Emf, Free Energy, pH, and Graphical Representation

Final Research Paper

CHEM 399 2 credit hours

April Kay Bobbie

Spring 2002

Emf and Free Energy

The following paper was presented at the South Dakota Academy of Science meeting in April, 2002: Sets of Half-Reactions Which Yield Different Emf for an Overall Reaction, But Equivalent Standard Gibbs Free Energy and Equilibrium Constants. INTRODUCTION Standard electrode potentials (redox potentials, oxidation-reduction potentials) provide information about the behavior of chemical reactions. This project investigated sets of half-reactions that produce the same cell reaction, different cell emf values (Ecell), but similar values of nEcell, standard Gibbs free energy (G) and equilibrium constants (Keq). For mercury, chromium, iron, sulfur, chlorine, copper, and indium, sets of half-reactions were determined and cell emf values, nEcell, equilibrium constants, and standard Gibbs free energy were calculated. E values for half-reactions are tabulated in several sources. (Atkins 1998, Bard 1985, Latimer 1952) Where the NBS Tables include Gf for the species in a half-reaction, E = -G/nF, and this was used as the preferred value. (Wagman 1982) Where the NBS Tables were incomplete, the source of the E used is referenced. METHODS OF CALCULATION For all calculations: F = 96485.3 C/mol R = 8.31451 J/mol*K T = 298.15 K G = -nFE Keq = e nFE/RT RESULTS Mercury: (Wagman 1982) 2 Hg = Hg22+ + 2 e2 Hg2+ + 2 e- = Hg22+ 2 Hg + 2 Hg2+ = 2 Hg22+ Hg + Hg2+ = Hg22+ G = -11.1 kJ mol-1 E = -0.7960 V E = +0.9110 V Ecell = +0.115 V n Ecell = +0.115 V Keq = 87.7

(n=1)

2 Hg = Hg22+ + 2 eHg2+ + 2 e- = Hg Hg + Hg2+ = Hg22+ G = -11.1 kJ mol-1 Chromium: (Atkins 1998) 3 (Cr2+ + 2 e- = Cr) 2 (Cr = Cr3+ + 3 e- ) 3 Cr2+ = 2 Cr3+ + Cr

(n=2)

E = -0.7960 V E = +0.8535 V Ecell = +0.0575 V n Ecell = +0.115 V Keq = 87.7

(n=6) G = 98.4 kJ mol-1 K 100 kJ mol-1 Cr3+ + 3 e- = Cr 3 (Cr2+ = Cr3+ + e-) 3 Cr2+ = 2 Cr3+ + Cr

E = -0.91 V E = +0.74 V Ecell = -0.17 V n Ecell = -1.02 V Keq = 5.74x10-18 E = -0.74 V E = +0.41 V Ecell = -0.33 V n Ecell = -0.99 V Keq = 1.84x10-17

(n=3)

G = 95.5 kJ mol-1 K 100 kJ mol-1 Iron: (Wagman 1982) 3 (Fe2+ + 2 e- = Fe) 2 (Fe = Fe3+ + 3 e- ) 3 Fe2+ = 2Fe3+ + Fe (n=6) G = 208 kJ mol-1 Fe3+ + 3 e- = Fe 3 (Fe2+ = Fe3+ + e-) 3 Fe2+ = 2Fe3+ + Fe G = 208 kJ mol-1

E = -0.409 V E = +0.049 V Ecell = -0.360 V n Ecell = -2.16 V Keq = 3.23x10-37 E = +0.049 V E = -0.769 V Ecell = -0.72 V n Ecell = -2.16 V Keq = 3.23x10-37

(n=3)

Sulfur: (Wagman 1982) 2 (S22- + 2 e- + 2 H+ = 2 HS-) 3 HS- = 3 H+ + 4 e- + S322 S22- + 4 H+ = HS- + 3 H+ + S322 S22- + H+ = HS- + S32(n=4) G = -73.3 kJ mol-1 S22- + 2 e- + 2 H+ = 2 HS3 S22- = 2 e- + 2 S324 S22- + 2 H+ = 2 HS- + 2 S32(n=1) 2 S22- + H+ = HS- + S32G = -73.3 kJ mol-1

E = +0.287 V E = -0.097 V Ecell = +0.190 V n Ecell = +0.760 V Keq = 6.91x1012 E = +0.287 V E = +0.473 V Ecell = +0.760 V n Ecell = +0.760 V Keq = 6.91x1012

Chlorine: (Wagman 1982) in basic solution ClO3- + H2O + 2 e- = ClO2- + 2 OH2 (ClO2- = ClO2(g) + e-) ClO3- + ClO2- + H2O = 2 ClO2(g) + 2 OH(n=2) G = 154.4 kJ mol-1 ClO3- + H2O + e- = ClO2(g) + 2 OH ClO2- = ClO2(g) + eClO3- + ClO2- + H2O = 2 ClO2(g) + 2 OH(n=1) G = 154.5 kJ mol-1

E = +0.271 V E = -1.071 V Ecell = -0.800 V n Ecell = -1.600 V Keq = 1.07x1027 E = -0.530 V E = -1.071 V Ecell = -1.601 V n Ecell = -1.601 V Keq = 1.12x1027

Examples where the number of electrons is equal: Copper: (Wagman 1982) 2 (Cu+ + e- = Cu) E = +0.520 V 2+ E = -0.340 V Cu = Cu + 2 e 2 Cu+ = Cu2+ + Cu Ecell = +0.180 V Cu2+ + 2 e- = Cu 2 (Cu+ = Cu2+ + e-) 2 Cu+ = Cu2+ + Cu n=2 G = -34.7 kJ mol-1 Indium: (Wagman 1982) 2 (In2+ + e- = In+) In+ = In3+ + 2 e2 In2+ = In3+ + In+ In3+ + 2 e- = In+ 2 (In2+ = In3+ + e-) 2 In2+ = In3+ + In+ n=2 G = -8.68 kJ mol-1 E = +0.340 V E = -0.160 V Ecell = +0.180 V n Ecell = +0.360 V Keq = 1.22x106 E = -0.400 V E = +0.445 V Ecell = +0.045 V E = -0.445 V E = +0.490 V Ecell = +0.045 V n Ecell = +0.090 V Keq = 33.1

DISCUSSION For mercury, chromium, iron, sulfur, chlorine, copper, and indium, the calculated G and Keq are equal for both sets of half-reactions. The cell reaction was the same for each set of half-reactions. For all of the ions, except for copper and indium, the number of electrons transferred in each set of half-reactions was different. Regardless of this difference, the standard Gibbs free energy, equilibrium constant, and nEcell were equivalent. Use of E data from sources other than the NBS Tables tended to lead to modest round-off error. CONCLUSION For each set of the two sets of half-reactions, the standard Gibbs free energy and equilibrium constant calculated were found to be equivalent. The same cell reaction is produced by both sets of half-reactions. Each set differs in the number of electrons transferred and the cell emf value, but agrees in their product, nEcell. Using 5

E values based on the NBS Tables tended to give the most consistent results. A paper addressing this same interesting quality of E values was published by Cooke and Willis, California State University, in the Journal of Chemical Eduction. Two general chemistry students discovered the two different ways of calculating the same value for standard Gibbs free energy with a copper half-reaction. They realized that both of their answers were correct and recommend that textbooks describe chemical reactions in terms of G rather than simply E (Cooke and Willis).

Latimer Diagrams
Wendell Latimer, a chemical pioneer in the application of thermodynamics to inorganic solution chemistry, introduced this simple diagram in which the value of the standard potential (in volts) is displayed above or below a horizontal line connecting the species of the element in different oxidation states. The Latimer diagram shows the relationships between various species of an element. A species has a thermodynamic tendency to disproportionate into its neighbors if the potential on the right of the species is higher than the potential on the left (Shriver 300). The equation G = -nFE allows calculation of standard Gibbs free energy from the standard potential given in the diagram. Latimer diagrams summarize a large amount of information in a compact and clear style. All diagrams are from data for acidic solution, except for chlorine.

Mercury: (Wagman 1982) 0.9110 0.7960 Hg2+---------------Hg22+---------------Hg |_________________________| 0.8535

Chromium: (Atkins 1998) -0.41 -0.91 Cr3+---------------Cr2+---------------Cr |________________________| -0.74 Iron: (Wagman 1982) 0.769 -0.409 Fe3+---------------Fe2+---------------Fe |________________________| -0.049 Sulfur: (Wagman 1982) -0.287 0.473 HS----------------S22----------------S32|_______________________| -0.097 Chlorine: (Wagman 1982) in basic solution -0.530 1.071 ClO3---------------ClO2(g)--------------ClO2|__________________________| 0.271 Copper: (Wagman 1982) 0.160 0.520 Cu2+---------------Cu+---------------Cu |________________________| 0.340

Indium: (Wagman 1982) -0.490 -0.400 In3+---------------In2+---------------In+ |_______________________| -0.445

Frost Diagrams
Arthur A. Frost developed a new type of diagram which plots the standard free energy versus the oxidation state for an element (Frost 2680). The slope of the line joining any two points in a Frost diagram is equal to the standard potential of the couple formed by the two species. The steeper the slope, the higher the standard reduction potential for the couple. In the Frost diagram, the lowest lying species corresponds to the most stable oxidation state of the element. Frost diagrams are most useful for the quick qualitative impression they provide for trends in the chemical properties of elements (Shriver 302). The oxidizing agent in the couple with the more positive slope may undergo reduction; the reducing agent in the couple with the less positive slope may undergo oxidation. If an ion lies above the line connecting the two adjacent species, it is unstable. Any two species may comproportionate into an intermediate species which lies below the line joining the two species. For the following Frost diagrams, the standard free energy was converted from kJ/mol to eV, using this relation: 1eV=96.485 kJ/mol. All diagrams are from data for acidic solution, except for chlorine.

element Hg Hg22+ Hg2+ Cr Cr2+ Cr3+ Fe Fe2+ Fe3+ HSS22S32ClO2ClO2(g) ClO3Cu Cu+ Cu2+ In+ In2+ In3+ OHH2O

standard free energy (kJ/mol) standard free energy (eV) oxidation state calculated delta G 0 0.0000 0 0.0000 -153.52 -1.5911 1 -0.8519 -164.4 -1.7039 2 -1.7039 0 0.0000 0 0.0000 -175.6 -1.8200 2 -1.4800 -214.197 -2.2200 3 -2.2200 0 0.0000 0 0.0000 -78.9 -0.8177 2 -0.0244 -4.7 -0.0487 3 -0.0487 12.08 0.1252 -2 0.1252 79.5 0.8240 -1 0.5927 73.7 0.7638 -0.67 0.7638 168.438 1.7457 3 1.7457 271.738 2.8164 4 2.0163 220.647 2.2869 5 2.2869 0 0.0000 0 0.0000 49.98 0.5180 1 0.3394 65.49 0.6788 2 0.6788 -12.1 -0.1254 1 -0.1254 -50.7 -0.5255 2 -0.5706 -98 -1.0157 3 -1.0157 -157.244 -1.6297 -237.129 -2.4577

Mercury
standard free energy (eV) 0 -0.5 -1 -1.5 -2 0 1 oxidation state 2 (Hg2)2+ Hg2+ Hg

Frost Diagram

Chromium
standard free energy (eV) 0 -0.5 -1 -1.5 -2 -2.5 0 1 2 oxidation state 3 Cr2+ Cr3+ Cr

Frost Diagram

Iron
standard free energy (eV) 0 -0.2 -0.4 -0.6 -0.8 -1 0 1 2 oxidation state 3 Fe2+ Fe

Frost Diagram
Fe3+

Sulfur
Frost Diagram
standard free energy (eV) 1 0.8 0.6 0.4 0.2 0 -3 -2 -1 oxidation state 0 HS(S2)2(S3)2-

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Chlorine
standard free energy (eV)

Frost Diagram (base)

3 2.8 2.6 2.4 2.2 2 1.8 1.6 2 ClO2(g) ClO3ClO23 4 oxidation state 5 6

Copper
Frost Diagram
standard free energy (eV) 0.8 0.6 0.4 0.2 0 Cu 0 1 oxidation state 2 Cu+ Cu2+

Indium
Frost Diagram
standard free energy (eV) 0 In+ -0.2 -0.4 -0.6 -0.8 -1 -1.2 1

In2+ In3+ 2 oxidation state 3

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Pourbaix Diagram
A Pourbaix diagram is a plot of potential versus pH. The regions in a Pourbaix diagram indicate the conditions of pH and potential under which each species is thermodynamically stable. The Pourbaix diagram of iron was created to include iron species found in natural water, at natural concentrations and pH levels. The normal pH range found in natural waters is from 4-9. The Nernst equation, E=E-(0.05916 v/n)logQ, was used to calculate the potential, E. Two sloping lines for the boundaries of the stability field of water have also been included. Any species with a more positive potential than the upper line will oxidize water to O2, just as any with potentials more negative than the lower line will reduce water to H2.

pH 0 1 2 3 3 4 5 6 7 8 9 9 10 11 12 13 14

E horizontal 0.769 0.769 0.769 0.769 2

E - diagonal E - diagonal E O2/H2O 1.3138 1.25464 1.19548 1.13632 0.769 1.13632 0.59152 1.07716 0.41404 1.018 0.23656 0.95884 0.05908 0.89968 -0.1184 0.84052 -0.29588 -2 0.78136 -0.25127 0.78136 -0.31043 0.7222 -0.36959 0.66304 -0.42875 0.60388 -0.48791 0.54472 -0.54707 0.48556

E H2/H2O 0 -0.05916 -0.11832 -0.17748 -0.17748 -0.23664 -0.2958 -0.35496 -0.41412 -0.47328 -0.53244 -0.53244 -0.5916 -0.65076 -0.70992 -0.76908 -0.82824

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Pourbaix Diagram
2 1 E (v) 0
H2O/H2 Fe(OH)2(s)

Iron

Fe3+ Fe2+

O2/H2O Fe(OH)3(s)

-1 -2 0 2 4 6 pH 8 10 12 14

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References:

Atkins, Peter W. Physical Chemistry 6th Ed. Freeman, New York. 1998. Bard, Allen J., Roger Parsons, and Joseph Jordan. Standard Potentials in Aqueous Solution. Marcel Dekker, New York. 1985. Cooke, Ron C. and Grover C. Willis. Which E Is It? Chemical Principles Revisited. J. of Chem. Ed. 1996, 73, 450. Frost, Arthur A. Oxidation Potential-Free Energy Diagrams. J. Am. Chem. Soc. 1951, 73, 2680. Gray, Harry B., and Gilbert P. Haight, Jr. Basic Principles of Chemistry. W.A. Benjamin, Inc., N.Y., 1967. Latimer, Wendell M. Oxidation Potentials 2nd Ed. Prentice-Hall, Englewood Cliffs, N.J. 1952. Phillips, C.S.G., and R.J.P. Williams. Inorganic Chemistry I Principles and Non-metals. Oxford University Press. 1965. Phillips, C.S.G., and R.J.P. Williams. Inorganic Chemistry II Metals. Oxford University Press. 1966. Pourbaix, Marcel. Atlas of Electrochemical Equilibria in Aqueous Solutions. National Association of Corrosion Engineers, TX, 1974. Shriver, D.F., Peter Atkins, and Cooper H. Langford. , D.F., Peter Atkins, and Cooper H. Langford. Inorganic Chemistry 2nd Ed. W.H. Freeman and Company, N.Y., 1994. Viste, Arlen. Chemistry 341 Lecture Notes. Fall, 1976. Wagman, Donald D., W.H. Evans, V.B. Parker, R.H. Schumm, Iva Halow, S.M. Bailey, K.L. Churney, and R.L. Nuttall. The NBS Tables of Chemical Thermodynamic Properties. Journal of Physical and Chemical Reference Data. 11: Supplement 2. American Institute of Physics, Inc., N.Y., 1982.

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