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pubs.acs.org/jchemeduc

Arrow Pushing: A Rational, Participatory Approach To Teaching

Descriptive Inorganic Chemistry
Steffen Berg and Abhik Ghosh*
Department of Chemistry, University of Tromsø, 9037 Tromsø, Norway

ABSTRACT: Inorganic chemistry at core consists of a vast array

of molecules and chemical reactions. To master the subject,
students must learn to think intelligently about this vast body of
facts, a feat seldom accomplished in an introductory course. All
too often, young undergraduate students perceive the field as an
amorphous and illogical body of information that has to be
memorized. Organic chemistry, by contrast, because of its
emphasis on the reaction mechanisms, is perceived as a far
more rational field. We have found that a mechanistic approach
also works well for introductory inorganic chemistry. Recogniz-
ing common inorganic species as electrophiles and nucleo-
philes, coupled with organic-style arrow pushing, provides a
gentle and stimulating introduction to the field. The inherently participatory nature of the arrow-pushing approach greatly enhances
the students’ sense of personal engagement in the course.
KEYWORDS: Second-Year Undergraduate, Upper-Division Undergraduate, Inorganic Chemistry, Problem Solving/Decision
Making, Descriptive Chemistry, Mechanisms of Reactions, Reactions

A major factor that contributes to the relative popularity of

organic chemistry among university students is its logic.
Mechanistic rationales are available for the great majority of synthetic
reactions and even beginning students learn to write mechanisms
and to predict products based on mechanistic arguments, in
other words, arrow pushing. A survey of major organic textbooks
showed that the mechanistic approach is universal in introduc-
tory organic courses at the university level. The situation with
inorganic chemistry is very different; no major introductory
textbook adopts a mechanistic approach in presenting descriptive
inorganic chemistry.1
5 This situation leads to a perception of
inorganic chemistry as an amorphous, illogical body of facts that
has to be memorized.
The chemistry of s- and p-block elements involves similar
bonding concepts as those encountered in organic chemistry. An
appreciation of the main ionic organic processes, such as nucleophilic
displacements, eliminations, nucleophilic additions to carbonyl
groups, and electrophilic additions to carbon
carbon multiple
bonds, can therefore aid the mechanistic understanding of p-block
chemistry.6 With this realization, a new approach was devised; a
standard inorganic text with an emphasis on descriptive chem-
istry was used in a one-semester introductory inorganic chem-
istry course; much of the final exam, however, consisted of
mechanism problems. There was a concern that the disconnect
between the textbook and the exams would lead to strong
student dissatisfaction. Gratifyingly, with one or two exceptions,
the students (about 100 over the last 10 years) did not express
any discontent with the strategy. Indeed, by the end of the
semester, the students find the idea of a “mechanism-free”
inorganic course old-fashioned and unthinkable.
Why do introductory inorganic texts eschew a mechanistic
approach? One reason is that, in contrast to many common
organic functional groups, simple p-block compounds such as
hydrides, oxides, halides, and so forth tend to be much more
reactive and their reactions have been far less thoroughly studied.
Understandably, textbook writers are hesitant to emphasize an
approach that has little basis in experimental fact. This is a valid
argument, but as explained below, the benefits of a mechanistic
approach outweigh it. Care was taken to point out that
mechanisms are seldom, if ever, proven; although, they are
often disproven. Equally, it was emphasized that the mecha-
nisms presented in the course were largely hypothetical.
Three major considerations, however, justify the mecha-
nistic approach.
• First, the mechanistic concepts are based on strong parallels
with well-studied organic processes.
• Second, mechanisms provide a logical framework students
can use to make sense of a vast body of factual information.
Even if a mechanism is unsubstantiated, it still provides a
rationale for how a given reaction might occur. This is possibly
the strongest justification for a mechanistic approach.
• Third, working on mechanism problems dramatically in-
creases student participation in the course. Thus, students
spent most of their time solving problems instead of being
lectured to. There is strong evidence that the participatory
approach has led to greatly improved student performance
in exams.
Published: September 16, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 1663 dx.doi.org/10.1021/ed200166z | J. Chem. Educ. 2011, 88, 1663–1666
Journal of Chemical Education
Six brief vignettes are presented below that illustrate the
mechanistic approach as applied to introductory inorganic
chemistry. The course textbook1 is replete with dozens of additional
reactions that serve as instructive mechanistic exercises.
’ SOME MECHANISTICALLY “OBVIOUS” REACTIONS
At the beginning of the inorganic course, the typical student is
familiar with the fact that ammonia is a base or nucleophile and
boron trihalides are electrophiles. When the following reaction is
presented,
many students immediately recognize that NH3 attacks BCl3 to
liberate Cl
:

+
The eliminated Cl ions combine with H from the positively
charged ammonium centers to generate gaseous HCl. The
nitrogen lone pair in the product, NH2
BCl2, then attacks
another BCl3 molecule.
Nitrogen-on-boron attacks continue until a B3N3 ring is
constructed. Once again, chloride ions pluck off protons from
the tetracoordinate nitrogen centers, generating fully conjugated
B3N3H3Cl3.
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Similar to most p-block elements, nitrogen forms both
nucleophilic and electrophilic compounds; well-known exam-
ples of the latter type typically involve species with N
O
linkages where the more electropositive nitrogen acts as an
electrophilic center. Consider the hydrolysis of N2O3 and
N2 O5 :
’ PRODUCTION OF AZIDE: A MORE COMPLEX
REACTION
Nitrogen
nitrogen linkages are fairly common and many of
them arise when a nucleophilic nitrogen attacks an electrophilic
one. Consider the production of sodium azide, the key consti-
tuent of automobile air bags, by passing N2O gas over NaNH2
solid at 200
270 °C:
200
270 °C
2NH2
þ N2 O sf NH3 þ N3
þ HO

When faced with a mechanistically less obvious reaction, it is
instructive to look carefully at the products; typically, this gives a
clue as to what bonds form and what bonds are broken. That, in
turn, suggests what must attack what. In this case, an N
N bond
forms and NH2
most likely is the initial nucleophile that attacks
one of the N2O nitrogens. One mechanistic possibility, in the
sense that it yields the observed products via reasonable elemen-
tary steps, is the following:
Note that OH
acts as a leaving group in the mechanism, which
is uncommon, but the high temperature of the reaction is a good
dx.doi.org/10.1021/ed200166z |J. Chem. Educ. 2011, 88, 1663–1666
Journal of Chemical Education
justification for invoking it. Interestingly, the same products can
also be obtained by letting NH2
attack the terminal nitrogen of
N2O:
Determining which of the above two pathways is more likely is
a more difficult proposition and may involve isotope labeling
experiments and possibly quantum chemical calculations.
’ HYDROLYSIS OF PCL3: AN INTRODUCTION TO HY-
PERCOORDINATE PHOSPHORUS
Phosphorus and its heavier congeners exhibit a greater ten-
dency to adopt higher coordination numbers than nitrogen.
Whereas a discussion of the bonding in these so-called hyper-
valent species is beyond the scope of this article,7,8 it is sufficient to
recognize that violations of the octet rule are permissible as long
as the electron-bookkeeping is done correctly. Consider the
hydrolysis of phosphorus trichloride, PCl3:
PCl3 þ 3H2 O f H3 PO3 þ 3HCl
Most students immediately think that the reaction must consist
of three successive displacements of Cl
by the three water
molecules, resulting in P(OH)3:
They are surprised when told that the dominant form of H3PO3
does not contain tricoordinate phosphorus but is best written as
HP+(OH)2(O
). Once again, it is useful to emphasize that the
clue to getting the right product should come from examining its
structure, which quickly leads the students to realize that the lone
pair on the tricoordinate phosphorus must pick up a proton to
form a P
H bond that is present in the product; from that point
on, things typically proceed smoothly:
’ NUCLEOPHILIC BREAKDOWN OF
CYCLOOCTASULFUR
The chemistry of sulfur and selenium provide numerous
examples for students to hone their arrow-pushing skills. The
complete breakdown of elemental sulfur rings, typified by S8, by
nucleophiles such as PPh3 and CN
, is discussed here:
S8 þ 8Ph3 P f 8Ph3 PS
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The first step is
and students readily see that the mechanism is repetitive.
The last steps of the overall reaction, however, are less
obvious. Once the sulfur chain has broken down to Ph 3 P +

S
S
, how exactly does this species react with the final mole
of Ph3 P? To avoid a step involving PPh3 attack on an anionic
sulfur center, a cyclic PS 2 ring with no formal charge on any
atom is invoked:
’ THE HALOGEN
ALKALI REACTION
The reaction of halogen molecules with cold aqueous alkali to
yield hypohalite and halide are beautiful examples of the far-
reaching concept of the SN2 displacement. The halogen
halo-
gen bond breaks easily because of its weakness (single bonds
between two electronegative atoms are typically weak):
With warm alkali, however, the same reactants give differ-
ent products. The hypohalite anions disproportionate on warming
to halate (XO3
) and halide, as shown below for chlorine:
3ClO
f ClO3
þ 2Cl

Clearly, oxygen must repeatedly attack chlorine to generate the
chlorate anion and the following mechanism is proposed:
This mechanism is surprising because, in the first step, both
the nucleophile and the electrophile are the same anion, ClO
.
However, there are not a lot of alternatives. On the basis of the
Sherlock Holmes dictum “When you have eliminated the im-
possible, whatever remains, however improbable, must be the
truth”, the above mechanism is favored.
’ SYNTHESIS OF HYDRAZINE
A highly instructive reaction for letting students exercise their
arrow-pushing skills is the synthesis of hydrazine involving the
oxidation of ammonia by hypochlorite:
2NH3 þ NaOCl þ H2 O f NaCl þ N2 H4 þ 2H2 O
Superficially, the reaction is little more than sequential nucleo-
philic displacements: ammonia attacks ClOH, thereby forming
dx.doi.org/10.1021/ed200166z |J. Chem. Educ. 2011, 88, 1663–1666
Journal of Chemical Education
NH2Cl, which has a leaving group, Cl
; a second ammonia then
attacks NH2Cl to generate the N
N bond of hydrazine:
An observant student might suggest that free hypochlorous acid,
ClOH, which is invoked as an electrophile in the above scheme, is
an unlikely species in the strongly alkaline solution where this
chemistry occurs. The following cyclic mechanism neatly avoids
the intermediacy of neutral ClOH, while generating the requisite
NH2Cl:
Obtaining experimental support for this pathway is difficult, but
basic organic knowledge suggests that it is not an unreasonable
proposal.
’ CONCLUDING REMARKS
Despite its inherently speculative nature, the value of the mechan-
istic approach in introductory inorganic chemistry has been described.
The idea that first- and second-year undergraduate students can
devise clockwork pictures of how inorganic reactions might occur
is a significant advance in chemical education. Admittedly, arrow
pushing does not explain the why of chemical reactions; thus,
pushing arrows clearly does not explain why SiCl4 is immediately
hydrolyzed, whereas CCl4 is not. More work is needed to extend this
approach to d- and f-element chemistry, where bonding scenarios are
more diverse. These are significant limitations, but arrow pushing
should not replace other theoretical concepts of the inorganic
curriculum. With those caveats the approach outlined above has
had a transformative effect on inorganic teaching at our institution.
A mechanistic approach naturally led to a more participatory
model of classroom learning. Thus, a significant fraction of
formal lectures have been abandoned in favor of in-class
problem-solving sessions, where students, often working in pairs
or small groups, solve mechanism problems. The students
sometimes volunteer to work out mechanisms on the blackboard
and explain their line of thinking to the rest of the class. Although
our small class sizes (10
20 students) are not ideal for statistical
analyses, the evidence suggests that this approach has been
effective. Thus, on an A
F grade scale, 50% or more of the
students have routinely obtained A’s, leaving a few B’s, and even
fewer C’s and often no failures, a level of performance that is
unusually good for an introductory course. To the authors, the
explanation seems obvious: the simple device of arrow pushing
wherever possible has transformed a descriptive, lecture-based
course into a fun, reasoning-based, participatory course.
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The value of active, participatory learning has been highlighted
on many occasions in the pedagogical literature, which is outside
the scope of this science-focused article. Mention may be made,
however, of a recent, large-scale study at the University of British
Columbia9 documenting the value of active learning in intro-
ductory physics classes. The experience presented here is clearly
in line with the study.
Finally, it should be a simple matter for inorganic professors to
adopt this approach. Most inorganic instructors at colleges and
universities also have significant experience in organic chemistry
and should be able to apply their “organic” skills to inorganic chem-
istry and look at inorganic reactions with organic eyes.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: abhik.ghosh@uit.no.
’ REFERENCES
(1) Housecroft, C.; Sharpe, A. G. Inorganic Chemistry, 3rd ed.;
Pearson, 2007, 1
1136. This is our favorite inorganic text and the
one we follow in our course. It has the best emphasis on descriptive
chemistry, in our opinion.
(2) Atkins, P. W.; Overton, T.; Rourke, J.; Weller, M.; Armstrong, F.
Shriver and Atkins’ Inorganic Chemistry, 5th ed.; Oxford University Press:
Oxford, 2009. An excellent book, with a more physical and theoretical
flavor.
(3) Rayner-Canham, G.; Overton, T. Descriptive Inorganic Chemistry,
5th ed.; Freeman: New York, 2010.
(4) Henderson, W. Main Group Chemistry; Royal Society of Chem-
istry: Cambridge, U.K., 2000. A delightfully short but informative book.
(5) Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chemistry;
Wiley: New York, 1995.
(6) The emphasis on p-block elements reflects the fact that s-block
chemistry is too ionic to involve much arrow pushing. We believe that
extending our methods to d-block chemistry should be possible, but, as
of now, we have not worked out the details.
(7) Magnuson, E. J. Am. Chem. Soc. 1990, 112, 7940–7951. This is a
seminal paper that provided a first theoretical framework for bonding in
hypervalent compounds. Among other things, this work showed that
such bonding is readily explained in terms of molecular orbital concepts
involving s and p orbitals and that d orbitals (and spd hybridization) do
not need to be invoked.
(8) Curnow, O. J. Chem. Educ. 1998, 75, 910–915.
(9) Deslauriers, L.; Schelew, E.; Wieman, C. Science 2011, 332,
862–854.
dx.doi.org/10.1021/ed200166z |J. Chem. Educ. 2011, 88, 1663–1666