Research: Science and Education

Variability of the Cell Potential of a Given Chemical Reaction

Ladislav H. Berka* Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, Worcester, MA 01609-2280; *lhberka@wpi.edu Ilie Fishtik Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, MA 01609-2280

In all of the general chemistry (1), physical chemistry (2), and thermodynamics textbooks (3) we have perused, it is implied that a given chemical reaction, whether a redox reaction or not, can be decomposed into a pair of half-reactions in a unique way. Consequently, one can infer from this that any given chemical reaction possesses a unique (standard) cell potential. While this is true for many simple processes, there are other chemical processes that may be decomposed into half-reactions in several different ways. Two examples are considered. Reaction i may be uniquely decomposed into two half-reactions, reaction ia and ib:
+ Zn(s) + Cu2 (aq) + Cu2 (aq) + 2e + Zn2 (aq) + Cu(s)

reactions. The values for the standard potentials were obtained using eq 1, = n F (1) GR where n is the number of electrons involved in each half-reaction and F is the Faraday constant, 96,487.0 Ce. The results obtained are given in eqs 25:
G( ii ) = G(ii a ) + G( ii b) = = 60.82 158.3 = 97.4 kJ

(2)

(i) (ia) (ib)

ii) = ( iia ) + ( iib ) ( = 0.1576 + 0.4101 = 0.252 V

G( ii ) = G( iic ) + G( ii d ) = 1, 066.09 + 968.6 = 97.4 kJ
ii ) = ( iic ) + ( (ii d ) = 0.345284 + 0.3137 = 0.0316 V

(3)

Cu(s)

(4)

Zn(s)

+ Zn2 (aq) + 2e

Conversely, using the species,1 H2SO3(aq), SO42(aq), S2O32(aq), H2S(g), H2O(l), and H+(aq), reaction ii
4H2SO3(aq)
2SO42 (aq)

(5)

S2O32 (aq)

+ 6H (aq) + H2O(l) (ii)

+

may be decomposed into half-reactions in different ways. For instance, one way is:
2H2SO3(aq) + 2H2O(l)
+ 2SO42 (aq) + 8H (aq) + 4e (iia)

2H2SO3(aq) + 2H+(aq) + 4e
S2O32 (aq) + 3H2O(l)

(iib)

Both pairs of half-reactions give the same value of the standard free energy change of reaction ii, 97.4 kJ, but differing values of the standard potentials for this reaction, 0.252 V versus 0.0316 V. In fact, these potentials are inversely proportional to the number of electrons, n, exchanged between the halfreactions, 4 and 32, respectively, as they must be from eq 1. As far as we are aware this phenomenon has not been treated in the literature.2 The purpose of this article is to illustrate, discuss, and explain this observation. The following considerations are purely thermodynamic and hence, independent of kinetics. Example 1: Redox Reaction Consider reaction iii:
+ NH4 (aq) + NO33 (aq)

Another way is:

+ 4H2SO3(aq) + SO42 (aq)+ 34H (aq) + 32e 5H2S(g) + 16H2O(l) (iic)

N2O(g) + 2H2O(l)

(iii)

5H2S(g) + 15H2O(l)

+ (iid) 3SO42 (aq) + S2O32 (aq) + 40H (aq) + 32e

At first glance there is nothing special in the above considerations. Indeed, these pairs of half-reactions may be understood as different ways to perform the same overall reaction in a galvanic or electrolytic cell. What is really surprising, however, is that the cell potential of the same reaction may be different, depending on the way the reaction is split into half-reactions. The standard free energies of half-reactions iiad were calculated using published values (4) of the free energies of formation, Gf, of the various species appearing in these half584 Journal of Chemical Education

Using the species,3 NH4+(aq), NO3(aq), N2O(g), H2O(l), and H+(aq), reaction iii can be obtained by adding together the half-reactions shown in Table 1. The pairs of half-reactions IVI in Table 1 represent the maximum number of ways (5) that these species can be combined to give reaction iii. The values of the standard free energies of reaction and standard potentials for the half-reactions given in Table 1 were calculated using the same methods given above for reactions iiad above. The sums of the values of GR and o for each of these pairs of half-reactions are also collected in Table 1. All of the sums of the pairs of half-reactions have GR = 182.01 kJ, which is the GR value of reaction iii. Again, the values of o and n in Table 1 are inversely proportional to each other.
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Table 1. Pairs of Half-Reactions Summing To Give Reaction iii Example Ia Ib SUM IIa IIb SUM IIIa IIIb SUM IVa IVb SUM Va Vb SUM VIa VIb SUM
+

Half-Reactions 2N2O + 20H + 16e 4NH4 + 2H2O 5NH4+ + NO3 3N2O + 20H+ + 16e NH4+ + NO3 N2O + 2H2O
+

GR/kJ 999.9 817.89 182.01 681.96 499.95 182.01 863.97 681.96 182.01 454.64 272.63 182.01 431.98 249.97 182.01 345.59 163.58 182.01

/V 0.64769 0.52979 0.11790 0.88348 0.64769 0.23579 1.1193 0.88348 0.23579 0.88348 0.52979 0.35369 1.1193 0.64769 0.47159 1.1193 0.52979 0.58948

NO3 + 10H+ + 8e NH4+ + 3H2O 2NH4+ + H2O N2O + 10H+ + 8e NH4+ + NO3 N2O + 2H2O 2NO3 + 10H+ + 8e N2O + 5H2O NH4+ + 3H2O NO3 + 10H+ + 8e NH4+ + NO3 N2O + 2 H2O 2/3NO3 + 20/3H+ + 16/3e 2/3NH4+ + 2H2O 5/3NH4+ + 1/3NO3 N2O + 20/3H+ + 16/3e NH4+ + NO3 N2O + 2H2O NO3 + 5H+ + 4e 1/2N2O + 5/2H2O NH4+ + 1/2H2O 1/2 N2O + 5H+ + 4e NH4+ + NO3 N2O + 2H2O 4/5NO3 + 4H+ + 16/5e 2/5N2O + 2H2O NH4+ + 1/5NO3 3/5N2O + 4H+ +16/5e NH4+ + NO3 N2O + 2H2O

Example 2: Nonredox Reaction Consider reaction iv, a nonredox reaction:

+ H (aq) + OH (aq)

cies NO3(aq) and NH4+(aq), each on the left side of of two half-reaction and the species N2O(g) on the right side of both half-reactions, that is, (iv)
NO3 (aq) NH4 (aq)
+

H2O(l)

N2O(g) N2O(g)

(v) (vi)

Using the species, 4 Mn(s), MnO 2 (s), MnO 4 2 (aq), MnO4(aq), H+(aq), OH(aq), and H2O(l), reaction iv can be obtained by adding together the half-reactions shown in Table 2. The sums of these half-reactions all give reaction iv. The values of GR and o for these half-reactions are also given in Table 2 along with the number of electrons, n, exchanged between the half-reactions. All of the sums of the pairs of half-reactions have GR = 79.9 kJ, which is the GR value of reaction iv. Again the values of o and n in Table 2 are inversely proportional. Significance If one is designing a voltaic cell in which to carry out a spontaneous chemical reaction, the value of the cell potential will depend on the half-reactions chosen to carry out the reaction. Likewise, if one wishes to use an electrolytic cell to carry out a nonspontaneous chemical reaction, that is, the reverse of reactions iii or iv, the value of the potential required to cause the reaction to occur will also depend on the half-reactions chosen to carry out the reaction. Additionally, in general chemistry courses we might use reaction iii as an exercise in learning to balance redox reactions. We would expect students to start by isolating the spewww.JCE.DivCHED.org

In acidic solution the balancing would then be completed by adding H2O(l), H+(aq), and electrons. The resulting balanced half-reactions would then correspond to half-reactions Va and Vb in Table 1, respectively. Consequently, the other remaining half-reactions given in Table 1 are never obtained in the classroom. Conclusion While the values of G and G for any chemical reaction are state functions (independent of path), it has been demonstrated that the values of o and n for many chemical reactions are not; that is, there is more than one way to carry them out. This arises because the redox reactions choosen to carry out a chemical reaction are often arbitrary. Reaction i is not of this type, however reactions ii, iii, and iv are. Notes
1. The S-containing species in this list are stable in their standard states in acidic solutions; see the diagram on p 81 of ref 6. 2. W. L. Masterton recently informed the corresponding author (LHB) that many years ago C. W. Moeller, Jr. (since deceased)

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Table 2. Pairs of Half-Reactions Summing To Give Reaction iv Example VIIa VIIb SUM VIIIa VIIIb SUM IXa IXb SUM Xa Xb SUM XIa X Ib SUM XIIa XIIb SUM XIIIa XIIIb SUM Half-Reactions H+ + e 1/2H2 OH + 1/2H2 H2O + e H+ + OH H2O 1/4O2 + H+ + e 1/2H2O OH 1/4O2 + 1/2H2O + e + H + OH H2O 1/4MnO2 + H+ + e 1/4Mn + 1/2H2O 1/4Mn + OH 1/4MnO2 + 1/2H2O + e H+ + OH H2O 1/8MnO4 + H+ + 7/8e 1/8Mn + 1/2H2O 1/8Mn + OH 1/8MnO4 + 1/2H2O + 7/8e H+ + OH H2O 1/8MnO42 + H+ + 3/4e 1/8Mn + 1/2H2O 1/8Mn + OH 1/8MnO42 + 1/2H2O + 3/4e H+ + OH H2O 1/4MnO4 + H+ + 3/4e 1/4MnO2 + 1/2H2O 1/4MnO2 + OH 1/4MnO4 + 1/2H2O + 3/4e H+ + OH H2O 1/4MnO42 + H+ + 1/2e 1/4MnO2 + 1/2H2O 1/4MnO2 + OH 1/4MnO42 + 1/2H2O + 1/2e H+ + OH H2O GR/kJ 0.00000 79.885 79.885 118.564 38.679 79.885 2.28 77.61 79.88 62.7 17.2 79.9 56.0 23.9 79.9 123.0 43.2 79.9 109.7 29.8 79.9 /V 0.00000 0.82794 0.82794 1.22881 0.40088 0.82794 0.0236 0.8043 0.8279 0.742 0.204 0.946 0.774 0.330 1.10 1.700 0.596 1.10 2.273 0.618 1.66

mentioned to him, as demonstrated in this article, that the standard cell potential of a reaction is not a state function. A problem in a textbook written by Masterton and Hurley (Masterton, W. L.; Hurley, C. N. Chemistry Principles and Reactions, 5th ed.; Brooks/ Cole: New York, 2004; p 504, problem 76) involves three ways to obtain the reaction 2Tl(s) + Tl3(aq) 3Tl(aq). The three unique sets of half-reactions give = 1.62, 1.08, and 0.54 V for n = 2, 3, and 6 electrons, respectively. All three reactions have the result that GR = 313 kJ. 3. The N-containing species in this list are stable in their standard states in acidic solutions; see the acid solution diagram on p 104 of ref 6. 4. The Mn-containing species in this list are stable in their standard states in both acidic and basic solutions; see 1 M H+ and 1 M OH diagrams on p 241 of ref 6.

3.

Literature Cited
1. (a) Moore, J. W.; Stanitski, C. L.; Jurs, P. C. Chemistry the Molecular Science; Brooks/Cole: New York, 2002. (b) Olmsted, J., III; Williams, G. M. Chemistry, 3rd ed.; Wiley: New York, 2002. (c) Zumdahl, S. S.; Zumdahl, S. A. Chemical Principles, 5th ed.; Houghton Mifflin: Boston, MA, 2000. (d) Kotz, J. C.; Treichel, P., Jr. Chemistry and Chemical Reactivity, 4th ed.; Saunders: New York, 1999. 2. (a) Atkins, P.; de Paula, J. Physical Chemistry, 7th ed.; Freeman: 4.

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New York, 2002. (b) Raff, L. M. Principles of Physical Chemistry; Prentice-Hall: Upper Saddle River, NJ, 2001. (c) Silbey, R. J.; Alberty, R. A. Physical Chemistry, 3rd ed.; Wiley: New York, 2001. (d) Barrow, G. M. Physical Chemistry, 6th ed.; McGraw-Hill: New York, 1996. (e) Daniels, F.; Alberty, R. A. Physical Chemistry, 3rd ed.; Wiley: New York, 1966. (f ) Glasstone, S. Elements of Physical Chemistry, 2nd ed.; Van Nostrand: New York, 1960. (a) DeVoe, H. Thermodynamics and Chemistry; Prentice-Hall: Upper Saddle River, NJ, 2001. (b) Sandler, S. I. Chemical and Engineering Thermodynamics, 3rd ed.; John Wiley & Sons: New York, 1999. (c) Pitzer, K. S. Thermodynamics, 3rd ed.; McGraw-Hill: New York, 1995. (d) Klotz, I. M.; Rosenberg, R. M. Chemical Thermodynamics, Basic Theory and Methods, 4th ed.; Benjamin/Cummings: Menlo Park, CA, 1986. (e) Glasstone, S. Thermodynamics for Chemists; D. Van Nostrand: New York, 1947. (f ) Lewis, G. N.; Randall, M. Thermodynamics, 2nd ed.; revised by Pitzer, K. S.; Brewer, L.; McGrawHill: New York, 1961. Wagman, D. D.; Evans, W. H.; Parker, V.; Schumm, R. H.; Harlow, I.; Bailey, S. M.; Churney, K. L.; Nuttall, R. L. J. Phy. Chem. Ref. Data 1982, 11, Supplement No. 2. Fishtik, I.; Berka, L. H. J. Chem. Educ., submitted for publication. Latimer, W. M. Oxidation Potentials, 2nd ed.; Prentice-Hall: New York, 1952.

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