Introduction Historic overview, Classification of (bio)chemical electrodes, definitions of sensors and biosensors and basic measuring techniques Fundamental Concepts Electrical conduction, electrodes, electrolytic cells, faradays law of electrolysis, Voltaic or Galvanic cells, The Nernst equation, reference and indicator electrodes, standard electrode potentials, liquid-junction potentials Potentiometric Methods and Electrodes Principles of potentiometric electrodes, experimental set-up and instrumentation (Galvanic cell), I di t electrodes: 1) metallic electrodes: fi t ( ti or redox electrode), second and ll) Indicator l t d t lli l t d first (cation d l t d ) d d third class or specie; 2) membrane electrodes: glass electrodes, polymer (liquid membranes) electrodes, crystalline and pressed powder solid electrodes, gas electrodes, enzymatic electrodes (biosensors) practical aspects and applications (biosensors),
References 1)R. W. Cattrall, Chemical Sensors, Oxford, Oxford Press, 1997 2) A. Evans, Potentiometry and Ion Selective Electrodes, Chichester, Wiley, 1987 3) F. Scholz, Electroanalytical methods-guide to experiments and applications, Berlin,SpringerVerlag, 2009 4) V. A. Gault, N. H. McClenaghan, Understanding Bioanalytical Chemistry- Principles and Applications, Oxford, Wiley-Blackwell, 2009 5) A. P. F. Turner, I. Karube, G. S. Wilson, Biosensors- Fundamentals and applications,Oxyford, Oxyford University Press, 1987 6) G. G. Guilbault, A. A. Suleiman, O. Fatibello-Filho, M. A. Nabirahni, Immobilized Bioelectrochemical Sensors, In: D. L. Wise, Bioinstrumentation and Biosensors, New York, Dekker, 659-692 , 7) O. Fatibello-Filho et al, Chapter 17 - Electrochemical biosensors based on vegetable p y tissues and crude extracts for environmental, food and pharmaceutical analysis, In: S. Alegret & A. Merkoi, Comprehensive Analytical Chemistry, Vol. 49-Electrochemical Sensor Analysis, Amsterdam, Elsevier , 355-375, 2007
Ano 1961 1962 1964 1966 1967 1970 1970 1974 1975 1979 1979 1980 1997 ?
Tipo de Sensor Sensor AgI(s) parafina p/ Ip g Biossensor para glicose Sensor piezeltrico Sensor de LaF3/EuF2 para FSensor de membrana liq. p/ Ca2+ Sensor de membrana de PVC p/ Ca2+ ChemFET Calorimtrico (enzimtico) ENFET Biossensor PC c/ ADH e LDH Biossensor de tecido Sensor de fibra-ptica Eletroantenograma Pncreas artificial implantvel
Investigador E. Pungor L.C. Clark & W. Lyons y W.H. King M.S. Frant & J.W. Ross J.W. Ross G. Moody et al P. Bergveld K. Mosbach & B. Danielson J. Janata T. Yao & S. Musha Rechnitz Rechnit et al J.I. Peterson et al J. J Pickett et al J Jaremko & O. Rorstad
Chemical energy
Electrolysis Coulometry Polarography/Voltammetry P l h /V l 5 Electrogravimetry
Potenciometry I~0
Electroanalytical methods Interfacial methods Static methods I=0 I 0 Potentiometry (E) Dinamic methods I>0 Potentiometric titrations Controlled potential Coulometric Titrations ( (Q = It) ) Amperometric titrations i i Bulk methods Conductometry (G = 1/R) Conductometric Titrations Ti i
Voltammetry [ I = f (E) ]
Electrogravimetry
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Esquemade(Bio)sensorqumico
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Detectores eletroqumicos
Potenciomtricos
Amperomtricos
Medidas realizadas sem a passagem de corrente eltrica Baseada na mudana de potencial da superfcie do t i ld f i d eletrodo de trabalho
Medidas de corrente eltrica realizadas sob a aplicao de um potencial eltrico constante Baseada nas reaes oxidao e reduo que ocorrem na superfcie do eletrodo
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2. 2 Fundamental Concepts
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Electrical conduction
Materiais Isolantes Condutores I nicos Solu es de Eletr litos Cristais Dopados
I = dQ/dt
e-
Electronic conductor
Ionic conductor
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Condutores Eletrnicos e Inicos Eletrnicos: Obedecem a lei de Ohm (E = IR) E = Diferena de Potencial (volts) devido ao movimento f ( ) de eltrons p g R = Resistncia (ohms) do condutor passagem de Corrente I = Corrente (amperes)
Inicos: Obedecem a lei de Ohm para pequenos valores de corrente l d E = Diferena de Potencial ( lts) devido ao movimento Dif d P t i l (volts) d id i t de ons R = Resistncia (ohms) do eletrlito passagem de corrente 13 I = Corrente(amperes)
Reaes de Oxi-Reduo Transferncia de eltrons de um reagente para outro 2 Ag+ + Cu(s) 2Ag(s) + Cu2+
Esta reao pode ser realizado por dois caminhos fisicamente dif fi i t diferentes t Caminho 1: Colocar os reagentes em contato direto
Cuo Cuo
Ag+ Ag A o
Ag+ Cu2+
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Eletrodo de Cobre
Eletrodo de Prata
nodo (oxidao)
Ctodo (reduo)
C p Componentes de uma C Clula Eletroqumica q 2 condutores imersos em uma soluo contendo eletrlitos (eletrodos) 1 condutor eletrnico externo para permitir o fluxo de eltrons 1 condutor inico para evitar o contato direto dos reagentes e permitir 15 o fluxo de ons
eee-
e-
e-
Reduo
NO3
Ag+
NO3
e-eee-
Cu2+
SO4
2-
Cu2+
CuSO4 K+
ClClK+
AgNO3 g
Ag+
NO3
Interface Eletrodo/soluo
Interface Eletrodo/soluo
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2+ Cuo + Zn2
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Relationship between the potential of an Fe3+/Fe2+ half cell relative half-cell to the reference electrodes. The potential relative to a standard hydrogen electrode is shown in blue, the potential relative to a y g , p saturated silver/silver chloride electrode is shown in red, and the potential relative to a saturated calomel electrode is shown in green.
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Junction Potentials
Fig. Fig Origin of the junction potential between a solution of 0 1 0.1 29 M HCl and a solution of 0.01 M HCl.
Potential of Junction
ti = nmero de transporte
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Caso 1
P. P Henderson (Z Physik Chem 59 118 (1907); 63 (Z. Physik. Chem., 59, 63, 325 (1908)): Clculo da juno lquida entre 2 solues com concentraes diferentes (C1 e C2) mas ), de mesma valncia Ag AgCl MCl(C1) MCl(C2) AgCl Ag Ej = 0,0591 (2 t+ -1) log C1/C2
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Caso 2
Lewis & Sargent (J. Am. Chem. Soc., 31, 363 (1909)): Clculo do potencial de juno lquida entre 2 eletrlitos univalentes diferentes de mesma concentrao com um on comum Ag AgCl M1Cl(C) M2Cl(C) AgCl Ag
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In potentiometry the potential p y p of an electrochemical cell is measured under static conditions. Because no current or only a negligible current flows through the electrochemical cell.
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Potenciometria
Equao de Nernst
1a)Electrodes of the First Kind or Class responds to the activity of Mn+ Examples: Ag, Hg, Cu, Pb in contact with Ag+, Hg2+, Cu2+, Pb2+ Cu2+(aq) + 2 e Cuo Eo = 0.34 V
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Potentiometric Titration
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Table. Standard EMF`s and pEO for some common redox couples p p
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This first kind electrode in presence of AgI has the following half-cell equation:
Where:
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Where:
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Ex:
Where :
Electrode Membranes
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If the smaller ions are able to diffuse through the membrane but the larger ions cannot, a potential difference will develop between the two solutions. This membrane potential can be observed by introducing a pair of platinum electrodes.
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K K- Constant The analytes interaction with the membrane generates a membrane potential if analyte s there is a difference in its activity on the membranes two sides.
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&
Eisenman
(1960-1975):
Alkaline
and
alkaline-earth
Reference electrolyte Inner solution Sample solution E1 = Outer potential of the glass membrane (a1); E2 = Asymmetry potential: glass thickness; asymmetry; wearing; E3 = Inner potential of the membrane (a1); E4 = Inner reference electrode potential (aCl-); E5 = Outer reference electrode potential; E6 = Junction potential; Glass membrane (0.2-0.5 mm) Gel layer (10-4 mm)
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aq = aqueous solution; g g sg = surface gel ; g = gel layer; v = dry glass layer layer.
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Schematic representation of the atomic structure of (a) soda silica glass; (b) soda aluminosilica glass
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Reference element Lead-off electrode Reference electrolyte Diaphragm Internal buffer Membrane
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Ideal application: a pH range of approximately 0.5 to 9; At more basic pH levels the glass membrane is more responsive to other cations cations, such as Na+ and K+ (alkaline error).
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zA and zI = charges of the analyte and the interferent; KA I = selectivity coefficient. A,I
(aA)e and (aI)e = activities of analyte and interferent; If KA,I is 1.0, the membrane responds equally to the analyte and the interferent; If a membrane shows good selectivity, KA,I << 1.0.
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NAS 11-18 from Na+ Na2O Al2O3 SiO2 11% (mol) 18% 71%
Seletividade: S l ti id d pH > 7 KNa,K = 10-3 pH = 7 KNa,K = 3 3 10-3 H 3.3.10 3 pH < 7 KNa,H > 1 Seletividade: H+ > Ag+ > K+ = NH4+ > Na+ >Li+ ....>> Ca2+ >>
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Potentiometric Titration
a)Anionic Species:
Ionic Pair
Preparation of the polimeric membrane with the active material 2 - 10 % (m/m) of ionic pair; ( / ) fi i i 60 68 % (m/m) of plasticizer DBP (dibutylphtalate), DOP (dioctylphtalate), or 2-nitrofeniloctileter (o-NPOE); 30 % (m/m) PVC; dissolve the mixture in 10 mL THF (tetrahydrofuran)
First L-ISE selective to Ca2+ developed by Ross ( p y (Science, 156, 1378 ( , , (1967). ) The membrane is placed at the end of a non-conducting cylindrical tube, and is in contact with two reservoirs. The outer reservoir contains di-(n-decyl) phosphate in di-n-octylphenylphosphonate, which soaks into the porous membrane. The inner reservoir contains a standard aqueous solution of Ca2+ and a Ag/AgCl reference
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electrode.
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Ag/AgCl electrode 0.1 mol L-1 CaCl solution PVC tube PVC membrane
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Coaxial cable
Outer conductor Paraffin Inner insulation Inner cond ctor conductor Polymeric membrane with ionic exchanger ith i i h
Cattrall, R. W. & Freiser, H.; Anal. Chem.; 43, 1905 (1971).
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Preparation of th t b l electrode. A = acrylic mold with 8 and 10 mm of i P ti f the tubular l t d li ld ith d f inner and outer diameters, respectively, 7 mm of length, a = 1mm diameter hole. B = adaptation of the central conductor of coaxial cable with welded copper plate. C = mold filled with graphite-epoxy paste. D = view of the electrode showing the 89 channel where it was deposited the PVC membrane.
copper plate l
coaxial cable
A = View of the support; B = View of the tubular electrode holder on the support. 1 = Acrylic holders. 2 = Screws, 3 = rings of silicone rubber, 4 = 90 coaxial cable, 5 = polyethylene tubes (input and output of fluid).
Potentiometric determination of saccharin using coated-carbon rod ISEs and a graphite-epoxy ISE
H3C H2N N S N (CH3)2
+
O N
-
SO2
4 2 cm
0.5 0 5 cm
6 cm m
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C S
L W
RE TISE coating
6 mm
1 mm
2-3 cm
Schematic diagram of the flow system and tubular ISE of carbon rod: 1) PVC membrane with ionic pair; 2) epoxy resin coating; 3) electric connection.
Manual
8.1 x 10-5 1.4 x 10-2 mol L-1 DL = 6.3 x 10-5 mol L-1 Slope = 58.9 + 0.9 mV dec-1 Lifetime = 9 months (over 1000 determinations)
FIA
1.0 x 10-4 1.0 x 10-2 mol L-1, DL = 8.0 x 10-5 mol L-1 Slope = 53.1 + 0.4 mV dec-1 Sampling frequency = 40 h-1
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2 4 1 1.0 1 0 x 10-2 1 0 x 10-4 mol L-1, 1.0 DL= 8.0 x 10-5 mol L-1 Slope= 53.1 + 0.4 mV dec-1 Sampling frequency = 40 h-1
Fatibello-Filho, O.; Aniceto, C. Lab. Rob. and Autom., 11, 234 (1999).
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