Chemical Education Today

Letters
Redox Challenges are sought, let the letters a through i stand for the
coefficients of the different compounds. All the following
In your December 1995 issue there were three Re- equations need to be satisfied to balance the equation:
dox Balancing Challenges put forth by Roland Stout (J. for chromium 7a = 2d
Chem. Educ. 1995, 72, 1125). He stated that he had of- for nitrogen 66a = g
fered an A for the entire course if a student could bal- hydrogen 96a + 2c = 2i
ance equation 3 (the hardest), and that no one had ever carbon 42a = f
achieved it. After reading this I decided to offer it to my oxygen 24a+4b = 7d+2f+3g+i
Chemistry II A.P. class, but only for a grade of 90 on the (excluding O present in SO4 ion)
semester exam. Surely no one would balance this mon- potassium b = 2d + g + 2h
ster equation. A week later Nathan Mettlach came in manganese b=e
sulfate ions
with this proof and the balanced equation. While talk- c = e+h
(since it is not broken apart)
ing with him I found out it had taken him only 2 hours.
I had never even thought of taking his approach, but Since all the equations need to be satisfied, combin-
once I read through the proof it all made sense. This is ing them while trying to eliminate as many variables
a remarkable student who deserves recognition for his as possible is the next step.
understanding of math and science, and how the two are c = e+h b = e, b = 2d + g + 2h
related. I believe this should be printed in your Journal c = (2d + g + 2h) + h 96a + 2c = 2i
so other less-enlightened individuals can see really how 96a + 2(2d + g + 3h) = 2i
easy this equation is to balance and to provide them with 24a + 4b = 7d + 2f + 3g + [48a + (2d + g + 3h)]
a new method for balancing equations. 4b = 24a + 9d + 2f + 4g + 3h d = 3.5a
4b = 24a + 31.5a + 84a + 264a + 3h h = 0.5b d 0.5g
h = 0.5b 3.5a 33a
A Large Equation Balanced by Nathan Mettlach
4b = 403.5a + 1.5b 10.5a 99a
2.5b = 294a (at this point, since d = 3.5a, the coefficient
[Cr(N2 H4CO) 6]4[Cr(CN)6]3 + KMnO 4 + H2SO 4 in front of b is even)
a b c 10b = 1176a (since a must be even, and the only factors
of ten are 5 and 2, these numbers are factors
K 2Cr 2O 7 + MnSO4 + CO2 + KNO3 + K 2SO4 + H2O
of the original equations coefficients)
d e f g h i
Using a = 10 and b = 1176, we can find the rest of
To balance this equation, balancing for mass seems the coefficients by substituting into the set of equations
to be the easiest way. The number of each type of ele- that needed to be satisfied.
ment should be the same on both sides. Since coefficients
c = 1399, d = 35, e = 1176, f = 420, g = 660, h = 223, i = 1879

The balanced equation is as follows:

Corrections
The following errors appear in my Letter (J. Chem.
Educ. 1996, 73, A226) :
1. The conservation relationship for H should
read 96a + 2c = 2i, rather than 96a + 2 = 2i.
2. The conservation relationship for O should
read 24a + 4b + 4c = 7d + 4e + 2f + 3g + 4h +
i, rather than 24a + 4b + 4c = 7d + 4e + 2f +
3e + 4h + i.
3. Equation 3 should read d = (7/84)f, rather
than d = (7/84).
David M. Hart
Department of Chemistry
University of Central Oklahoma
Edmond, OK 73034
of the reagents. Students should be able to predict the prod-
One of my students recently found an error in Table 2
of our article, The pH of Sweat of Horses (J. Chem. Educ.
1997, 74, 1135). The treatment J-Flex is incorrectly listed
as a vitamin. J-Flex is instead chondroitin sulfate.
John Tierney
Department of Chemistry
Penn State UniversityDelaware County Campus
Media, PA 19063
10[Cr(N2H4CO)6]4[Cr(CN)6]3 + 1176KMnO4 + 1399H2SO4
35K2Cr2O7 + 1176MnSO4 + 420CO2 + 660KNO3
+ 223K2SO4 + 1879H2O
Rodger S. Nelson
Harlingen High School
1201 E. Marshall
Harlingen, TX 78550
The problem of balancing redox equations has been
under considerable discussion in the Journal lately (15).
However, as was shown by Hart (3), chemical knowledge is
not necessary for properly balancing chemical equations.
Therefore, in the process of teaching redox reactions, the
importance of proper balancing should not be overempha-
sized. Instead, it is worth concentrating on the properties
ucts for given substrates and next to balance the equation.
Some examples, which represent a middle level of difficulty,
are listed below (students know only the left-hand side of
an equation).
a. KMnO4 + KI + H 2SO4 [MnSO4 + K 2SO4 + I2 + H2O]
b. KMnO4 + Na2SO3 + H2O [MnO2 + Na2SO 4 + KOH]
c. KMnO4 + NaNO 2 + KOH [K2MnO4 + NaNO3 + H2O]
d. CuS + HNO3 (concd) [CuSO 4 + NO2 + H2O]

1256 Journal of Chemical Education Vol. 74 No. 11 November 1997


e. Cu + HNO3 (dil) [Cu(NO3)2 + NO + H2O]
f. Na2S2O3 + I2 [Na2S4O6 + NaI]
g. NaBr + NaBrO3 + H2SO 4 [Na2SO 4 + Br2 + H2O]
h. K2Cr2O7 + FeSO4 + H2SO4 [Cr2(SO4)3 + Fe2(SO4)3
+ K2SO 4 + H2O]
i. SnCl2 + K2Cr2O7 + HCl [SnCl4 + CrCl3 + KCl + H2O]
j. KMnO4 + HCl [MnCl2 + Cl2 + KCl + H2O]
k. KMnO4 + H2O2 + H2SO4 [MnSO4 + K2SO4 + O2 + H2O]
l. H2O2 + KI [I2 + KOH]
m. KI + KClO3 + H2SO4 [I2 + KCl + K2SO4 + H2O]
n. KNO2 + KI + H2SO4 [NO + I2 + K2SO4 + H2O]
o. Cl2 + KOH (hot) [KClO3 + KCl + H2O]
The solution of such formulated problems gives the
chemical sense of the reactions and enables students to
learn more about redox properties of chemical compounds.
Thus, the first three reactions show the oxidative proper-
ties of permanganate in acidic, neutral, and basic media, re-
spectively. Reactions d and e indicate the properties of ni-
tric acid according to its concentration. Reaction f is fre-
quently used in analytical chemistry, whereas reaction g is
Vol. 74 No. 11 November 1997 Journal of Chemical Education
Chemical Education Today
an example when an oxidant and a reductant give the same
product. The oxidative property of dichromate is shown in
reaction h. Reactions i and j indicate that in contrast to
dichromate, permanganate can oxidize Cl{ to Cl2 and there-
fore, in the latter case, HCl cannot be used as a reaction
medium. Oxidative and reductive properties of hydrogen
peroxide are visualized by reactions k and l, respectively.
Reaction m shows the oxidative properties of chlorates and
reaction n shows the oxidative properties of nitrate, which
are not always recognized by students. Finally, reaction o is
an example of the dismutation reaction.
Literature Cited
1. Stout, R. J. Chem. Educ. 1995, 72, 1125.
2. Ludwig, O. D. J. Chem. Educ. 1996, 73, 507.
3. Hart, D. M. J. Chem. Educ. 1996, 73, A226.
4. Zaugg, N. S. J. Chem. Educ. 1996, 73, A226.
5. Stout, R. J. Chem. Educ. 1996, 73, A227.
Andrzej Sobkowiak
Faculty of Chemistry
Rzeszw University of Technology
35-959 Rzeszw, Poland
continued on page 1270
1257
 Chemical Education Today

Letters
continued from page 1257
On Balancing Redox Challenges by Unconventional
Oxidation Numbers
Oliver G. Ludwig in his recent article (1) balances
Stouts redox challenges (2) by unconventional oxidation
numbers. I agree that it is pedagogically useful to show to
the students that the oxidation numbers are conventional
tools for interpretation and balancing redox reactions. How-
ever, in my opinion, balancing chemical equations by
nonconventional oxidation numbers is permitted in case of
need only. It may be a powerful method for balancing com-
plicated chemical equations such as double disproportion-
ations or double redox reactions.
For example, the equation
P2 I4 + P4 + H2 O PH4I + H 3PO4
is chemically reasonable is not supported by any evidence
(see J. Chem. Educ. 1988, 65, 45 for conventions used). In
fact semiempirical or ab initio calculations show that nitro-
gen is the negative partner, as does the experimentally de-
rived electron distribution obtained from the X-ray struc-
ture of LiCN. (N varies from 0.046e more negative than C
on PM3 to 0.295e on 6.13G**).
Students are likely to be more confused than enlight-
ened when cations can have variable negative and some-
times nonintegral ONs. They need a systematic procedure
to generate consistent integral numbers linked to concepts
such as electronegativities and Lewis structures taught in
their courses.
Also, Ludwigs method is hardly a great time saver over
conventional balancing. For example, in dealing with the
third equation he has to assign conventional ONs to all but
one of the molecules. The conventional numbers required
in the remaining molecule are shown.

published in this Journal (3), is a really serious redox chal- NH2

lenge for balancing by conventional oxidation numbers (4
[( )] [ ]
III IV II II -III

6). Introducing unusual oxidation numbers we can convert Cr O C Cr ( C N )6

-III
6 4 3
this double disproportionation into a simple redox reaction NH2
as follows: Taking the oxidation number of P in P 2I4 , and
PH4I equal to its conventional value in H3PO4 (P: +5), we The increase in overall oxidation number has to be bal-
get only P is oxidized in the reaction. If we select iodine as anced by the 5-electron reduction Mn(VII) Mn(II). Thus
the other redox element among those kinds of atoms that 558/5 permanganates are required to oxidize each molecule
occur in only one substance on each side of the equation (I, of the chromium complex.
O) and assign H and O their usual oxidation numbers of
+1, and 2, respectively, we get unconventional oxidation
Mean ON's ON's in No. of Increase
number of 2, 5 for I in P2 I4, and 9 in PH4I. Thus, the P is in reactant products atoms in ON
oxidized from 0 to +5, and I is reduced from 2, 5 to 9, giv-
ing stoichiometric coefficients of 6, 5/4, 5/4 and 5 for P4, P 2I4, Cr 18/7 6 7 24
and PH4I, respectively. After balancing in P, then O atoms, C 132/42 4 42 36
and multiplying through by 8, we obtain the balanced equa- N {3 5 66 528
tion:
10P2 I4 + 13P4 +128H 2O = 40PH4 I + 32H3 PO4 Interestingly in the second equation Ludwig considers
the CN group on the thiocyanate and cyanide ions to be un-
Literature Cited changed. In terms of conventional ONs this is only true if
the former is formulated as
1. Ludwig, O. G. J. Chem. Educ. 1996, 73, 507.
2. Stout, R. J. Chem. Educ. 1995, 72, 1125. 0 II {III
3. Carrano, S. A. J. Chem. Educ. 1978, 55, 382.
4. Kolb, D. J. Chem. Educ. 1979, 56, 181. S|= C (= N
5. Cardinali, M. E., Giomini, C., Marrsu, G. J. Chem. Educ. 1995, 72,
716.
6. Cardinali, M. E.; Giomini, C.; Marrosu, G. Educ. Chem. 1996, 51. since the electronegativities of C and S are so close; other-
wise the ONs of C and S both vary and only N remains con-
Zoltn Tth stant.
Lajos Kossuth University
H-4010 Debrecen, P. O. Box 66 A.A. Woolf
Hungary Faculty of Applied Sciences
University of the West of England
Frenchay Campus
Unconventional oxidation numbers Bristol BS16 1QY, UK
If oxidation numbers (ONs) merely serve as bookkeep-
ing numbers for balancing equations, then Ludwigs method
(J. Chem. Educ. 1996, 73, 507) would be acceptable. How- The author replies:
ever ONs have a chemical reality in that they can show,
albeit in an exaggerated fashion, the direction of charge dis- A. A. Woolf takes exception to my note on balancing
tribution and its change in a reaction. The claim, for ex- redox equations (J. Chem. Educ. 1996, 73, 507), remark-
ample, that reversing the electron distribution in the cya- ing that oxidation numbers do have a chemical reality
nide ion from in the CN ion, for example. As Woolf mentions, Gaussian
II {III {IV III orbital and perturbation calculations do show that the
|C ( N| to |C ) N| N end of the ion is the more negative, but hardly by a
full electronic charge. My comment was that further in-

1270 Journal of Chemical Education Vol. 74 No. 11 November 1997

 Chemical Education Today

formation than would be available to a freshman learn- obtained in this way is actually correct, and that the others
ing to balance equations would be needed to lead to a can somehow be negated. The fact is that all of the equa-
preference in oxidation numbers. The beginning student tions that he presents are correctly balanced, and that none
has seen N in the {3 and +3 oxidation states, and car- can be negated on this basis. He suggests that there is a
bon in the +2 and {4, but ordinarily would not have met constraint beyond the balancing of atomsthat is, the bal-
the concepts of either Lewis structures or electronega- ancing of the transfer of electrons. However, if charge is bal-
tivity so early in the course. anced (it is in all these cases), and if each of the atom types
I consider it important that oxidation number not in the equation is correctly balanced (they are), then the
be confused with charge; only the latter has physical re- number of electrons in the equation is trivially balanced.
ality. (Surely the Mn atom in MnO4{ does not have a Based on the mathematics of equation balancing, none
charge of +7; Coulombs law would certainly not permit of these equations is more correct than any of the others.
such charge separation.) Students would get even more There is frequently more than one correct answer to any
confused later in the course when they see formal given question, and often new insights into a problem come
charges if they were to consider them to be real as well. from the unconventional answer. To answer the question
Woolf rejects my use of nonintegral oxidation num- of what ratios of reactant and product masses are actually
bers yet uses mean oxidation numbers, which are non- obtained requires experimental data that are not part of the
integral. I fail to see a difference. algebraic equation-balancing theory.
I do mention using oxidation numbers as tools, ir-
respective of whether they make chemical sense or not. Wade A. Freeman
Similarly, almost everyone speaks of electrons in orbit- Department of Chemistry
als, although, strictly, the orbital concept fails for more University of Illinois at Chicago
than one electron system. Later in the course, when the 845 W. Taylor St.
sophistication of the student has increased, we can talk Chicago, IL 60607
about models versus reality.
By the way, I use the ionelectron/half-reaction N. K. Goh and L. S. Chia
method when I teach balancing redox equations. I con- Division of Chemistry
sider it closer to reality. National Institute of Education
Nanyang Technological University
Oliver Ludwig 469 Bukit Timah Road
Department of Chemistry Singapore 259756
Villanova University
Villanova, PA 19085 David M. Hart
Department of Chemistry
University of Central Oklahoma
Edmond, OK 73034-0177
How Do I Balance Thee?Let Me Count the Ways! Eric A. Lucas
219 Altamont Place
We read with interest How Do I Balance Thee?Let Somerville, NJ 08876
Me Count the Ways! (J. Chem. Educ. 1996, 73, 1129). The
author points out an interesting dilemma in balancing David J. Peery
equations, namely, situations in which the number of vari- 4978 Wayland Ave.
ables (in this case, the number of coefficients of the species San Jose, CA 95118
involved) is more than the number of independent con-
straints (in most cases, the number of elements to be bal- R. Subramaniam
anced) plus one. This situation has been described previ- Singapore Science Centre
ously in this Journal (1991, 68, 984; 1994, 71, 490; 1995, Science Centre Road
72, 894). It results in an infinite number of algebraically Singapore 609081
balanced equations, each of which is a combination of two
equations. One such pair of equations is Marten J. ten Hoor
4 HCl + ClO 2 2 H2O + 2.5 Cl2 J. W. Frisolaan 40
9602 GJ Hoogezand
2 KClO3 + 1.5 Cl2 2 KCl + 3 ClO2 The Netherlands
Ferguson correctly points out that the number of de-
grees of freedom in choosing a balanced equation for this Sidney Toby
system is two, and that one way to choose these degrees of Department of Chemistry
freedom is to set the coefficients of KClO3 and ClO2. From Rutgers University
these, all other coefficients are uniquely determined. P. O. Box 939
[Note: There were two misprints in the table of coeffi- Piscataway, NJ 08855-0939
cients in Fergusons paper. Line 3 should have coefficients
4, 16, 4, 8, 7, 2 and line 5 should have 5, 22, 5, 11, 10, 2.] Richard S. Treptow
However, in his final paragraph, he goes one step too Chicago State University
far and incorrectly implies that only one of the equations Chicago, IL 60628

Vol. 74 No. 11 November 1997 Journal of Chemical Education 1271