Читать книгу Electroanalytical Chemistry - Gary A. Mabbott - Страница 4

1 Chapter 1Figure 1.1 The electric (or electrostatic) potential energy at a point, A, in ...Figure 1.2 a) The absolute electrical potential of a given point cannot be mea...Figure 1.3 Electronic circuits form a continuous loop including all components...Figure 1.4 Basic arrangement of an electrochemical cell. Two electrodes are re...Figure 1.5 The Helmholtz model of the electrified boundary between a metal sur...Figure 1.6 The inner Helmholtz plane (IHP) is a plane parallel to the electrod...Figure 1.7 (a) Gouy–Chapman model of electrical double layer showing a diffuse...Figure 1.8 Stern model of the electrical double layer. Charges and solvent at ...Figure 1.9 The electrical double layer plays an important role in the suspensi...Figure 1.10 The electrical double layer can be modeled as a capacitor where th...Figure 1.11 Conductance cell.Figure 1.12 The definition of flux is the net number of moles of molecules per...Figure 1.13 A salt bridge is a liquid junction between two solutions that allo...Figure 1.14 The measured potential between the indicator and reference electro...Figure 1.15 Microscopic pores in a glass frit used as a salt bridge. The elect...

2 Chapter 2Figure 2.1 Null point method for measuring a voltage. The arrow pointing to th...Figure 2.2 Electron transfer at a Pt electrode for Fe(III)/Fe(II) oxidation–re...Figure 2.3 Structures of nicotinamide adenine dinucleotide in the oxidized for...Figure 2.4 A metallic silver surface in electrochemical equilibrium with silve...Figure 2.5 Plot of the half‐cell potential at a silver metal electrode as a fu...Figure 2.6 AgCl/Ag electrode. A coating of silver chloride provides silver ion...Figure 2.7 The reduction of AgCl to metallic Ag by two paths.Figure 2.8 Plot of the potential of a silver/silver chloride electrode versus Figure 2.9 A complete potentiometric cell with a silver/silver chloride refere...Figure 2.10 Saturated calomel electrode (SCE).Figure 2.11 The standard hydrogen electrode (SHE). The half‐cell is based on t...Figure 2.12 In calibrating a calomel electrode, the electrode is introduced di...Figure 2.13 Diagramming half‐cell potentials on an energy ladder using the SHE...Figure 2.14 General shape of redox titration as monitored by potentiometry. Th...Figure 2.15 The platinum indicator electrode attains a potential where the net...Figure 2.16 (a) Diagram of soil experiment. (b) The redox potential of a water...Figure 2.17 Soil chemistry changes with depth corresponding to the availabilit...Figure 2.18 E _H–pH diagram shows the equilibrium between iron species in natura...Figure 2.19 Some important redox agents in biochemical reactions. NADP⁺/NA...Figure 2.20 Methods for controlling the redox potential of growth media in fer...

3 Chapter 3Figure 3.1 General diagram of an electrochemical cell for a measurement based ...Figure 3.2 Diagram of an electrochemical cell using an ISE showing the interna...Figure 3.3 An aqueous solution of tetrabutyl ammonium nitrate (TBA⁺ NO3−...Figure 3.4 (a) The structure of valinomycin. Valinomycin is a neutral complexi...Figure 3.5 Conventional liquid membrane K⁺ ISE. The membrane is usually a ...Figure 3.6 Examples of common hydrophobic counter ions used as ionic sites in ...Figure 3.7 Ionophore that binds adenosine monophosphate.Figure 3.8 Early apparatus for pH titration. A calomel reference electrode wit...Figure 3.9 Glass structure. (a) Silicate tetrahedron. (b) Conceptual model for...Figure 3.10 Hydrogen ion transfer across the phase boundary from the outer Hel...Figure 3.11 Haugaard's demonstration of sodium conductivity in glass. Beaker A...Figure 3.12 (a) Glass electrode response to pH deviates from the ideal in the ...Figure 3.13 Combination pH glass electrode. Both reference electrodes are AgCl...Figure 3.14 Carbon dioxide sensor based on a combination pH electrode known as...Figure 3.15 Carbon dioxide electrode response in mV as a function of dissolved...Figure 3.16 Conceptual views of lanthanum trifluoride lattice. (a) Top view. E...Figure 3.17 The response of an ISE made from a silver chloride membrane to sil...Figure 3.18 IUPAC method for estimating the detection limit for an anion ISE c...Figure 3.19 Calibration plot of response for an iodide selective electrode pot...Figure 3.20 A concentration gradient of analyte ion, I⁺ (not to be confuse...Figure 3.21 Improved detection limits for a lead ion selective electrode. The ...Figure 3.22 Assembly for an “all‐solid‐state ISE” using three dimensionally or...Figure 3.23 Components for fluorinated membrane ISEs. Structures 1 and 2 have ...Figure 3.24 Partial Lewis dot structures for silicon and doped silicon semicon...Figure 3.25 (a) Diagram of a conventional field effect transistor (FET) design...Figure 3.26 Ion‐sensing field effect transistor (ISFET). (a) Diagram of the tr...

4 Chapter 4Figure 4.1 Calculated junction potential for a 3 M KCl salt bridge electrolyte...FIGURE 4.2 Calibration plot for the cell potential using a fluoride ISE and st...Figure 4.3 Gran's method for a standard additions experiment. Fluoride standar...Figure 4.4 Two pathways for conversion of creatine to creatinine, the enzymati...Figure 4.5 Jaffé reaction traditionally used to determine creatinine levels in...Figure 4.6 (a) Structure of creatininium ion, (b) Structure of calix[4]pyrrole...Figure 4.7 (a) Plot of E _sensor versus solution pH. The data show the sensor vo...Figure 4.8 Various types of double junction salt bridges. The additional chamb...Figure 4.9 ISE method validation. Comparison of results for creatinine levels ...Figure 4.10 Autonomous multichannel analyzer. (a) Upper diagram: flow from one...Figure 4.11 pH titration of potassium hydrogen phthalate (KHP) with NaOH. (a) ...Figure 4.12 Gran plot for the titration of acetic acid by a standardized NaOH....

5 Chapter 5Figure 5.1 (a) Three‐electrode cell for controlled potential experiments. The ...Figure 5.2 Graphical analogy between spectroscopy and voltammetry. (a) The hei...Figure 5.3 Plot of the potential energy well for the reactants and the potenti...Figure 5.4 The net current is the sum of the individual anodic and cathodic cu...Figure 5.5 (a) Commercial flow cell assembly. (b) Cross‐sectional view of flow...Figure 5.6 The current in a voltammetry experiment is dependent on, at least, ...Figure 5.7 The concentration profile for a reducible species near the electrod...Figure 5.8 (a) Rotated disk electrode assembly. (b) Cross‐section and bottom v...Figure 5.9 Hydrodynamic voltammograms for reversible, quasi‐reversible, and ir...Figure 5.10 The chronoamperometry experiment. (a) Potential step. (b) The init...Figure 5.11 The CV experiment. (a) The applied potential starts at some initia...Figure 5.12 The shape of cyclic voltammograms for reversible, quasi‐reversible...Figure 5.13 Three methods for estimating the peak current for both the anodic ...Figure 5.14 Cyclic voltammograms of aniline and related compounds at a carbon ...Figure 5.15 Double‐layer charging current response of a 3 mm diameter carbon d...Figure 5.16 Scanning the voltage in a linear manner introduces charging curren...Figure 5.17 “Pulse voltammetry” techniques for overcoming background currents....Figure 5.18 Mercury electrodes. (a) Hanging mercury drop electrode (HMDE). By ...Figure 5.19 Structures of carbon electrode materials. (a) Graphene sheet. (b) ...Figure 5.20 Carbon paste electrode. A purified graphite powder is mixed with a...Figure 5.21 The influence of the electrode surface conditions upon electron tr...Figure 5.22 Cyclic voltammograms of ascorbic acid on glassy carbon electrode i...Figure 5.23 Background scans in aqueous pH 7 phosphate buffer showing the usef...Figure 5.24 (a) Mass transport to a millimeter‐size electrode follows a path t...Figure 5.25 The development of the reactant concentration depletion zone near ...Figure 5.26 Reduction of 4.8 mM 9‐bromoanthracene at a 3 μm Au disk electrode ...Figure 5.27 Fast scan CVs were recorded for a carbon fiber placed in the brain...Figure 5.28 HPLC separation and pulse amperometric detection of a mixture of a...Figure 5.29 Diagram of an anodic stripping voltammetry experiment. The bottom ...Figure 5.30 Anodic stripping experiments performed on a solution of four metal...Figure 5.31 (a) Expanded view of a commercial glucose test strip. The blood sa...Figure 5.32 (a) KF coulometric titration cell. (b) Close‐up view of the iodine...Figure 5.33 (a) Detection electrodes in Karl Fischer cell. (b) Voltammogram of...Figure 5.34 The structure of a liquid membrane sensor for ion transfer strippi...Figure 5.35 (a) Perchlorate stripping voltammograms of 10, 7, 5, 3, 2, 1, and ...Figure 5.36 The diagram on the left shows the double polymer membrane ISE for ...Figure 5.37 (a) ITSV of potassium ions in lab water after five‐minute preconce...Figure 5.38 Multiple CV scans of 10 mM NaCl with a polyurethane membrane on th...Figure 5.39 Two ions at once. (a) Separate ionophores for Li⁺ and K⁺ w...

6 Chapter 6Figure 6.1 Cyclic voltammograms of [Ru(EDTA)(H₂O)]⁻ and [Ru(EDTA)(DMSO)]Figure 6.2 Equilibria relating the different forms of some ruthenium–EDTA comp...Figure 6.3 The reduction of A_Ox by reagent, B_Red, as mediated by a catalyst, C...Figure 6.4 General structures for a series of Mn(II) complexes that were studi...Figure 6.5 A plot of the formal potential for complexes versus Hammet constant...Figure 6.6 Cyclic voltammogram of 2 mM uric acid in pH 7.5 phosphate buffer re...Figure 6.7 (a) Simulated cyclic voltammograms of an electron transfer step fol...Figure 6.8 Example calculation for the rate constant for the following chemica...Figure 6.9 Double potential step chronoamperometry. (a) The general current re...Figure 6.10 Spectroelectochemistry apparatus for observing UV spectra of elect...Figure 6.11 UV spectra recorded during oxidation of uric acid at an optically ...Figure 6.12 Proposed mechanism for the reduction process associated with peak ...Figure 6.13 Proposed mechanism for the formation of allantoin from the interme...Figure 6.14 Redox catalysis with a freely diffusing catalyst is a variant of a...Figure 6.15 Theoretical cyclic voltammograms for the redox catalysis of carbon...Figure 6.16 Zone diagram depicting the shape of cyclic voltammograms for the c...Figure 6.17 (a) Simulated curves at different scan rates (increasing from bott...Figure 6.18 Structure of the iron–porphyrin complex used in this case study. I...Figure 6.19 Cyclic voltammograms recorded in the presence of 2 M water in DMF ...

7 Chapter 7Figure 7.1 Simple circuit for demonstrating Kirchhoff's and Ohm's laws and The...Figure 7.2 The equivalent circuit for Figure 7.1 where R* represents the equiv...Figure 7.3 (a) A voltage divider made from two resistors provides a voltage at...Figure 7.4 (a) Sketch of 8‐pin dual in‐line op amp package, (b) sketch of op a...Figure 7.5 Schematic representation of an op amp for circuit diagrams. Positiv...Figure 7.6 The voltage follower. The signal, V _in, is applied to the noninverti...Figure 7.7 Current follower op amp configuration. The signal current cannot en...Figure 7.8 A simple gain amplifier multiplies the input voltage, V _in, by a gai...Figure 7.9 An op amp circuit for applying a potential in a three‐electrode vol...Figure 7.10 Faraday cage for ultramicroelectrode voltammetry experiments. The ...Figure 7.11 (a) BNC connector for mounting on an instrument frame. (b) BNC con...Figure 7.12 Some working electrode fabrication techniques. Soft glass can make...Figure 7.13 Arrangement for coating a silver wire with silver chloride [7].Figure 7.14 Assembled reference electrode made in the lab.