Aula 3- Breve histrico dos eletrodos, conceitos fundamentais e potenciometria

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

Breve histrico sobre os sensores

Tabela- Breve histrico sobre o desenvolvimento dos sensores qumicos
Ano 1888 1906 1922 1930 1934 1936 1956 1958 1958 1959 Tipo de sensor Eletrodos metlicos/ons Eletrodo de vidro Eletrodo gotejante de Hg Eletrodo de vidro/Corning 015 Eletrodo d id El t d de vidro para N (I) Na(I) Eletrodo c/ CaF2 para Ca(II) Eletrodo para Oxignio Eletrodo para CO2 Eletrodo de pasta de carbono Sensor piezeltrico Investigador W. Nernst M. Cremer J. Heyrovsky D. Innes & M. Dole B. Lengyel & E. Bl B L l E Blum H.J.C. Tenderloo L.C. L C Clark W. Severinghaus & A. Bradley R.N. Adams G.Z. Sauerbrey

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

Electrical energy energ

Non-electrolytic cells (gavanic) Spontaneous process G < 0 E > 0 Electrolytic cells Non-Spontaneous p process G > 0 E < 0

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

Constant current Electrogravimetry (wt)

Const. electrode potential coulometry (Q = 01 idt

Voltammetry [ I = f (E) ]

Electrogravimetry
6

Esquemade(Bio)sensorqumico
7

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
8

2. 2 Fundamental Concepts

11

Electrical conduction
Materiais Isolantes Condutores I nicos Solu es de Eletr litos Cristais Dopados

Eletr nicos Metais, xidos Inorg nicos, Pol meros Condutores

I = dQ/dt
e-

Electronic conductor

Ionic conductor

12

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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Clula Eletroqumica Caminho 2: Separar os reagentes em um arranjo apropriado

ee-

Eletrodo de Cobre

Ponte Salina (KCl sat.)

Eletrodo de Prata

[Cu2+] = 1.00 mol/L Cu(s) Cu2+ + 2eAg+ + e-

[Ag+] = 1.00 mol/L Ag(s)

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

Clula Eletroqumica Movimento de cargas

eee-

e-

e-

Oxidao e- Cu2+ eeeSO4

2-

Reduo
NO3

Ag+
NO3

e-eee-

Cu2+
SO4
2-

Cu2+

CuSO4 K+

ClClK+

AgNO3 g

Ag+
NO3

Interface Eletrodo/soluo

Interface Eletrodo/soluo

Voltaic or Galvanic Cell

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Ecell = Ecatt Ean + Ej ll

18

Schematic diagram showing the standard hydrogen electrode t d dh d l t d

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Voltaic or Galvanic Cell

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2+ Galvanic Cell: Zno + Cu2

2+ Cuo + Zn2
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Schematic diagram showing the saturated calomel electrode

Schematic diagram showing a Ag/AgCl electrode.

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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

Potencial de Juno Lquida: Origem e Clculos

Devido a diferena de mobilidade dos ons que transportam pela juno (ponte salina) Max Planck (Ann. Phys., 39, 161 (1890); 40, 561 (1890)

sendo Zi = nmero atmico

ti = nmero de transporte

1 1 i = mobilidade inica (cm2 s-1V-1) bilid d i i (

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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

Onde a condutncia inica equivalente a diluio infinita de cada eletrlito a ee o

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3. Potentiometric Methods and Electrodes

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Potentiometric Methods and electrodes: Principles

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

E = E* + 0,059 / n log [ox] / [red]

Equao de Nernst

Metallic Indicator Electrodes

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

ECu2+/Cu = EoCu2+/Cu + 0.0592/2 + log [Cu2+]

Ecell = Eind Eref + Ej

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1b) Redox Electrodes Pt, Au and Pd electrodes

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Potentiometric Methods: Redox Electrodes

Treatment of platinum electrode The platinum electrode generally form a monolayer of PtO on its surface that causes changes in its potential and also delay its response, The l Th electrode can b attacked b d be k d by: a) Oxidizing solutions containing Cl- with formation of PtCl4-; b) Natural waters or other oxidant solutions with formation of PtO; c) Cr(II) in acid medium reduces H+ by formation of adsorbed H2 on Pt Pre-treatment of Pt electrode a) Mechanical with Al2O3 or CeO2 or diamond powder; b) Chemical (alcoholic KOH , sulphochromic, aqua regia or Ce(SO4)2 solution) ; c) Electrolytic: a) Cathodic - remove the oxide layer; b) Anodic - remove adsorbed H2
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Potentiometric Titration

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Potentiometric Methods and electrodes: Electron activity and pE

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Potentiometric Methods and electrodes: Electron activity and pE

Continuing...

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Potentiometric Methods and electrodes:

Principles Electron activity and pE

Table. Standard EMF`s and pEO for some common redox couples p p

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Potentiometric Methods: Electrodes of the Second kind

The electrode of the second kind responds to the activity of another specie in equilibrium with Mn+ (precipitate or stable complexes) Generally this species are complexes). anions. Ex: the potential of a A electrode i a solution of A + i h i l f Ag l d in l i f Ag is:

This first kind electrode in presence of AgI has the following half-cell equation:

Where:

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Potentiometric Methods: Electrodes of the Second kind

Another examples: Ag/AgCl(s), Ag/AgBr(s), (Hg/HgY2-).

Where:

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Potentiometric Methods: Electrodes of the Second kind

Electrode of the second kind: metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H3O+ (pH). Ex:

Ex:

Potentiometric Methods: Electrodes of the third kind

Electrode of the third kind responds to the activity of another Cation in specific conditions. conditions Some times when an electrode of the second kind is subjected to a redox reaction and another reaction, such as a solubility reaction (involving more than two reactions) an electrode of the third kind is found found. Ex:

Where :

Electrode Membranes

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Origin of a membrane potential

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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Potentiometric Methods: Membrane potential

A typical potentiometric electrochemical cell equipped with an ion-selective electrode. The electrochemical cell includes two reference electrodes: one immersed in the ion-selective electrodes internal solution and one in the sample. The cell potential, therefore, is: Variable

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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Potentiometric Methods: Glass Selective Electrodes

Fritz Haber (1901): discovered that there is a change in potential across a g glass membrane when its two sides are in solutions of different acidity. y Harber & Klemensiewicz (1909): First glass electrode + Nernst equation; Mc-Innes & Dole (1930): Corning 015 (commercial); Lengyel & Blum (1934): Na+ electrode; Nikolsky electrodes;
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&

Eisenman

(1960-1975):

Alkaline

and

alkaline-earth

Potentiometric Methods: pH Glass Electrode

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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Potentiometric Methods: Glass Selective Electrodes

Schematic representation of the reactions in a glass membrane

aq = aqueous solution; g g sg = surface gel ; g = gel layer; v = dry glass layer layer.

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Potentiometric Methods: Glass Selective Electrodes

Schematic representation of the atomic structure of (a) soda silica glass; (b) soda aluminosilica glass
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Potentiometric Methods: Combined pH Glass Electrode

Screw Cap Filling port Connecting plug

Reference element Lead-off electrode Reference electrolyte Diaphragm Internal buffer Membrane

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An early Beckman pHmeter

Arnold Beckman (1934 -1939)

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Potentiometric Methods: Glass Selective Electrode

Asymmetry potential and pHmeter calibration

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Potentiometric Methods: Glass Selective Electrodes

pHmeter calibration Dependence of the factor pre-Nernstian with T

K is found using buffer solutions

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Potentiometric Methods: Glass Ion-Selective Electrodes

Corning 015 (first commercial) = 22% Na2O, 6% CaO and 72% SiO2. When immersed in an aqueous solution for 7 h, the outer approximately 10 nm of the membranes surface becomes hydrated, resulting in negatively charged sites, SiO. Na+, serve as counter ions. H+ displace the Na+, giving rise to the membranes selectivity for H+.

Corning 015 obeys the following equation:

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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Potentiometric Methods: Selectivity of Membranes

Most membranes are not selective toward a single analyte. Instead, the membrane potential is proportional to the concentration of each ion that interacts with the membranes active sites.

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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Nikolsky s Nikolskys equation:

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+ >>

NAS 27-4 from K+ Na N 2O Al2O3 SiO2 27% ( l) (mol) 4% 69%

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Potentiometric Titration

Solid-based graphite-epoxy electrodes for potentiometric measurements of pH and acid-base titration

Graphite-epoxy composite 40% m/m PbO2 30% m/m silica gel 30% m/m -MnO2 30% m/m Fe2O3 20% magnesium silicate Cu/Cu2S film pH range 1.0 11 2.0 13 2.0 13 1.7 12.5 1.0 12.0 acid-base titrations Slope / mV pH-1 -58.7 + 0.3 -40.5 + 0.4 -53.6 + 0.5 -39.7 + 0.6 -39.2 + 0.3 -59.0 + 0.5 Lifetime / mon (det) > 8 (> 1200) > 12 (> 6000) > 4 (1500) > 6 (2000) > 8 (1500) > 3 (400) Ref. 1 2 3 4-6 7 8
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Potentiometric Methods: Liquid-Based Selective Electrodes

This class of ISEs uses a hydrophobic membrane containing a liquid organic complexing agent that reacts selectively with the analyte. Three types of organic complexing agents have been used: Cation exchangers; Anion exchangers; Neutral ionophores. One example of a liquid-based ion-selective electrode is that for Ca2+, which uses a porous plastic membrane saturated with th cation exchanger di ( d l) l ti b t t d ith the ti h di-(n-decyl) phosphate.
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Potentiometric Methods: Kind of ionic exchangers

Cationic exchangers: Calcium di-(n-decyl) phosphate: (Ca[PO2 (CH3(CH2)9O)2]; Sodium tetraphenylborate: (NaB4); Anionic exchangers: g Tricaprylylmethylammonium chloride (Aliquat 336) : CH3N[(CH2)7CH3]3Cl ; Protonated tertiary amine ( y (tri-n-octylamine); y ); Tri-n-benzylamine; Tetraphenylarsonium chloride ((AsPh4)Cl) Neutral exchangers: Valinomycin; Crown ether.
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Preparation of the ionic pair and polimeric membrane

Preparation of the active material P ti f th ti t i l a)Cationic Species: ) p
Ionic Pair

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)

Potentiometric Methods: Liquid-Based Selective Electrodes

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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Potentiometric Methods: PVC membrane electrode

PVC membrane electrode b l t d developed by Moody et al (Analyst, 95, 910 (1970). Electric conection Silicone rubber Glass junction

Ag/AgCl electrode 0.1 mol L-1 CaCl solution PVC tube PVC membrane
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Potentiometric Methods: Polymeric membrane

Experimental arrangement for casting PVC membrane

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Potentiometric Methods: Polymeric membrane with ionic exchanger

First Coated-wire Fi t C t d i PVC ion-selective electrode i l ti l t d

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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Coated graphite ion-selective electrode

Coated graphite ion-selective electrode

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Potentiometric Methods: Tubular electrode

Tubular electrode made of graphite-epoxy with a PVC film

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.

Potentiometric Methods: Tubular electrode

acrylic mold

copper plate l

graphite-epoxy paste Shielded Connector

coaxial cable

Details of the tubular electrode based on graphite-epoxy PVC film

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

Toluidine blue O-saccharinate O saccharinate Ion-pair: 5:30:65 % m/m ionpair:DBPh:PVC

4 2 cm

0.5 0 5 cm

6 cm m

Coated-carbon rod ISEs (1 and 2) and graphite-epoxy ISE (3)

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FI-Potentiometric determination of saccharin using a tubular ISE

pH R
3 2 1

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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Transient potentiometric signals for saccharin determination

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).

Eletrodo para gases (Severinghaus e Bradley)

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