In the Classroom

edited by
Chemical Principles Revisited W. Cary Kilner
Exeter High School
Newmarket, NH 03857
The Extent of Reaction, ⌬␰—Some Nuts and Bolts
Gavin D. Peckham
Department of Chemistry, University of Zululand, Private Bag X 1001, Kwa Dlangezwa, 3886, South Africa;
gpeckham@pan.uzulu.ac.za

The concept of the “extent of reaction” was first formu-
lated more than 80 years ago. Since then it has undergone
regular refinements and modifications. The chronology of this
development was presented by Dumon et al. (1), who referred
to the multiplicity of concepts, symbols, and terminology that
have been used to describe the extent of a chemical reaction.
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From a graphical point of view, having ∆ξ vary over a
fixed range from 0 to 1 along the x axis allows one to draw a
vertical y axis at x = 0 and another at x = 1. The y axis on the
left may then be associated with pure reactants at the start of
the reaction, and that on the right may be associated with
pure products at the completion of the reaction. A further

Currently, the most widely used form of the extent of
reaction is that which has been recommended by IUPAC (2).
According to IUPAC the approved symbol for the extent
of reaction is ∆ξ and the names “extent of reaction” and
“advancement” are equally acceptable. For a particular chemical
Publication Date (Web): April 1, 2001 | doi: 10.1021/ed078p508
benefit of the 0 to 1 range is that it forms a close parallel
with the way in which mole fractions are used, particularly
as in the case of two-component phase diagrams.
The problem then, is to retain the convenient 0 to 1
range for ∆ξ without transgressing the requirements of

reaction involving a substance B, the extent of reaction is IUPAC. This can be most easily achieved by first understand-
defined by IUPAC as ing how values of ∆ξ are influenced by (i) the way in which
the chemical equation is written, (ii) the effect of differing
∆ξ = ∆nB/νB
initial amounts of reactants and products, and (iii) the role
where ∆nB = nf,B – ni,B (ni,B and nf,B represent the initial of a limiting reagent.
and final amounts of substance B, respectively) and ν B is These effects may be easily understood by using a few simple
the stoichiometric coefficient of substance B. It is negative if numerical examples. For convenience we shall use examples
B is a reactant and positive if B is a product. involving the well-known Haber process, N2 + 3H2 = 2NH3.
From the definition of ∆ξ given above, it is clear that For consistency, an arbitrary value of 15 moles will be used
∆ξ is an extensive quantity that has units of moles. as the initial amount (ni) of reactants and products wherever
Garst (3) made some useful suggestions about how the possible.
extent of reaction could be used as a unifying basis for
stoichiometry and showed how the usefulness of this concept
may be profitably extended to elementary levels of chemistry. Example 1
However, the extent of reaction, ∆ξ, is more widely used in
textbooks of physical chemistry, particularly in the sections At any given stage of a reaction, ∆ξ is the same for all
that deal with free energy, chemical equilibrium, and kinetics. reactants and products.
In earlier texts, sketch graphs of G versus ∆ξ were typically
labeled with the independent variable, ∆ξ, ranging from its N2 + 3H2 = 2NH3
minimum value of zero to a maximum value of one (4 ). Of
course, this is not necessarily correct, since the definition of ν ᎑1 ᎑3 +2
∆ξ has no theoretical upper limit. In recognition of this fact, ni /mol 15 15 15
some highly reputable texts have recently changed their sketch
graphs to leave the ∆ξ axis open ended (5). It is clear from this After the consumption of 2 mol of N2:
lack of consistency that the use of ∆ξ is still somewhat woolly.
From a pedagogical point of view, there is something
nf /mol 13 9 19
elegantly satisfying about having the extent of reaction range
from zero at the start of the reaction to a maximum value of ∆n /mol ᎑2 ᎑6 +4
exactly one, provided that the reaction goes to completion. ∆ξ/mol 2 2 2
If the upper limit were known to be one, then ∆ξ = 0.9, for
example, clearly indicates that the reaction is 90% of the way After the consumption of 4 mol of N2:
to completion and most of the reactants have been converted
into products. If, however, we report that ∆ξ = 0.9 without
nf /mol 11 3 23
knowing the value of the upper limit, then, although we know
the “amount of reaction” that has taken place, the fraction ∆n /mol ᎑4 ᎑12 +8
of reactants that has been converted into products is not ∆ξ/mol 4 4 4
obvious without further computation.

508 Journal of Chemical Education • Vol. 78 No. 4 April 2001 • JChemEd.chem.wisc.edu

 In the Classroom

Example 2
1
⁄2NH2 + 11⁄2H2 = NH3 N2 + 3H2 = 2NH3 2N2 + 6H2 = 4NH3
Even when the initial and final amounts of reactants and ν ᎑1⁄2 ᎑11⁄2 +1 ᎑1 ᎑3 +2 ᎑2 ᎑6 +4
products are fixed, the value of ∆ξ may vary in a way that n i /mol
1
⁄2 11⁄2 0 1 3 0 2 5 0
depends on how the corresponding equation is written. This
n f /mol 0 0 1 0 0 2 0 0 4
variation in ∆ξ results from the changes that occur when the
∆n /mol ᎑ ⁄2
1
᎑1 ⁄2
1
+1 ᎑1 ᎑3 +2 ᎑2 ᎑6 +4
stoichiometric coefficients, ν, are altered.
∆ξ /mol 1 1 1 1 1 1 1 1 1
1
⁄2NH2 + 1 ⁄2H2 = NH3 N2 + 3H2 = 2NH3 2N2 + 6H2 = 4NH3
1
Some of the advantages of having ∆ξ vary over a fixed range
ν ᎑1⁄2 ᎑11⁄2 +1 ᎑1 ᎑3 +2 ᎑2 ᎑6 +4 of 0 to 1 were mentioned above. Example 4 shows how this
n i /mol 15 15 15 15 15 15 15 15 15 may be achieved, without violating IUPAC specifications—
n f /mol 13 9 19 13 9 19 13 9 19 by writing down a chemical equation and then specifying that
∆n /mol ᎑2 ᎑6 +4 ᎑2 ᎑6 +4 ᎑2 ᎑6 +4
the reaction starts with amounts of reactants equal to the sto-
ichiometric coefficients in the equation.
∆ξ /mol 4 4 4 2 2 2 1 1 1

Comments
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If one is prepared to go beyond the limitations of IUPAC

Example 3
In cases where nonstoichiometric amounts of reactants and
products are used, the maximum value of ∆ξ will be achieved
Publication Date (Web): April 1, 2001 | doi: 10.1021/ed078p508
restrictions, then a simpler and more elegant solution is the
reaction advancement ratio, χ , suggested by Dumon et al. (1),
where χ = ∆ξ/∆ξmax and ∆ξ and ∆ξmax have the definitions

already given above. It would make even more sense if IUPAC

when all the limiting reactant (LR) has been used up. This were prepared to support the definition ξ = ∆ξ/∆ξmax. In this
maximum value, ∆ξmax, is given by ∆ξmax = ᎑ nLR/νLR and not case there would be no need to introduce the new name and
by nLR as has been reported (6 ). This is illustrated below and symbol suggested by Dumon and the new definition could
in example 4. become an extension of existing IUPAC recommendations.
This definition would allow ξ to vary from 0 to 1 in the same
N2 + 3H2 = 2NH3 N2 + 3H2 = 2NH3
way that ∆ξ varies in example 4 above. However, it would
have the additional benefit of being an intensive, dimensionless
ν ᎑3 ᎑3
quantity similar to a mole fraction and would thus be inde-
᎑1 +2 ᎑1 +2
pendent of the initial amounts of reactants.
ni /mol 15 15(LR) 15 3(LR) 15 15
nf /mol 10 0 25 0 6 21 Literature Cited
∆n /mol ᎑5 ᎑15 +10 ᎑3 ᎑9 +6 1. Dumon, A.; Lichanot, A.; Poquet, E. J. Chem. Educ. 1993,
∆ξmax/mol 5 5 5 3 3 3 70, 29–30.
2. IUPAC Quantities, Units and Symbols in Physical Chemistry;
Mills, I., Ed.; Blackwell Scientific: Oxford, 1988; p 38.
3. Garst, J. F. J. Chem. Educ. 1974, 51, 194–196.
Example 4 4. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University
Press: Oxford, 1994; pp 272–276.
For any reaction, provided that we start with amounts 5. Atkins, P. W. Physical Chemistry, 6th ed.; Oxford University
of reactants equal to the stoichiometric coefficients in the Press: Oxford, 1998; pp 216–217.
equation, we will always have ∆ξ max = 1 . This stage will be 6. Atkins, P. W. Concepts in Physical Chemistry; Oxford University
reached when (if ) the reaction goes to completion. Press: Oxford, 1995; p 126.

JChemEd.chem.wisc.edu • Vol. 78 No. 4 April 2001 • Journal of Chemical Education 509

 In the Classroom

A Note from W. Cary Kilner, Editor of Chemical Principles Revisited

The 77-year history of the Journal of Chemical Education provides an opportunity to look back over the evolution of the
craft of teaching chemistry. As we examine the various reforms that occurred, we can see how much more informed we have
become in our labs and classrooms owing to burgeoning research in the cognitive sciences (Herron, J. D.; Nurrenbern, S. C. J.
Chem. Educ. 1999, 76, 1353–1361). And we are proud to see how many classroom teachers have used the valuable informa-
tion presented in this Journal to transform their instructional practices and have in turn shared their ideas and successes
with their colleagues by submitting them for publication.
Many pedagogical techniques have changed how we teach, including cooperative-learning strategies, the use of analogies,
probing for misconceptions, harnessing multiple intelligences, and the designing of inquiry-based activities. These tools can
be effective in fostering higher-order thinking skills. However, we still must answer the question: what is it that we want our
students to learn?
It is chemical principles! Numerous articles attest to the importance of teaching and learning that lead to conceptual under-
standing and the ability to apply knowledge, as contrasted with merely short-term memorization and the mechanical use of
algorithms (Herron, J. D.; Greenbowe, T. J. J. Chem. Educ. 1986, 63, 529–531). The understanding of chemical principles
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empowers every learner to become a more informed voter on increasingly technical social issues and a more savvy consumer
of increasingly technical products. It may even inspire students to continue their education into a field that uses chemistry as
foundation material for a lifetime occupation.
In some areas of chemistry there have been changes in knowledge and emphasis as our understanding of this scientific
enterprise deepens. In light of this, it is imperative to revisit fundamental chemical principles frequently to see how they have
Publication Date (Web): April 1, 2001 | doi: 10.1021/ed078p508

been altered by progress in the chemical as well as in the cognitive sciences. Therefore, I ask you to share with your colleagues
how you introduce and present various chemical principles, how your students apply them, how your students investigate
them in the laboratory, and how you assess your students’ understanding, by writing an article for the Journal. (The Mission
Statement for Chemical Principles Revisited appeared on page 679 of the June 2000 issue.)

Biographical Sketch, W. Cary Kilner

After spending spent a sabbatical year at the University of New Hampshire
five summers in the working on lecture-demonstration experiments.
chemical industry, In 1995 he earned his MST degree in chemical educa-
Cary Kilner earned his tion from the University of New Hampshire and in 1998–
Bachelor’s degree in 99 he spent a second sabbatical leave there doing more gradu-
chemical engineering ate work in chemistry and auditing biology and calculus.
from Michigan State He has a strong interest in Writing Across the Curriculum,
University in 1969. which he uses extensively in his teaching. Cary is also work-
There followed study ing toward the integration of Physical Science with Algebra I
toward an MBA and and Chemistry with Algebra II at Exeter High School and is
several years as a pro- a strong proponent of the national School-to-Work initiative.
fessional jazz pianist. Cary serves as the New Hampshire delegate to the New
Then, in 1980, he joined the staff of Exeter High School in England Science Teachers at MIT (NEST) and teaches sum-
Exeter, New Hampshire, where he undertook the redesign mer school at the Phillips Exeter Academy. He has published
of the chemistry program. four articles in this Journal, two in the NEACT Journal, and
In 1984 he became a Dreyfus Master Teacher, in 1985 five in the NEST Journal. In 1997 he received the New En-
he served as the Northern Chair of the New England Asso- gland Institute of Chemists Secondary Teacher Award and
ciation of Chemistry Teachers (NEACT), and in 1989 he in 1998 the NEST Teacher Award for New Hampshire.

W. Cary Kilner • Exeter High School • 7 Salmon Street • Newmarket, NH 03857

phone 603/659-6825 • fax 603-775-8989 • email Car yPQ@aol.com

510 Journal of Chemical Education • Vol. 78 No. 4 April 2001 • JChemEd.chem.wisc.edu