elements are the stoichiometric coefficients [ νi k ].
The maximum and minimum for any ξk occur whenever the first of the reactants is depleted for the forward reaction; or the first of the "products" is depleted if the reaction as viewed as being pushed in the reverse direction. This is a purely kinematic restriction on the reaction simplex, a hyperplane in composition space, or N‑space, whose dimensionality equals the number of linearly independent chemical reactions. This is necessarily less than the number of chemical components, since each reaction manifests a relation between at least two chemicals. The accessible region of the hyperplane depends on the amounts of each chemical species actually present, a contingent fact. Different such amounts can even generate different hyperplanes, all of which share the same algebraic stoichiometry.
In accord with the principles of chemical kinetics and thermodynamic equilibrium, every chemical reaction is "reversible", at least to some degree, so that each equilibrium point must be an interior point of the simplex. Consequently, extrema for the ξ's will not occur unless an experimental system is prepared with zero initial amounts of some products.
The number of physically independent reactions can be even greater than the number of chemical components, and depends on the various reaction mechanisms. For example, there may be two (or more) reaction paths for the isomerism above. The reaction may occur by itself, but faster and with different intermediates, in the presence of a catalyst.
The (dimensionless) "units" may be taken to be molecules or moles. Moles are most commonly used, but it is more suggestive to picture incremental chemical reactions in terms of molecules. The N's and ξ's are reduced to molar units by dividing by Avogadro's number. While dimensional mass units may be used, the comments about integers are then no longer applicable.
Thats about all I know about it.
2007-12-10 09:04:23
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answer #8
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answered by Anonymous
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