CHAPTER

Electroanalytical Methods

CONTENTS Detection Limits for Various Electrochemical Techniques Values of (2.3026 RT/F) (in mV) at Different Temperatures Potential of Zero Charge (Eecm) for Various Electrode Materials in Aqueous Solutions at Room Temperature Variation of Reference Electrode Potentials with Temperature pH Values of Standard Solutions Used in the Calibration of Glass Electrodes Temperature vs. pH Correlation of Standard Solutions Used for the Calibration of Electrodes Solid Membrane Electrodes Liquid Membrane Electrodes Standard Reduction Electrode Potentials for Inorganic Systems in Aqueous Solutions at 25C Standard Reduction Electrode Potentials for Inorganic Systems in Nonaqueous Solutions at 25C Redox Potentials for Some Biological Half Reactions Standard emf Values for the Cell H2/HCl/AgCl, Ag in Various Aqueous Solutions of Organic Solvents at Various Temperatures Temperature Dependence of the Standard Potential of the Silver Chloride Electrode Standard Electrode Potentials of Electrodes of the First Kind Standard Electrode Potentials of Electrodes of the Second Kind Polarographic Half-Wave Potentials (E1/2) of Inorganic Cations Polarographic E1/2 Ranges (in V vs. SCE) for the Reduction of Benzene Derivatives Vapor Pressure of Mercury Organic Functional Group Analysis of Nonpolarographic Active Groups Coulometric Titrations

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DETECTION LIMITS FOR VARIOUS ELECTROCHEMICAL TECHNIQUES The following table provides guidance in selection of electrochemical techniques by providing the relative sensitivities of various methods.1 The limit of detection of lead, dened as the minimum detectable quantity (on a mole basis), is used as the basis of comparison.

REFERENCES
1. Batley, G.E., Trace Element Speciation: Analytical Methods and Problems, CRC Press, Boca Raton, FL, 1989.
Detection Limits for Various Electrochemical Techniques Electrochemical Technique DC polarography (DME) DC polarography (SMDE) DP polarography (SMDE) DP anodic stripping voltammetry (HMDE) SW anodic stripping voltammetry (HMDE) DC anodic stripping voltammetry (TMFE) DP anodic stripping voltammetry (TMFE) SW anodic stripping voltammetry (TMFE) Limit of Detection for Lead (Mole) 2 106 1 107 1 107 2 1 5 1 5 1010 1010 1011 1011 1012

Note: DC = direct current; DP = differential pulse; SW = square wave; DME = dropping mercury electrode; SMDE = static mercury drop electrode; HMDE = hanging mercury drop electrode; TMFE = thin mercury lm electrode.

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VALUES OF (2.3026 RT/F) (IN mV) AT DIFFERENT TEMPERATURES The following table gives the variation of (2.3026 RT/F) (mV) with temperature (C).1 Electronic pH meters are voltmeters with scale divisions that are equivalent to the value of 2.3026 RT/F (in mV) per pH unit. Generally, a reproducibility of 0.005 pH unit is feasible when the pH meter is reproducible to 0.2 mV.

REFERENCES
1. Shugar, G.J. and Dean, J.A., The Chemists Ready Reference Handbook, McGraw-Hill Book Company, New York, 1990.
Values of (2.3026 RT/F) (in mV) at Different Temperatures T (C) 0 5 10 15 18 20 25 30 35 38 40 45 2.3026 RT/F (mV) 54.199 55.191 56.183 57.175 57.770 58.167 59.159 60.152 61.144 61.739 62.136 63.128 T (C) 50 55 60 65 70 75 80 85 90 95 100 2.3026 RT/F (mV) 64.120 65.112 66.104 67.096 68.088 69.080 70.073 71.065 72.057 73.049 74.041

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POTENTIAL OF ZERO CHARGE (Eecm) FOR VARIOUS ELECTRODE MATERIALS IN AQUEOUS SOLUTIONS AT ROOM TEMPERATURE The table below lists the potential of zero charge (Eecm) values (in volts) for various electrode materials in aqueous solutions at room temperature (25C).1 All values are with respect to the normal hydrogen electrode.

REFERENCES
1. Parsons, R., Handbook of Electrochemical Constants, Butterworths, London, 1959.
Potential of Zero Charge (Eecm) for Various Electrode Materials in Aqueous Solutions at Room Temperature Electrode Ag Cd Ga Hg Ni Pb Platinized Pt Smooth Pt Oxidized Pt Te Tl TlHg (satd) Zn Graphite Activated charcoal
a

Eecm (V) +0.05 0.90 0.60 0.192 0.06 0.69 +0.11 +0.27 (+0.4)(0.1) +0.61 0.80 0.65 0.63 0.07 (0.0)(+0.2)

Solution Composition 0.1 N KNO3 0.0001 N KCl 1 N KCl + 0.1 N HCl Capillary inactive saltsa 0.001 N HCl 0.001 N KCl N Na2SO4 + 0.1 N H2SO4 N Na2SO4 + 0.1 N H2SO4 N Na2SO4 + 0.1 N H2SO4 1 N Na2SO4 0.001 N KCl 1 N KCl 1 N Na2SO4 0.05 N KCl N Na2SO4 + 0.1 N H2SO4

1 1 1

Any salt that is nonreactive with the capillary can be used.

satd = saturated.

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VARIATION OF REFERENCE ELECTRODE POTENTIALS WITH TEMPERATURE The following table lists the potentials of various (0.1 M KCl calomel, saturated KCl calomel, and 1.0 M KCl Ag/AgCl) electrodes at different temperatures (in C).13 The values include the liquidjunction potential.

REFERENCES
1. Bates, R.G. et al., pH standards of high acidity and high alkalinity and the practical scale of pH, J. Res. Natl. Bur. Stand., 45, 418, 1950. 2. Bates, R.G. and Bower, V.E., Standard potential of the silver silver-chloride electrode from 0-degrees C to 95-degrees C and the thermodynamic properties of dilute hydrochloric acid solutions, J. Res. Natl. Bur. Stand., 53, 283, 1954. 3. Shugar, G.J. and Dean, J.A., The Chemists Ready Reference Handbook, McGraw-Hill Book Company, New York, 1990.
Variation of Reference Electrode Potentials with Temperature Temperature (C) 0 5 10 15 20 25 30 35 38 40 45 50 55 60 70 80 90 0.1 M KCl Calomel 0.3367 0.3362 0.3361 0.3358 0.3356 0.3354 0.3351 0.3350 0.3345 0.3315 0.3248 Saturated KCl Calomel 0.25918 0.25387 0.2511 0.24775 0.24453 0.24118 0.2376 0.2355 0.23449 0.22737 0.2235 0.2083 1.0 M KCl Ag/AgCl 0.23655 0.23413 0.23142 0.22857 0.22557 0.22234 0.21904 0.21565 0.21208 0.20835 0.20449 0.20056 0.19649 0.18782 0.1787 0.1695

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pH VALUES OF STANDARD SOLUTIONS USED IN THE CALIBRATION OF GLASS ELECTRODES The following table gives the pH values of operational standard solutions recommended for the calibration of glass electrodes at 25 and 37C.1

REFERENCES
1. Hibbert, D.B. and James, A.M., Dictionary of Electrochemistry, 2nd ed., John Wiley & Sons, New York, 1984.

pH Values of Standard Solutions Used in the Calibration of Glass Electrodes pH at Standard Solution 0.1 mol/kg potassium tetroxalate 0.1 mol/dm3 hydrochloric acid + 0.09 mol/dm3 potassium chloride 0.05 mol/kg potassium hydrogen phthalate 0.10 mol/dm3 acetic acid + 0.10 mol/dm3 sodium acetate 0.10 mol/dm3 acetic acid + 0.01 mol/dm3 sodium acetate 0.02 mol/kg pipezazine phosphate 0.025 mol/kg disodium hydrogen phosphate + 0.025 mol/kg potassium dihydrogen phosphate 0.05 mol/kg tris(hydroxymethyl)methane hydrochloride + 0.01667 mol/kg tris(hydroxymethyl)methane 0.05 mol/kg disodium tetraborate (borax) 0.025 mol/kg sodium bicarbonate + 0.025 mol/kg sodium carbonate Saturated calcium hydroxide 25C 1.48 2.07 4.005 4.644 4.713 6.26 6.857 7.648 9.182 9.995 12.43 37C 1.49 2.08 4.022 4.647 4.722 6.14 6.828 7.332 9.074 9.889 12.05

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TEMPERATURE VS. pH CORRELATION OF STANDARD SOLUTIONS USED FOR THE CALIBRATION OF ELECTRODES The following table gives the temperature vs. pH correlation of common standard solutions that are used for the calibration of electrodes.13 Such solutions should be stable and easily prepared solutions whose solutes do not require further purication because of factors such as their hygroscopic nature. It is worth noting that the buffering capacity of these solutions is of little interest.

REFERENCES
1. Hibbert, D.B. and James, A.M., Dictionary of Electrochemistry, 2nd ed., John Wiley & Sons, New York, 1984. 2. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970. 3. Robinson, R.A. and Stokes, R.H., Electrolytic Solutions, Butterworths, London, 1959.
Temperature vs. pH Correlation of Standard Solutions Used for the Calibration of Electrodes pH of 0.05 M Potassium Hydrogen Phthalate 4.012 4.005 4.001 4.000 4.001 4.005 4.011 4.019 4.022 4.030 4.043 4.059 4.077 4.097 4.12 4.16 4.20 4.23 0.025 M K2HPO4 + 0.02 M NaH2PO4 6.893 6.950 6.922 6.896 6.878 6.860 6.849 6.842 6.838 6.837 6.834 6.833 6.836 6.840 6.85 6.86 6.88 6.89

Temperature C 0 5 10 15 20 25 30 35 37 40 45 50 55 60 70 80 90 95
a

0.05 M Potassium Tetroxalate 1.671 1.671 1.669 1.674 1.676 1.681 1.685 1.693 1.697 1.704 1.712 1.719 1.726 1.74 1.77 1.80 1.81

Potassium Hydrogen Tartratea 3.555 3.547 3.545 3.543 3.545 3.549 3.556 3.565 3.58 3.61 3.65 3.68

0.01 M Potassium Tartrate 3.710 3.690 3.671 3.655 3.647 3.637 3.633 3.629 3.630 3.634 3.640 3.646 3.654

0.01 M Na2B4O7 9.463 9.389 9.328 9.273 9.223 9.177 9.135 9.100 9.074 9.066 9.037 9.012 8.987 8.961 8.93 8.89 8.85 8.83

Ca(OH)2a 13.428 13.208 13.004 12.809 12.629 12.454 12.296 12.135 12.05 11.985 11.841 11.704 11.575 11.454

Saturated at 25C.

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SOLID MEMBRANE ELECTRODES The following table lists the most commonly used solid membrane electrodes, their applications, and major interferences.1 Often the membrane is composed of a salt (listed rst) and a matrix (listed second). Thus, a AgClAg2S electrode involves the nely divided AgCl in a Ag2S matrix. The salt should be more soluble than the matrix, but insoluble enough so that its equilibrium solubility gives a lower anion (Cl) activity than that of the sample solution.

REFERENCES
1. Fritz, J.S. and Schenk, G.H., Quantitative Analytical Chemistry, 5th ed., Prentice Hall, Englewood Cliffs, NJ, 1987.
Solid Membrane Electrodes Membrane LaF3 Ag2S AgClAg2S AgBrAg2S AgIAg2S AgSCNAg2S CdSAg2S CuSAg2S PbSAg2S Ion Measured F S2, Ag+ Cl Br I SCN Cd+2 Cu+2 Pb+2

Major Interferences OH Hg+2 Br, I, S2, CN, NH3 I, S2, CN, NH3 S2, CN Br, I, S2, CN, NH3 Ag+, Hg+2, Cu+2 Ag+, Hg+2 Ag+, Hg+2, Cu+2

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LIQUID MEMBRANE ELECTRODES The following table gives the basic information on several liquid membrane electrodes.13 The selectivity of a membrane electrode for a given ion is determined primarily by the liquid ion exchanger used. Thus, as the preference of the ion exchanger for a specic ion increases, its selectivity increases. The selectivity is also affected by the organic solvent in which the liquid exchanger is dissolved. In this table, R- may be any organic radical or group.

REFERENCES
1. Durst, R.A., Ed., Ion-Selective Electrodes, National Bureau of Standards Special Publication 314, Washington, D.C., 1969, p. 70. 2. Frant, M.S. and Ross, J.W., Potassium ion specic electrode with high selectivity for potassium over sodium, Science, 167, 987, 1970. 3. Fritz, J.S. and Schenk, G.H., Quantitative Analytical Chemistry, 5th ed., Prentice Hall, Englewood Cliffs, NJ, 1987.
Liquid Membrane Electrodes Ion Measured K+ Ca+2 Exchange Site Valinomycin (RO)2POO Selectivity Coefcients Na+, 0.0001 Na+, 0.0016 Mg+2, Ba+2, 0.01 Sr+2, 0.02 Zn+2, 3.2 H+, 107 Na+, 0.01 Sr+2, 0.54 Ba+2, 0.94 Na+, K+, 0.0005 Mg+2, 0.001 Ca+2, 0.002 Ni+2, 0.01 Zn+2, 0.03 F, 0.0009 SO42, 0.0006 PO43, 0.0003 Cl, CH3COO, 0.006 HCO3, CN, 0.02 NO2, 0.06 Br, 0.9

Ca+2 and Mg+2

(RO)2POO

Cu+2

RSCH2COO

NO3

+2

N Ni N

ClO4

+2

N Fe N

Cl, SO42, 0.0002 Br, 0.0006 NO3, 0.0015 I, 0.012 OH, 1.0

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STANDARD REDUCTION ELECTRODE POTENTIALS FOR INORGANIC SYSTEMS IN AQUEOUS SOLUTIONS AT 25C A summary of the potentials, E, in volts (at 25C), of the most useful reduction half reactions is presented below.15 The reactions are arranged in order of decreasing oxidation strength. When comparing two half reactions, the oxidizing agent of the half reaction with the higher (more positive) E will react with the reducing agent of the half reaction with its lower (less positive) E. Thus, Br2 (l) (E = 1.065 V) will oxidize H2O2 to O2(g) (E = 0.682 V), but O2(g) cannot oxidize Br . No predictions can be made on the rate of reaction. If two or more reactions between two substances are possible, the reaction that involves half reactions that are farthest apart in the table will be most thermodynamically favorable. For instance, in the case of O2(g) reacting with Cu, O2(g) + 4H+ + 4e 2H2O (E = 1.229 V) O2(g) + 2H+ + 2e H2O2 (E = 0.682 V) Cu+2 + 2e Cu (E = 0.337 V) (6.1) (6.2) (6.3)

The reaction between Equation 6.1 and Equation 6.3 will be most favorable. However, if Equation 6.3 is replaced with Equation 6.4, Cl2(g) + 2e 2Cl (E = 1.36 V) the reactions between Equation 6.2 and Equation 6.4 will take place rst. (6.4)

REFERENCES
1. Bard, A.J. and Faulkner, L.R., Electrochemical Methods, 2nd ed., John Wiley & Sons, New York, 2001. 2. Day, R.A. and Underwood, A.L., Quantitative Analysis, 6th ed., Prentice Hall, Englewood Cliffs, NJ, 1991. 3. Dean, J.A., Ed., Langes Handbook of Chemistry, 14th ed., McGraw-Hill Book Co., New York, 1999. 4. Ebbing, D.D., General Chemistry, 6th ed., Houghton Mifin Co., Boston, 1999. 5. Shugar, G.J. and Dean, J.A., The Chemists Ready Reference Handbook, McGraw-Hill Book Co., New York, 1990.

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Standard Reduction Electrode Potentials for Inorganic Systems in Aqueous Solutions at 25C Half Reaction F2(g) + 2H + 2e O3 + 2H+ + 2e S2O82 + 2e Ag2+ + e H2O2 + 2H+ + 2e MnO4 + 4H+ + 3e Ce(IV) + e H5IO6 + H+ + 2e Bi2O4 + 4H+ + 2e BrO3 + 6H+ + 5e MnO4 + 8H+ + 5e PbO2 + 4H+ + 2e Cl2 + 2e Cr2O72 + 14H+ + 6e MnO2(s) + 4H+ + 2e O2(g) + 4H+ + 4e IO3 + 6H+ + 5e Br2(liq) + 2e ICl2 + e VO2+ + 2H+ + e HNO2 + H+ + e NO3 + 3H+ + 2e 2Hg2+ + 2e Cu2+ + I + e Ag+ + e Hg22+ + 2e Fe3+ + e O2(g) + 2H+ + 2e 2HgCl2 + 2e Hg2SO4(s) + 2e H3AsO4 + 2H+ + 2e Sb2O5 + 6H+ + 4e I3 + 2e Cu+ + e VO2+ + 2H+ + e Fe(CN)63 + e Cu2+ + 2e UO22+ + 4H+ + 2e BiO+ + 2H+ + 3e Hg2Cl2(s) + 2e AgCl(s) + e SbO+ + 2H+ + 3e CuCl32 + e SO42 + 4H+ + 2e Sn4+ + 2e S + 2H+ + 2e TiO2+ + 2H+ + e S4O62 + 2e AgBr(s) + e 2H+ + 2e Pb2+ + 2e Sn2+ + 2e AgI(s) + e Mo3+ + 3e N2 + 5H+ + 4e Ni2+ + 2e V3+ + e
+

E, V 3.06 2.07 2.01 2.00 1.77 1.70 1.61 1.6 1.59 1.52 1.51 1.455 1.36 1.33 1.23 1.229 1.20 1.065 1.06 1.00 1.00 0.94 0.92 0.86 0.799 0.79 0.771 0.682 0.63 0.615 0.581 0.559 0.545 0.52 0.361 0.36 0.337 0.334 0.32 0.2676 0.2223 0.212 0.178 0.17 0.154 0.141 0.10 0.08 0.071 0.00 0.126 0.136 0.152 0.2 0.23 0.246 0.255

2HF O 2 + H 2O 2SO42 Ag+ 2H2O MnO2(s) + 2H2O Ce(III) (in 1 M HClO4) IO3 + 3H2O 2BiO+ + 2H2O 1/2Br2 + 3H2O Mn2+ + 4H2O Pb2+ + 2H2O 2Cl 2Cr3+ + 7H2O Mn2+ + 2H2O 2H2O 1/2I2 + 3H2O 2Br 1/2I2 + 2Cl VO2+ + H2O NO(g) + H2O HNO2 + H2O Hg22+ CuI Ag 2Hg Fe2+ H2O2 Hg2Cl2(s) + 2Cl 2Hg + SO42 HAsO2 + 2H2O 2SbO+ + 3H2O 3I Cu V3+ + H2O Fe(CN)64 Cu U4+ + 2H2O Bi + H2O 2Hg + 2Cl Ag + Cl Sb + H2O Cu + 3Cl SO2(aq) + 2H2O Sn2+ H2S(g) Ti3+ + H2O 2S2O32 Ag + Br H2 Pb Sn Ag + I Mo H2NNH3+ Ni V2+

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Standard Reduction Electrode Potentials for Inorganic Systems in Aqueous Solutions at 25C (continued) Half Reaction Co + 2e Ag(CN)2 + e Cd2+ + 2e Cr3+ + e Fe2+ + 2e 2CO2 + 2H+ + 2e H3PO3 + 2H+ + 2e U4+ + e Zn2+ + 2e Cr2+ + 2e Mn2+ + 2e Zr4+ + 4e Ti3+ + 3e Al3+ + 3e Th4+ + 4e Mg2+ + 2e La3+ + 3e Na+ + e Ca2+ + 2e Sr2+ + 2e K+ + e Li+ + e
2+

E, V 0.277 0.31 0.403 0.41 0.440 0.49 0.50 0.61 0.763 0.91 1.18 1.53 1.63 1.66 1.90 2.37 2.52 2.714 2.87 2.89 2.925 3.045

Co Ag + 2CN Cd Cr2+ Fe H2C2O4 H3PO2 + H2O U3+ Zn Cr Mn Zr Ti Al Th Mg La Na Ca Sr K Li

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STANDARD REDUCTION ELECTRODE POTENTIALS FOR INORGANIC SYSTEMS IN NONAQUEOUS SOLUTIONS AT 25C The following table lists some standard electrode potentials (in V) in various solvents. The rubidium ion, which possesses a large radius and shows a low deformability, has a rather low and constant solvation energy in all solvents.1 As a result, the rubidium electrode is taken as a standard reference electrode in all solvents.

REFERENCES
1. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970.
Standard Reduction Electrode Potentials for Inorganic Systems in Nonaqueous Solutions at 25C System Li/Li+ Rb/Rb+ Cs/Cs+ K/K+ Ca/Ca+2 Na/Na+ Zn/Zn+2 Cd/Cd+2 Tl/Tl+ Pb/Pb+2 H2/H+ Cu/Cu+2 Cu/Cu+ Hg/Hg+2 Ag/Ag+ Hg/Hg+2 I/I2 Br/Br2 Cl/Cl2 H 2O 0.03 0.00 +0.06 +0.06 +0.14 +0.27 +2.22 +2.58 +2.64 +2.85 +2.98 +3.32 +3.50 +3.78 +3.78 +3.84 +3.52 +4.04 +4.34 CH3OH 0.16 0.00 +0.21 +2.20 +2.51 +2.56 +2.74 +2.94 +3.28 +3.68 +3.70 +3.30 +3.83 +4.16 CH3CN 0.06 0.00 +0.01 +0.01 +0.42 +0.30 +2.43 +2.70 +3.05 +3.17 +2.79 +2.89 +3.40 +3.42 +3.24 +3.64 +3.75 HCOOH 0.03 0.00 0.01 +0.10 +0.25 +0.03 +2.40 +2.70 +2.73 +3.45 +3.31 +3.63 +3.62 +3.42 +3.97 +4.22 N 2H 4 0.19 0.00 0.01 +0.10 +0.18 +1.60 +1.91 +2.36 +2.01 +2.23 +2.78 NH3 0.35 0.00 0.02 0.05 +0.29 +0.08 +1.40 +1.73 +2.25 +1.93 +2.36 +2.34 +2.76 +2.08 +3.38 +3.76 +3.96

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REDOX POTENTIALS FOR SOME BIOLOGICAL HALF REACTIONS The following table lists the standard redox potentials of some common biological half reactions (in V) at 298 K and pH = 7.0.1

REFERENCES
1. Hibbert, D.B. and James, A.M., Dictionary of Electrochemistry, 2nd ed., John Wiley & Sons, New York, 1984.
Redox Potentials for Some Biological Half Reactions Biological System Acetate/pyruvate Fe+3/Fe+2 (ferredoxin) H+/H2 NADP+/NADPH NAD+/NADH FAD/FADH2 Acetaldehyde/ethanol Pyruvate/lactate Oxaloacetate/malate Half-Cell Reaction CH3COOH + CO2 + 2H + 2e CH3COCOOH + H2O Fe+3 + e Fe+2 2H+ + 2e H2(g) NADP+ + 2H+ + 2e NADPH + H+ NAD+ + 2H+ + 2e NADH + H+ FAD + 2H+ + 2e FADH2 CH3CHO + 2H+ + 2e CH3CH2OH CH3COCOOH + 2H+ + 2e CH3CH(OH)COOH
+

E, V 0.70 0.432 0.421 0.324 0.320 0.219 0.197 0.185 0.166

CH2COOH Methylene Blue (ox) (MB)/ Methylene Blue (red) (MBH2) Fumarate/succinate

+ 2H+ + 2e

CH2COOH HOCHCOOH 0.011 0.031

O C COOH MB + 2H+ + 2e MBH2

CHCOOH

+ 2H+ + 2e

CH2COOH CH2COOH 0.046 0.050 0.10 0.254 0.29 0.365 0.540 0.816

Fe+3/Fe+2 (myoglobin) Fe+3/Fe+2 (cytochrome b) Ubiquinone/ubihydroquinone (cytochrome c)+3/(cytochrome c)+2 (cytochrome a)+3/(cytochrome a)+2 (cytochrome f)+3/(cytochrome f)+2 Cu+2/Cu+ (hemocyanin) O2/H2O

CHCOOH Fe+3 + e Fe+2 Fe+3 + e Fe+2 Ub + 2H+ + 2e UbH2 Fe+3 + e Fe+2 Fe+3 + e Fe+2 Fe+3 + e Fe+2 Cu+2 + e Cu+ O2(g) + 4H+ + 4e 2H2O

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STANDARD emf VALUES FOR THE CELL H2/HCl/AgCl, Ag IN VARIOUS AQUEOUS SOLUTIONS OF ORGANIC SOLVENTS AT VARIOUS TEMPERATURES The table below lists the standard emf values of the cell H2/HCl/AgCl, Ag in water as well as in various aqueous solutions of three common organic solvents, all alcohols, at different temperatures.1,2 The compositions are given as mass percent of the alcohol in water. All emf values are expressed in volts.

REFERENCES
1. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970. 2. Robinson, R.A. and Stokes, R.H., Electrolytic Solutions, Butterworths, London, 1959.
Standard emf values for the Cell H2/HCl/AgCl, Ag in Various Aqueous Solutionsa of Organic Solvents at Various Temperatures C 0 5 10 15 20 25 30 35 40
a

100% Water 0.23655 0.23413 0.23142 0.22857 0.22557 0.22234 0.21904 0.21565 0.21208

10% Aq. Methanol 0.22762 0.22547 0.22328 0.22085 0.21821 0.21535 0.21220 0.20892 0.20350

10% Aq. Ethanol 0.22726 0.22527 0.22328 0.22164 0.21901 0.21467 0.21383 0.21082 0.20783

10% Aq. 2-Propanol 0.22543 0.22365 0.22158 0.21922 0.21667 0.21383 0.21081 0.20754 0.20410

20% Aq. Methanol 0.22022 0.21837 0.21631 0.21405 0.21155 0.20881 0.20567 0.20246 0.19910

20% Aq. Ethanol 0.21606 0.21486 0.21367 0.21190 0.21013 0.20757 0.20587 0.20275 0.19962

20% Aq. 2-Propanol 0.21612 0.21492 0.21336 0.21138 0.20906 0.20637 0.20341 0.20009 0.19652

The percentages provided above are expressed as (vol/vol).

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TEMPERATURE DEPENDENCE OF THE STANDARD POTENTIAL OF THE SILVER CHLORIDE ELECTRODE The following table gives the standard potential (in V) of the silver chloride electrode (saturated KCl) at different temperatures (in C).1,2 The uncertainty is 0.05 mV.

REFERENCES
1. Conway, B.E., Theory and Principles of Electrode Process, Ronald Press, New York, 1965. 2. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970.

Temperature Dependence of the Standard Potential of the Silver Chloride Electrode Temperature (C) 0 5 10 15 20 25 30 Eo,V 0.23634 0.23392 0.23126 0.22847 0.22551 0.22239 0.21912 Temperature (C) 35 40 45 50 55 60 Eo,V 0.21563 0.21200 0.20821 0.20437 0.20035 0.19620

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STANDARD ELECTRODE POTENTIALS OF ELECTRODES OF THE FIRST KIND The following table lists the standard electrode potentials (in V) of some electrodes of the rst kind.13 These are divided into cationic and anionic electrodes. In cationic electrodes, equilibrium is established between atoms or molecules of the substance and the corresponding cations in solution. Examples include metal, amalgam, and the hydrogen electrode. In anionic electrodes, equilibrium is achieved between molecules and the corresponding anions in solution. The potential of the electrode is given by the Nernst equation in the form E = E0 + (RT)/(ZF) ln a where: Eo = standard electrode potential (in V) R = gas constant T = temperature (in K) Z = charge, with sign, of the cation (+) or anion () F = Faraday a = activity of the cation (+) or anion () Note that the equation uses the natural logarithm of the activity. Electrodes of the rst kind differ distinctly from the redox electrodes in that in the latter case, both oxidation states can be present in variable concentrations, while in electrodes of the rst kind, one of the oxidation states is the electrode material.

REFERENCES
1. Koryta, J., Dvork, J., and Karan, L., Principles of Electrochemistry, 2nd ed., John Wiley & Sons, New York, 1993. 2. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970. 3. Lide, D.R., Ed., CRC Handbook of Chemistry and Physics, 83rd ed., CRC Press, Boca Raton, FL, 2002.
Standard Electrode Potentials of Electrodes of the First Kind Electrode Li+/Li Rb+/Rb Cs+/Cs K+/K Ba+2/Ba Sr+2/Sr Ca+2/Ca Na+/Na Mg+2/Mg Be+2/Be Al+3/Al Zn+2/Zn Fe+2/Fe Cd+2/Cd In+3/In Tl+/Tl Co+2/Co Eo(V)a 3.0403 2.98 2.92 2.931 2.912 2.89 2.868 2.71 2.372 1.847 1.662 0.7620 0.447 0.4032 0.3384 0.336 0.27 Electrode Ni+2/Ni In+/In Sn+2/Sn Pb+2/Pb Cu+2/Cu Cu+/Cu Te+4/Te Hg+2/Hg Ag+/Ag Au+3/Au Pt, Se2/Se Pt, S2/S Pt, OH/O2(g) Pt, I/I2 Pt, B/Br2 Pt, Cl/Cl2(g) Pt, F/F2(g) Eo(V)a 0.23 0.203 0.1377 0.1264 +0.3417 +0.52 +0.56 +0.851 +0.7994 +1.42 0.78 0.51 +0.401 +0.536 +1.066 +1.35793 +2.866

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STANDARD ELECTRODE POTENTIALS OF ELECTRODES OF THE SECOND KIND The following table lists the standard electrode potentials (in V) of some electrodes of the second kind.13 These consist of three phases. The metal is covered by a layer of its sparingly soluble salt and is immersed in a solution of a soluble salt of the anion. Equilibrium is established between the metal atoms and the solution anions through two partial equilibria: one between the metal and its cation in the sparingly soluble salt and the other between the anion in the solid phase of the sparingly soluble salt and the anion in solution. The silver chloride electrode is preferred for precise measurements.

REFERENCES
1. Koryta, J., Dvork, J., and Karan, L., Principles of Electrochemistry, 2nd ed., John Wiley & Sons, New York, 1993. 2. Koryta, J., Dvork, J., and Bohckov, V., Electrochemistry, Methuen and Co., London, 1970. 3. Lide, D.R., Ed., CRC Handbook of Chemistry and Physics, 83rd ed., CRC Press, Boca Raton, FL, 2002.

Standard Electrode Potentials of Electrodes of the Second Kind Electrode PbSO4, SO42/Pb, Hg AgI, I/Ag AgBr, Br/Ag HgO, OH/Hg Hg2Br2, Br/Hg AgCl, Cl/Ag Hg2Cl2, Cl/Hg Hg2SO4, SO42/Hg PbO2, PbSO4, SO42/Pb Eo(V)a 0.351 0.152 +0.071 +0.0975 +0.140 +0.22216 +0.26791 +0.6123 +1.6912

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POLAROGRAPHIC HALF-WAVE POTENTIALS (E1/2) OF INORGANIC CATIONS The following table lists the polarographic half-wave potentials (E1/2, in volts, vs. SCE, the standard calomel electrode) of inorganic cations and the supporting electrolyte used during the determination.16 All supporting electrolyte solutions are aqueous unless noted. See page 629 for a description of the concentration nomenclature.

REFERENCES
1. Skoog, D.A., West, D.M., and Holler, F.J., Analytical Chemistry: An Introduction, 6th ed., Saunders, Philadelphia, 1994. 2. Vogel, A.I., A Textbook for Quantitative Inorganic Analysis, 3rd ed., John Wiley & Sons, New York, 1968. 3. Fritz, J.S. and Schenk, G.H., Quantitative Analytical Chemistry, 4th ed., Prentice Hall, Englewood Cliffs, 1987. 4. Christian, G.D., Analytical Chemistry, 5th ed., John Wiley & Sons, New York, 1994. 5. Ewing, G.W., Instrumental Methods of Analysis, 5th ed., McGraw-Hill, New York, 1985. 6. Meites, L., Polarographic Techniques, 2nd ed., Wiley Interscience, New York, 1965.

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Supporting Electrolytes 0.5 M Tartrate and NaOH pH = (0.1 F) 4.5 1.00 0.23

Cation Ba Bi+3 Cd+2 Co+2 Cr+3

+2

KCl (0.1 F)

NH3 (1 F) NH4Cl (1 F)

NaOH (1 F)

H3PO4 (7.3 F)

KCN (1 F)

(CH3)4NCl (0.1 F) 1.94

HCl (1 F) 0.09

H2SO4 (0.5 M ) 0.04

Others

0.64 (0.60) 1.20

0.81 1.29 1.43 (to Cr+2) 1.71 (to Cr 0) 0.24 (to Cu+) 0.51 (to Cu0) 1.49

0.78 1.46

0.77 1.20 1.02 (to Cr+2)

1.18 1.45 1.38 (to Cr+2)

HNO3 (1.0 F), 0.59 KI (1.0 F), 0.74 Pyridine (0.1 F)/ pyridinium (0.1 F), 1.07

Cu+2

Fe+2 Fe+3

+0.04 (to Cu+) 0.22 (to Cu0) 1.3

0.41

0.09

No reaction

0.09

1.12 (to Fe+2) 1.74 (to Fe0)

+0.06 (to Fe+2)

1.20, 1.73

EDTA (0.1 F)/ CH3COONa (2.0 F), 0.17, 1.30 (CH3)4NOH (0.1 M, 50% C2H5OH), 2.10 (CH3)4NOH (0.1 M, 50% C2H5OH), 2.31 H2P2O72 (0.2 M ), pH = 2.2, +0.1

K+ Li+ Mn+2 1.51

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Supporting Electrolytes (continued) 0.5 M Tartrate and NaOH pH = (0.1 F) 4.5

Cation Na Ni+2
+

KCl (0.1 F) 1.1

NH3 (1 F) NH4Cl (1 F) 1.10

NaOH (1 F)

H3PO4 (7.3 F)

KCN (1 F) 1.36

(CH3)4NCl (0.1 F) 2.07

HCl (1 F)

H2SO4 (0.5 M )

Others KSCN (1.0 F), 0.7; pyridine (1.0 F)/HCl, pH = 7, 0.78 pH = 110 (buffered), 0.05 and 0.90 HNO3 (1 F), 0.40 F (0.1 F), 0.611; F (0.5 F), 0.683 HCl (1.0 F)/NH4+ (4.0 F), 0.25 and 0.52

O2 Pb+2 Sn+2 Sn+4 Te+ Zn+2 0.48 1.00 0.48 1.34 0.40 0.75 0.75 0.48 1.53 1.15 0.72 0.47 0.75 0.48

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POLAROGRAPHIC E1/2 RANGES (IN V vs. SCE) FOR THE REDUCTION OF BENZENE DERIVATIVES The following table lists the polarographic E1/2 potential ranges (in V vs. SCE) obtained at pH = 59 in unbuffered media in the reduction of benzene derivatives.1

REFERENCES
1. Zuman, P., The Elucidation of Organic Electrode Processes, Academic Press, New York, 1969.
Polarographic E1/2 Ranges (in V vs. SCE) for the Reduction of Benzene Derivatives Benzene Derivativea Diaryl alkene Methyl aryl ester Aryl iodide Aryl methyl ketone Aromatic aldehyde Methyl ,-unsaturated aryl ketone Diaryl ketone Azobenzenes Nitroarenes Nitrosoarenes Diaryl iodonium salts
a b

Formulaa ArCH=CHAr ArCOOCH3 ArI ArCOCH3 ArCHO ArCH=CHCOCH3 ArCOAr ArN=NAr ArNO2 ArNO Ar2I+

Polarographic E1/2 Potential Rangeb 1.8 1.0 1.2 1.1 1.1 1.0 0.7 0.3 0.3 0.1 0.2 to to to to to to to to to to to 2.3 2.4 1.9 1.8 1.7 1.6 1.4 0.8 0.7 0.4 0.3

Ar = aromatic ring. In V vs. SCE.

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VAPOR PRESSURE OF MERCURY The following table provides data on the vapor pressure of mercury, useful for assessing and controlling the hazards associated with use of mercury as an electrode.1

REFERENCES
1. Lide, D.R., Ed., CRC Handbook of Chemistry and Physics, 83rd ed., CRC Press, Boca Raton, FL, 2002.

Vapor Pressure of Mercury Temperature, C 0 10 20 22 24 26 Vapor Pressure, mmHg 0.000185 0.000490 0.001201 0.001426 0.001691 0.002000 Vapor Pressure, Pa 0.0247 0.0653 0.1601 0.1901 0.2254 0.2666 Temperature, C 28 30 40 50 100 Vapor Pressure, mmHg 0.002359 0.002777 0.006079 0.01267 0.273 Vapor Pressure, Pa 0.3145 0.3702 0.8105 1.689 36.4

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ORGANIC FUNCTIONAL GROUP ANALYSIS OF NONPOLAROGRAPHIC ACTIVE GROUPS Often an organic functional group is not (or may not be) reduced polarographically at an accessible potential range. In this case it is necessary to convert this functional group to a derivative whose reduction is feasible within such an accessible potential range. The table below lists the most common functional groups, the reagent needed, and the polarographically active derivative as well as the polarographically active group.14 Such conversions enlarge the number of organic compounds that can be determined by polarography.

REFERENCES
1. Svoronos, P., Horak, V., and Zuman, P., Polarographic study of structure-properties relationship of ptosyl sullimines, phosphorus, Sulfur Silicon, 42, 139, 1989. 2. Willard, H.H., Dean, J.A., Settle, F.A., and Merritt, L.L., Instrumental Methods of Analysis, 7th ed., Wadsworth Publishing Co., Belmont, CA, 1995. 3. Zuman, P., Chemical and Engineering News, March 18, 1968, p. 94. 4. Zuman, P., Substituent Effects in Organic Polarography, Plenum, New York, 1967.

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Organic Functional Group Analysis of Nonpolarographic Active Groups Functional Group Carbonyl (aldehyde, ketone), >C=O Reagent Semicarbazide H2NHNCNH2 O Hydroxylamine H2NOH Primary amine, RNH2 Piperonal C8H6O3 Carbon disulde, CS2 R N C S Cupric phosphate, Cu3(PO4)2, suspension Secondary amine, R2NH Primary alcohols, RCH2OH Nitrous acid, HNO2 H [Cu+2amine complex] >C=NOH C7H3O2CH=NR S H
Dithiocarbonate N C S

Polarographically Active Derivative

Active Polarographic Group Semicarbazide, >C=NN

>C

NHC O

NH2

Oxime, >C=NOH Azomethine, >C=NR

[Cu+2amine] complex

R2NN=O Nitroso, N N O R Aldehyde carbonyl, C H O

Chromic acid, HCrO4

RCHO

Secondary alcohols, R2CH2OH

Chromic acid, HCrO4

R2C=O

R Ketone carbonyl, C R O

1,2-Diols

Periodic acid, HIO4 R C H O R

R C O

Aldehyde and/or ketone carbonyl >C=O

Carboxylic acid, R C OH O Phenyl, C6H5, Suldes (thioethers), >S

Thiourea, (H2N)2C=S

RCO2 [(H2N)2CSH]+

Protonated thiocarbonyl, [>C=SH]+

Conc. nitric/conc. sulfuric acid, HNO3/H2SO4 Hydrogen peroxide, H2O2 or mchloroperbenzoic acid, 1,3-Cl-C6H4COOH Chloramine-T, CH3 SO2NClNa

C6H5NO2

Nitro, NO2

>S+O Sulfoxide, S+

>S=NSO2C6H4CH3

Sullimine, >S=N

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COULOMETRIC TITRATIONS The following table lists some common coulometric (also known as constant-current coulometry) titrations.14 Since the titrant is generated electrolitically and reacted immediately, the method gets widespread applications. The generating electrolytic concentrations need to be only approximate, while unstable titrants are consumed as soon as they are formed. The technique is more accurate than methods where visual end points are required, such as in the case of indicators. The unstable titrants in the table below are marked with an asterisk.

REFERENCES
1. Christian, G.D., Analytical Chemistry, 5th ed., John Wiley & Sons, New York, 1994. 2. Christian, G.D., Electrochemical methods for analysis of enzyme systems, in Advances in Biomedical Engineering and Medical Physics, Vol. 4, Levine, S.N., Ed., Wiley Interscience, New York, 1971, p. 95. 3. Skoog, D.A., West, D.M., and Holler, J.F., Fundamentals of Analytical Chemistry, 6th ed., Saunders, Philadelphia, 1996. 4. Harris, D.C., Quantitative Chemical Analysis, 5th ed., W.H. Freeman, San Francisco, 1998.

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Coulometric Titrations Reagent Ag+ Ag+2 *Biphenyl radical anion *Br2 Generator Electrode Reaction Ag Ag+ + e Ag+ Ag+2 + e (C6H5)2 + e (C6H5)2 2 Br Br2 + 2e Typical Generating Electrolyte Ag anode in HNO3 Substances Determined Br, Cl, thiols Ce+3, V+4, H2C2O4, As+3 Anthracene As+3, Sb+3, U+4, Tl+, I, SCN, NH2OH, N2H4, phenols, aromatic amines, mustard gas, olens, 8-hydroxyquinoline NH3 Fe+2, Ti+3, U+4, As+3, I, Fe(SCN)64 As+3, I O2 V+5, Cr+6,IO3 Ca+2, Cu+3, Zn+2, Pb+2 Ca+2 (in the presence of Mg+2) Cr+6, Mn+7, V+5, Ce+4 As+3, Sb+3, S2O32, H2S, H2O Pyridine H2C2O4, Fe+2, As+3, H 2O 2 Cr2O72 Mn+3 (in enzymes) HCl V+5, Fe+3, Ce+4, U+6 Cr+6, Ce+4

Biphenyl/(CH3)4NBr in DMF 0.2 M NaBr in 0.1 M H2SO4

*BrO Ce+4 *Cl2 *Cr+2 *CuCl32 EDTA

Br + 2 OH BrO+ H2O + 2e Ce+2 Ce+4 + 2e 2 Cl Cl2 + 2e Cr+3 + e Cr+2 Cu+2 + 3Cl + e CuCl32 HgNH3(EDTA)+2 + NH4+ + 2e Hg + 2NH3 + (HEDTA)3 HgNH3(EGTA)+2 + NH4+ + 2e Hg + 2NH3 + (HEGTA)+1 Fe+3 + e Fe+2 2I I2 + 2e

1 M NaBr in borate buffer, pH = 8.6a 0.1 M CeSO4 in 3 M H2SO4 Cr2(SO4)3 in H2SO4 0.1 M CuSO4 in 1 M HCl 0.02 M Hg+2/EDTA in ammoniacal buffer, pH = 8.5, Hg cathode 0.1 M Hg+2/EGTA in triethanolamine, pH = 8.6, Hg cathode Acid solution of FeNH4(SO4)2 0.2 M KI in pH = 8 buffer, pyridine, SO2, CH3OH, KI (Karl Fisher titration) 0.1 M Na2SO4 (water electrolysis) MnSO4 in 2 M H2SO4 0.7 M Mo+6 in 4 M H2SO4 0.1 M Na2SO4 (water electrolysis) 3.6 M TiCl4 in 7 M HCl Acid solution of UO2+2

EGTA Fe+2 I2

H+ *Mn+3 Mo+5 *MV+b OH Ti+3 U +4

a b

2H2O 4H+ + O2 + 4e Mn+2 Mn+3+ e Mo+6 + e Mo+5 MV+2 + e MV+ 2H2O + 2e H2 + 2OH Ti+4 + e Ti+3 or TiO+2 + 2H+ + e Ti+3 + H2O UO2+2 + 4H+ + 2e U+4 + 2H2O

See page 573 for the preparation of this buffer. MV+ = methyl viologen radical cation; MV+2 = methyl viologen radical cation.

+ CH3N

+ NCH3 + e

+ CH3N

NCH3

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