Stoichiometry

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This article may be too technical for most readers to understand. Please improve
this article to make it understandable to non-experts, without removing the technical
details. (January 2010)
Stoichiometry (pronounced /ˌstɔɪkiˈɒmɨtri/, STOY-kee-AHM-ə-tree) is a branch of
chemistry that deals with the quantitative relationships that exist among the reactants and
products in chemical reactions. In a balanced chemical reaction, the relations among
quantities of reactants and products typically form a ratio of whole numbers. For example, in
a reaction that forms ammonia (NH3), exactly one molecule of nitrogen (N2) reacts with three
molecules of hydrogen (H2) to produce two molecules of NH3:
N2 + 3H2 → 2NH3
Reaction stoichiometry describes the quantitative relationships among substances as they
participate in chemical reactions. In the example above, reaction stoichiometry describes the
1:3:2 ratio of molecules of nitrogen, hydrogen, and ammonia.
Composition stoichiometry describes the quantitative (mass) relationships among elements
in compounds. For example, composition stoichiometry describes the nitrogen to hydrogen
(mass) relationship in the compound ammonia.
Stoichiometry can be used to calculate quantities such as the amount of products that can be
produced with given reactants and percent yield (the percentage of the given reactant that is
made into the product).
A stoichiometric amount or stoichiometric ratio of a reagent is the amount or ratio where,
assuming that the reaction proceeds to completion:
1. all reagent is consumed,
2. there is no shortfall of reagent, and
3. no residues remain.
Gas stoichiometry deals with reactions involving gases, where the gases are at a known
temperature, pressure, and volume, and can be assumed to be ideal gases. For gases, the
volume ratio is ideally the same by the ideal gas law, but the mass ratio of a single reaction
has to be calculated from the molecular masses of the reactants and products. In practice, due
to the existence of isotopes, molar masses are used instead when calculating the mass ratio.
While almost all reactions have integer-ratio stoichiometry in amount of matter units (moles,
number of particles), some nonstoichiometric compounds are known.
Stoichiometry is based on the law of conservation of mass. The mass of the reactants equals
the mass of the products.

Contents
[hide]
• 1 Etymology
• 2 Different stoichiometries in competing reactions
 • 3 Stoichiometric coefficient
• 4 Stoichiometry matrix
• 5 Gas stoichiometry
• 6 Stoichiometric air-fuel ratios of common fuels
• 7 References
• 8 External links

[edit] Etymology
"Stoichiometry" is derived from the Greek words στοιχεῖον (stoicheion, meaning element])
and μέτρον (metron, meaning measure.) In patristic Greek, the word Stoichiometria was used
by Nicephorus to refer to the number of line counts of the canonicalNew Testament and some
of the Apocrypha.
[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), through
a Friedel-Crafts reaction using AlCl3 as catalyst, may produce singly-methylated
(C6H5CH3), doubly-methylated (C6H4(CH3)2), or still more highly-methylated
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
In layman's terms, the stoichiometric coefficient of any given component is the number of
molecules which participate in the reaction as written.
For example, in the reaction CH4 + 2 O2 → CO2 + 2 H2O, the stoichiometric coefficient of
CH4 would be 1 and the stoichiometric coefficient of O2 would be 2.
In more technically-precise terms, the stoichiometric coefficient in a chemical reactionsystem
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 ξ can be regarded as a real (or hypothetical) product, one molecule of
which is produced each time the reaction event occurs. It is the extensive quantity describing
the progress of a chemical reaction equal to the number of chemical transformations, as
indicated by the reaction equation on a molecular scale, divided by the Avogadro constant (it
is essentially the amount of chemical transformations). The change in the extent of reaction is
given by dξ = dnB/nB, where nB is the stoichiometric number of any reaction entity B (reactant
or product) an dnB is the corresponding amount.[1]
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 rationalfractions. There are often
chemical species present that do not participate in a reaction; their stoichiometric coefficients
are therefore zero. Any chemical species that 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 are conserved, and this
imposes corresponding constraints on possible values for the stoichiometric coefficients.
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. As a consequence, 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.
[edit] Stoichiometry matrix
In complex reactions, stoichiometries are often represented in a more compact form called the
stoichiometry matrix. The stoichiometry matrix is denoted by the symbol, .
If a reaction network has n reactions and m participating molecular species then the
stoichiometry matrix will have corresponding n columns and m rows.
For example, consider the system of reactions shown below:
S1 → S2
5S3 + S2 → 4S3 + 2S2
S3 → S4
S4 → S5.
This systems comprises four reactions and five different molecular species. The
stoichiometry matrix for this system can be written as:

where the rows correspond to S1, S2, S3, S4 and S5, respectively. Note that the process of
converting a reaction scheme into a stoichiometry matrix can be a lossy transformation, for
example, the stoichiometries in the second reaction simplify when included in the matrix.
This means that it is not always possible to recover the original reaction scheme from a
stoichiometry matrix.
Often the stoichiometry matrix is combined with the rate vector, v to form a compact
equation describing the rates of change of the molecular species:

[edit] Gas stoichiometry

Gas stoichiometry is the quantitative relationship (ratio) between reactants and products in a
chemical reaction with reactions that produce gases. Gas stoichiometry applies when the
gases produced are assumed to be ideal, and the temperature, pressure, and volume of the
gases are all known. The ideal gas law is used for these calculations. Often, but not always,
the standard temperature and pressure (STP) are taken as 0°C and 1 bar and used as the
conditions for gas stoichiometric calculations.
Gas stoichiometry calculations solve for the unknown volume or mass of a gaseous product
or reactant. For example, if we wanted to calculate the volume of gaseous NO2 produced
from the combustion of 100 g of NH3, by the reaction:
4NH3 (g) + 7O2 (g) → 4NO2 (g) + 6H2O (l)
we would carry out the following calculations:

There is a 1:1 molar ratio of NH3 to NO2 in the above balanced combustion reaction, so
5.871 mol of NO2 will be formed. We will employ the ideal gas law to solve for the volume
at 0 °C (273.15 K) and 1 atmosphere using the gas law constant of R = 0.08206 L · atm · K−1 ·
mol−1 :
PV = nRT

Gas stoichiometry often involves having to know the molar mass of a gas, given the density
of that gas. The ideal gas law can be re-arranged to obtain a relation between the density and
the molar mass of an ideal gas:

and
and thus:

where:
P = absolute gas pressure
V = gas volume
n = number of moles
R = universal ideal gas law constant
 T = absolute gas temperature
ρ = gas density at T and P
m = mass of gas
M = molar mass of gas
[edit] Stoichiometric air-fuel ratios of common fuels
Fuel By mass By volume [2] Percent fuel by mass
Gasoline 14.7 : 1 — 6.8%
Natural gas 17.2 : 1 9.7 : 1 5.8%
Propane (LP) 15.5 : 1 23.9 : 1 6.45%
Ethanol 9:1 — 11.1%
Methanol 6.4 : 1 — 15.6%
Hydrogen 34 : 1 2.39 : 1 2.9%
Diesel 14.6 : 1 0.094 : 1 6.8%
Gasoline engines are run at stoichiometric air-to-fuel ratio, because gasoline is so volatile that
mixes properly with the air. Diesel engines, in contrast, run lean, with more air available than
simple stoichiometry would require. Diesel fuel is heavier and does not burn immediately to
give gaseous products. Thus, it would form soot (black smoke) at stoichiometric ratio.
[edit] References
1. ^IUPAC Compendium of Chemical Terminology 2nd Edition (1997)
2. ^ North American Mfg. Co.: "North American Combustion Handbook", 1952
• Ilya Prigogine & R. Defay, translated by D.H. Everett; Chapter IV (1954). Chemical
Thermodynamics. Longmans, Green & Co. Exceptionally clear on the logical
foundations as applied to chemistry; includes non-equilibrium thermodynamics.
• Ilya Prigogine (1967). Thermodynamics of Irreversible Processes, 3rd ed..
Interscience: John Wiley & Sons. A simple, concise monograph. Library of Congress
Catalog No. 67-29540
• E.A. Guggenheim (1967). Thermodynamics: An Advanced Treatment for Chemists
and Physicists, 5th ed.. North Holland; John Wiley & Sons (Interscience). A
remarkably astute treatise. Library of Congress Catalog No. 67-20003
• Zumdahl, Steven S. Chemical Principles. Houghton Mifflin, New York, 2005, pp
148–150.
[edit] External links
• Engine Combustion primer from the University of Plymouth
• Free Stoichiometry Tutorials from Carnegie Mellon's ChemCollective
Retrieved from "http://en.wikipedia.org/wiki/Stoichiometry"
Categories: Stoichiometry | Chemical engineering
Hidden categories: Wikipedia articles that are too technical from January 2010 | Articles
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