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Lecture Date: April 27h, 2008
Skoog, Holler and Crouch: Ch. 22 (An Introduction to Electroanalytical Chemisty) See also Skoog et al. Chapters 23-25. Cazes: Chapters 16-19 For those using electroanalytical chemistry in their work, the following reference is recommended:
A. J. Bard and L. R. Faulkner, ³Electrochemical Methods´, 2nd Ed., Wiley, 2001.
Advantages of Electroanalytical Methods
y Matched against a wide range of spectroscopic
and chromatographic techniques, the techniques of electroanalytical chemistry find an important role for several reasons:
± Electroanalytical methods are often specific for a particular oxidation state of an element ± Electrochemical instrumentation is relatively inexpensive and can be miniaturized ± Electroanalytical methods provide information about activities (rather than concentration)
´ y Walter Nernst: the Nernst equation (Nobel Prize 1920) y Jaroslav Heyrovsky: the invention of polarography: (Nobel Prize 1959) Michael Faraday (1791-1867) Walter Nernst (1864-1941) Jaroslav Heyrovsky (1890-1967) .History of Electroanalytical Methods y Michael Faraday: the law of electrolysis ± ³«the amount of a substance deposited from an electrolyte by the action of a current is proportional to the chemical equivalent weight of the substance.
t = time. G = conductance. vol = volume of a standard solution. R = resistance. Q = quantity of charge. Holler and Crouch. m = mass of an electrodispensed species . 6th ed.Main Branches of Electroanalytical Chemistry Interfacial methods Bulk methods Static methods (I = 0) Dynamic methods (I > 0) Conductometry (G = 1/R) Potentiometry (E) Based on Figure 22-9 in Skoog. Controlled potential Constant current Voltammetry (I = f(E)) Amperometric titrations (I = f(E)) Electrogravimetry (m) Coulometric titrations (Q = It) y Key to measured quantity: I = current. E = potential.
g.Main Branches of Electroanalytical Chemistry y Potentiometry: measure the potential of electrochemical cells without drawing substantial current ± Examples: pH measurements. ³chloridometers´ (AgCl) measures current as a function of applied potential under conditions that keep a working electrode polarized ± Examples: cyclic voltammetry. ion-selective electrodes. KF endpoint determination) y Coulometry: measures the electricity required to drive an electrolytic oxidation/reduction to completion ± Examples: titrations (KF titrant generation). titrations (e. many biosensors y Voltammetry: .
010 Anode Cu2+ (aq) + 2e.m Cu(s) a Cu 2+ = 0.010M ZnSO4 solution 0.Electrochemical Cells y y Zinc (Zn) wants to ionize more than copper (Cu).010M CuSO4 solution Zn m Zn2+ (aq) + 2ea Zn 2+ = 0. We can use this behavior to construct a cell: Voltmeter eSalt bridge (KCl) Cu electrode Zn electrode e- 0.010 Cathode .
measures I as function of time Coulometry: Control E. measure total Q over a period of time control measurement e- e- working electrode indicator electrode detector electrode reference electrode counter electrode .Electrochemical Cells and Analytical Methods Potentiometry: Measures equilibrium E Amperometry: Control E.
Electrochemical Cells y Galvanic cell: a cell that produces electrical energy y Electrolytic cell: a cell that consumes electrical energy y Chemically-reversible cell: a cell in which reversing the direction of the current reverses the reactions at the two electrodes .
Conduction in an Electrochemical Cell y Electrons serve as carriers (e.g. moving from Zn through the conductor to the Cu) y In the solution. electricity involves the movement of cations and anions ± In the salt bridge both chloride and potassium ions move y At the electrode surface: an oxidation or a reduction occurs ± Cathode: the electrode at which reduction occurs ± Anode: the electrode at which oxidation occurs .
GER = gain an electron is reduction For example. the chemical reaction can be decomposed into two half reactions: .³Leo the Lion Says Ger´ Oxidation occurs when a chemical species loses an electron. LEO = lose electron is oxidation Reduction is when a species gains an electron.
oxidation at one and reduction at the other electrode Non-Faradaic: increasing charge of the double layer . i.Faradaic and Non-Faradaic Currents Mass Transfer occurs by: Convection Migration Diffusion Figure 22-2 y Faradaic (governed by Faraday¶s law): direct transfer of y electrons.e.
. Ohm's law relates current to potential (E) through the resistance (R) of a circuit by E=IR. is measured in Amperes (A). The potential is measured in Volts (V) and the resistance in Ohms (.500) C/mole.). The charge associated with chemical species is related to the number of moles through the Faraday constant.485.3 (~96. F=96. Current is the amount of charge that passes in a unit time interval (seconds). Electrical current. is measured in coulombs (C). q. I.Fundamentals Electrical charge.
is given by (G°=-n F E° where n is the number of electrons transferred and superscript on E0 refers to µstandard state.¶ . The work is measured in Joules (J) and is related to the potential and the amount of charge by work=q E. (G° (J/mole). E° (V). and the standard electromotive force (EMF).Fundamentals Power (P) is measured in Watts (W = J/s) and is related to the current and potential by P= IE. The relationship between the standard Gibb's free energy change.
For low-concentration solutions (low ionic strengths): . For the generic reaction: Q is given by: The A¶s are activities.Fundamentals: The Nernst Equation The Nernst equation gives the cell potential E (in volts): F = faraday (constant) n = # moles electrons in process E0 = standard potential for cell Q (the activity quotient) is the ratio of products over reactants as in equilibrium calculations.
and gas pressure at 1 bar). always written as reductions y Standard electrode potential (E0): the measure of individual potential of an electrode at standard ambient conditions (298K.Electrode Potentials y The reactions in an electrochemical cell can be thought of as two half-cell reactions. each with its own characteristic electrode potential ± These measure the driving force for the reaction ± By convention. solutes at a concentration of 1 M. .
Ag(s) Cu2+ + 2e. for a more complete list .000 -0.337 +0. Cu(s) Hg2Cl2 + 2e. H2 (g) AgI(s) + e. Cd(s) Zn2+ + 2e.359 +1.268 0.799 +0.403 -0. 2Hg(l) + 2 Cl2 2H+ + 2e.763 See appendix 3 in Skoog et al.151 -0. 2 H2O Ag+ + e.229 +0.Some Standard Electrode Potentials Reaction Cl2(g) + 2e. Zn(s) E0 at 298K (Volts) +1. Ag(s) + I2 Cd2+ + 2e. 2 Cl2 O2 (g) + 4H+ + 4e.
and H+ ion activity y Because the SHE is difficult to make.The Standard Hydrogen Electrode (SHE) y A universal reference. ± Calomel = mercury (I) chloride . which at its surface oxidizes 2H+ to H2 gas. ± Very sensitive to temperature. the saturated calomel electrode (SCE) is used instead. pressure. but is really a hypothetical electrode (not used in practice) ± Uses a platinum electrode.
But the reaction is comprised of two components .01 M) ? The overall reaction for this electrode is This reaction cannot be found in tables of reduction potentials.Electrode Potentials Q: What is the electrode potential for the electrode Ag/AgI(s)/I-(0.
.Electrode Potentials We can initially ignore the fact that the electrode contains AgI and find E for the silver ion reduction.
A typical glass pH electrode is configured as shown here: .The Glass pH Electrode One of the most common potentiometric measurements is pH (a so-called ³p-Ion´ measurement). The common glass pH electrode makes use of junction potentials to determine the hydronium ion concentration in a sample solution.
A small frit or hole connects the reference electrode and the sample solutions . For most modern pH electrodes the reference electrode is incorporated with the pH indicator electrode.The Glass pH Electrode The glass pH electrode is used with a Ag/AgCl reference electrode.
g the frit in a salt bridge) . Junction potential: occurs at the interface of two electrolytes. The potential of this cell is: where Eij and Eoj are the junction potentials at the inner and outer layers of the glass membrane.pH Measurements A combination pH electrode combines the indicator and reference into a single unit. caused by unequal diffusion rates of cation and anions across the boundary (e.
dry glass and hydrated glass on the inside. There are four interface regions. hydrated glass and dry glass on the outside.More About pH Measurements The surface of the glass is hydrated. the external solution and hydrated glass. which allows exchange of hydronium ions for the cation in the glass (sodium or lithium). and hydrated glass and the internal solution. the junction potential is then the difference between the internal and external solutions. . the two hydrated glass/dry glass interfaces should be identical and should have the same junction potential. Since the glass interface junction potentials then cancel each other. If the glass is uniform.
sol'n.pH Measurements aH + .sol'n.sol'n.out If the two solutions are identical a H+ .glass.out logaH + .out aH + .in = aH + . then RT RT + logaH + .glass.out aH + .sol'n.in F aH + .glass.in = k + F 0.sol'n.out RT RT =log log log Emem = F aH + .glass.in RT aH + .inaH + .glass.out RT log Emem = F aH + .sol'n.sol'n.05916pH F F Emem = - . glass.out F aH + .sol'n.in if the internal solution has a fixed composition.inaH + .
the two surfaces will not be identical and the constant k needs to be determined experimentally. The constant k is termed the asymmetry potential. . The constant F is termed the electromotive efficiency.pH Measurements y For a real electrode.
pH Measurements .
Also. More explanation about how a pH meter really works: The sodium ions must move through the dry part of the membrane and this process is slow. .pH Measurements Q: Why does the pH change the interfacial potential of the glass/aqueous interface? A: The motion of the sodium ions leave behind a negatively charged glass layer that is neutralized to a lesser or greater extent according to the pH. For this reason. the membrane is made very thin. a nonperturbing (low-current) voltmeter is used to read the cell voltage so that only a few sodium ions must move through the dry glass in a given time period.
02 pH units ± Precision = +/. Accuracy and Precision y Errors in pH measurements with glass electrodes arise from the following effects: ± Calibration problems (e. or error in the calibration) ± Junction potential ± High [Na+] interacting with electrode ± High acid concentration ± Equilibration time ± Temperature control y Typical electrodes have the following performance: ± Accuracy = +/.0.0.pH Electrodes: Errors.g. drift.002 pH units .
and a glass membrane electrode. Schematically.The Combination pH Electrode Modern pH electrodes are usually of the "combination" type. Cl-/AgCl(s)/Ag . meaning that a single cylinder contains both the reference electrode. the total cell may be expressed as SCE//test solution ([H3O+]=a1)/glass membrane/[H3O+]=a2.
A Modern Combination pH Electrode .
00.Electrochemical pH Measurements Concluded Consider a typical problem related to the use of the combination pH electrode.115 V at a pH of 4. Recall that Ecell = L . what is the pH of a solution for which Ecell is -0.0.0592 V pH QUESTION: If Ecell = -0.352 V? .
122 V -(-0. L = 0.0592 x 4.352 V))/0.115 V = L -0.122 V .0592 x pH -0.352 V = 0.ANSWER: First.0592 V x pH pH = (0.0592 pH = 7.00 Therefore. use this value of L to find pH: -0.115 V = L -0. find L from the measurement of the standard: -0.122 V Second.0.84 .
QUESTION: What does the pH meter read if the pH is 7.00 in a 1 M salt solution having 1 M Na+ ions present? ANSWER: [H+]obs = 1 x 10-7 + 1 x 10-12 Conclusion -.the pH meter reads the true pH under these conditions. .
an internal reference electrode. and a voltmeter.The Ion Selective Electrode (ISE) An ISE generally consists of the ion-selective membrane. Example: an ISE for fluoride (F-) . an external reference electrode.
receptors and cell membranes liquid dispensors reagents The Sirius GLpKa system: combination pH electrode sample tray .Automatic pKa and log P Determination pKa (ionization constant) and log P (octanol/water partition) are important physical parameters that play critical roles in determining how compounds behave in physiological environments and how they interact with enzymes.
Conductometry y Conductometry: conductivity Detection of electrical ± Key analytical applications: conductometric detection in ion-exchange chromatography (IEC or IC) and capillary electrophoresis (CE) y Used to detect titration endpoints .
Homework Problems (for Study Only) y Chapter 22: ± 22-1 y Chapter 23: ± 23-11 .