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Aula 3- Breve histórico 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, faraday’s 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), Indicator electrodes: 1) metallic electrodes: first (cation or redox electrode), second and 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

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,Springer- Verlag, 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 tissues and crude extracts for environmental, food and pharmaceutical analysis, In: S. Alegret & A. Merkoçi, Comprehensive Analytical Chemistry, Vol. 49-Electrochemical Sensor Analysis”, Amsterdam, Elsevier , 355-375, 2007

Breve histórico sobre os sensores

Tabela- Breve histórico sobre o desenvolvimento dos sensores químicos

Ano

Tipo de sensor

Investigador

1888

Eletrodos metálicos/íons

W. Nernst M. Cremer J. Heyrovsky D. Innes & M. Dole B. Lengyel & E. Blum H.J.C. Tenderloo L.C. Clark W. Severinghaus & A. Bradley R.N. Adams G.Z. Sauerbrey

1906

Eletrodo de vidro

1922

Eletrodo gotejante de Hg

1930

Eletrodo de vidro/Corning 015

1934

Eletrodo de vidro para Na(I)

1936

Eletrodo c/ CaF 2 para Ca(II)

1956

Eletrodo para Oxigênio

1958

Eletrodo para CO 2

1958

Eletrodo de pasta de carbono

1959

Sensor piezelétrico

Ano

Tipo de Sensor

Investigador

1961

Sensor AgI(s) parafina p/ I - Biossensor para glicose Sensor piezelétrico Sensor de LaF 3 /EuF 2 para F - Sensor de membrana liq. p/ Ca 2+ Sensor de membrana de PVC p/ Ca 2+ ChemFET Calorimétrico (enzimático) ENFET

E. Pungor L.C. Clark & W. Lyons 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 et al J.I. Peterson et al J. Pickett et al J Jaremko & O. Rorstad

1962

1964

1966

1967

1970

1970

1974

1975

1979

Biossensor PC c/ ADH e LDH

1979

Biossensor de tecido

1980

Sensor de fibra-óptica

1997

Eletroantenograma

?

Pâncreas artificial implantável

Electrical energy
Electrical energy

Non-electrolytic cells (gavanic)

Electrol tic cells

y

Non-Spontaneous

process ΔG > 0 ΔE < 0 Chemical energy
process
ΔG > 0
ΔE < 0
Chemical energy

Spontaneous

process

ΔG < 0

ΔE>0

Potenciometry I ~ 0

Electrolysis Coulometry Polarography/Voltammetry Electrogravimetry

5

Electroanalytical methods Interfacial Bulk methods methods Static methods I=0 Dinamic methods I > 0
Electroanalytical
methods
Interfacial
Bulk
methods
methods
Static methods
I=0
Dinamic methods
I > 0
Conductometry
(G = 1/R)
Conductometric
Titrations
Potentiometry P o en t ti ome r c t i C ons an t
Potentiometry
P
o en
t
ti
ome r c
t i
C
ons an
t
t
(E)
titrations
current
Controlled
Const.
potential
Coulometric
Titrations
(Q = It)
Electrogravimetry
(wt)
electrode
potential
coulometry
Amperometric
(Q
0
Voltammetry
[ I = f (E) ]
Electrogravimetry
= ∫ 1 id
t
titrations

6

Esquema de (Bio)sensor químico 7

Esquema de (Bio)sensor químico

Detectores eletroquímicos

Potenciométricos

Detectores eletroquímicos Potenciométricos Medidas realizadas sem a passagem de corrente elétrica Baseada na mudança
Detectores eletroquímicos Potenciométricos Medidas realizadas sem a passagem de corrente elétrica Baseada na mudança

Medidas realizadas sem a passagem de corrente elétrica

Baseada na mudança de potencial da supercie do eletrodo de trabalho

Amperométricos

de trabalho A m p e r o m é t r i c o s

Medidas de corrente elétrica realizadas sob a aplicação de um potencial elétrico constante

Baseada nas rea ões

ç

oxidação e redução que ocorrem na superfície do eletrodo

2. Fundamental Concepts

Electrical conduction

Materiais Isolantes Condutores Eletrô nicos Iô nicos Metais, Óxidos Inorgâ nicos, Polí meros Condutores Soluç
Materiais
Isolantes
Condutores
Eletrô nicos
Iô nicos
Metais, Óxidos Inorgâ nicos,
Polí meros Condutores
Soluç õ es de Eletró litos
Cristais Dopados

I = dQ/dt

meros Condutores Soluç õ es de Eletró litos Cristais Dopados I = dQ/dt e - Electronic
e -
e
-

Electronic conductor

meros Condutores Soluç õ es de Eletró litos Cristais Dopados I = dQ/dt e - Electronic

Ionic conductor

12

Condutores Eletrônicos e Iônicos

Eletrônicos : Obedecem a lei de Ohm (E = IR)

E

= Diferença de Potencial (volts) devido ao movimento de elétrons

R

= Resistência (ohms) do condutor à passagem de Corrente

I

= Corrente (amperes)

Iônicos : Obedecem a lei de Ohm para pequenos valores de corrente

E

R

I

= Diferença de Potencial (volts) devido ao movimento de íons

ê

l

= Resist ncia (ohms) do e etr

ól

ito

= Corrente(amperes)

à

passagem de corrente

13

Reações de Oxi-Redução

Transferência de elétrons de um reagente para outro

2 A g

+ + C

( )

u s

de elétrons de um reagente para outro 2 A g + + C ( ) u

2A

( ) + C

g s

u

2+

Esta reação pode ser realizado por dois caminhos fisicamente diferentes

Caminho 1: Colocar os reagentes em contato direto

Cu o

te dif eren t es Caminho 1: Colocar os reagentes em contato direto Cu o Ag

Ag +

te dif eren t es Caminho 1: Colocar os reagentes em contato direto Cu o Ag

Ag o

Cu o

te dif eren t es Caminho 1: Colocar os reagentes em contato direto Cu o Ag

Ag +

Cu 2+

14

Célula Eletroquímica

Caminho 2: Separar os reagentes em um arranjo apropriado

e - e - Ponte Salina Eletrodo de Cobre Eletrodo de Prata (KCl sat.) [Cu
e
-
e
-
Ponte
Salina
Eletrodo de Cobre
Eletrodo de Prata
(KCl sat.)
[Cu 2+ ] = 1.00 mol/L
[Ag + ] = 1.00 mol/L

Cu(s)

sat.) [Cu 2+ ] = 1.00 mol/L [Ag + ] = 1.00 mol/L Cu(s) Cu 2

sat.) [Cu 2+ ] = 1.00 mol/L [Ag + ] = 1.00 mol/L Cu(s) Cu 2

Cu 2+ + 2e -

Ânodo (oxidação)

Ag + + e -

Ag(s)Cu 2 + + 2e - Ânodo (oxidação) Ag + + e - Cátodo (redução) Comp Cu 2 + + 2e - Ânodo (oxidação) Ag + + e - Cátodo (redução) Comp

Cátodo (redução)

Componentes de uma Célula Eletroquímica • 2 condutores imersos em uma solução contendo eletrólitos (eletrodos)

• 1 condutor eletrônico externo para permitir o fluxo de elétrons

1 condutor iônico para evitar o contato direto dos reagentes e permitir o fluxo de íons

15

Célula Eletroquímica – Movimento de cargas

e - e - e -
e
- e -
e
-
e - e - Oxidação Redução e - Cu 2+ NO 3 e - -
e -
e -
Oxidação
Redução
e - Cu 2+
NO 3
e -
-
2-
e
-
SO 4
Ag +
e -
Cu
2+
NO 3
e -
2-
e -
SO
Ag +
4
CuSO 4
Cl -
AgNO 3
e -
e
-
Cu
2+
K +
NO 3
Cl -
K +
Interface Eletrodo/solução

Interface Eletrodo/solução

Voltaic or Galvanic Cell

16

17
17
17
17
17

17

E = E

cell

cat

E

an

+ E

j

Schematic diagram showing the standard hyd rogen e lect ro de 19

Schematic diagram showing the standard hydrogen electrode

Voltaic or Galvanic Cell 20

Voltaic or Galvanic Cell

20

21
Galvanic Cell: Zn o + Cu 2 + Cu o + Zn 2 + 22

Galvanic Cell: Zn o + Cu 2+

Cu o + Zn 2+

Schematic diagram showing the saturated calomel electrode Schematic diagram showing a Ag/AgCl electrode. 23
Schematic diagram showing the saturated calomel electrode Schematic diagram showing a Ag/AgCl electrode. 23

Schematic diagram showing the saturated calomel electrode

Schematic diagram showing a Ag/AgCl electrode.

24
25
26
26
27
27
3+ 2+ Relationship between the potential of an Fe /Fe half-cell relative to the reference

3+

2+

Relationship between the potential of an Fe /Fe half-cell relative to the reference electrodes. The potential relative to a standard hydrogen electrode is shown in blue, the potential relative to a saturated silver/silver chloride electrode is shown in red, and the potential relative to a saturated calomel electrode is shown in green.

Junction Potentials

Junc t ion Po t en t ials Fig . Origin of the junction potential between

Fig. Origin of the junction potential between a solution of 0.1 M HCl and a solution of 0.01 M HCl.

29

Po t en t ial of Junc t ion

Potential of Junction

Potencial de Junção Líquida: Origem e Cálculos

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

Max Planck ( Ann. Phys ., 39 , 161 (1890); 40 , 561 (1890) sendo Z

sendo Z i = número atômico

(1890); 40 , 561 (1890) sendo Z i = número atômico t i = número de

t i = número de transporte

µ i = mobilidade iônica (cm 2 s -1 V -1 )

Caso 1

P. Henderson (Z. Physik. Chem., 59, 118 (1907); 63, 325 (1908)): Cálculo da junção líquida entre 2

soluções com concentrações diferentes (C de mesma valência

mas

e C )

2 ,

1

Ag AgCl MCl(C 1 )│ │ MCl(C 2 ) AgCl Ag

E j = 0,0591 (2 t + -1) log C 1 /C 2

Caso 2

Lewis & Sargent (J. Am. Chem. Soc., 31, 363 (1909)):

Cálculo do potencial de junção líquida entre 2 eletrólitos univalentes diferentes de mesma concentração com um íon comum

Ag AgCl M 1 Cl(C)│ │ M 2 Cl(C) AgCl Ag

│ M 1 Cl(C) │ │ M 2 Cl(C) │ AgCl │ Ag Onde Λ é

Onde Λ é a condutância iônica equivalente a diluição infinita de cada eletrólito

34

34

3. Potentiometric Methods and Electrodes

Potentiometric Methods and electrodes: Principles
Potentiometric Methods and electrodes: Principles
is 36
is
36
Potentiometric Methods and electrodes: Principles is 36 cell In p otentiometr y the p otential of

cell

In potentiometry the potential

of

measured

conditions. Because no current

or

the

flows

current

electrochemical

a

under

negligible

through

an

static

only

electrochemical cell.

Potenciometria

Potenciometria E = E * + 0,059 / n log [ox] / [red] Equação de Nernst

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

Potenciometria E = E * + 0,059 / n log [ox] / [red] Equação de Nernst

Metallic Indicator Electrodes

1a)Electrodes of the First Kind or Class responds to the activity of M

n+

Examples: Ag, Hg, Cu, Pb in contact with Ag + , Hg 2+ , Cu 2+ , Pb 2+

Cu 2+ (aq) + 2 e

Cu o

E o = 0.34 V

E Cu2+/Cu = E o Cu2+/Cu + 0.0592/2 + log [Cu 2+ ]

E cell = E ind E ref + E j

1b) Redox Electrodes

Pt, Au and Pd electrodes

1b) Redox Electrodes Pt, Au and Pd electrodes 40
1b) Redox Electrodes Pt, Au and Pd electrodes 40
1b) Redox Electrodes Pt, Au and Pd electrodes 40
Potentiometric Methods: Redox Electrodes
Potentiometric Methods: Redox Electrodes

Treatment of platinum electrode

Th

changes in its potential and also delay its response,

The electrode can be attacked by:

a) Oxidizing solutions containing Cl - with formation of PtCl 4 -;

b) Natural waters or other oxidant solutions with formation of PtO;

c) Cr(II) in acid medium reduces H+ by formation of adsorbed H 2 on Pt

Pre-treatment of Pt electrode

l

e p a

ti

l

t

d

ll

f

l

f PtO

it

f

s sur ace

num e ec ro e genera

y

orm a mono ayer o

on

th

t

a causes

a) Mechanical with Al 2 O 3 or CeO 2 or diamond powder;

b) Chemical (alcoholic KOH , sulphochromic, aqua regia or Ce(SO 4 ) 2 solution) ;

c) Electrolytic: a) Cathodic - remove the oxide layer; b) Anodic - remove adsorbed H 2

41

Potentiometric Titration

Potentiometric Titration 42
Potentiometric Titration 42
Potentiometric Methods and electrodes: Electron activity and pE
Potentiometric Methods and electrodes: Electron activity and pE
Potentiometric Methods and electrodes: Electron activity and pE 43
Potentiometric Methods and electrodes: Electron activity and pE 43

43

Potentiometric Methods and electrodes: Electron activity and pE
Potentiometric Methods and electrodes: Electron activity and pE

Continuing

Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44
Potentiometric Methods and electrodes: Electron activity and pE Continuing 44

44

Potentiometric Methods and electrodes: Principles Electron activity and pE Table. Standard EMF ` s and

Potentiometric Methods and electrodes: Principles Electron activity and pE

Potentiometric Methods and electrodes: Principles Electron activity and pE

Table. Standard EMF ` s and pE O for some common redox couples

Principles Electron activity and pE Table. Standard EMF ` s and pE O for some common
Principles Electron activity and pE Table. Standard EMF ` s and pE O for some common

45

Potentiometric Methods: Electrodes of the Second kind
Potentiometric Methods: Electrodes of the Second kind

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

n+

of a Ag el ectro de in a solution of Ag + is: n+ This first

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

solution of Ag + is: n+ This first kind electrode in presence of AgI has the

Where:

solution of Ag + is: n+ This first kind electrode in presence of AgI has the
solution of Ag + is: n+ This first kind electrode in presence of AgI has the
solution of Ag + is: n+ This first kind electrode in presence of AgI has the

46

Potentiometric Methods: Electrodes of the Second kind
Potentiometric Methods: Electrodes of the Second kind

Another examples: Ag/AgCl(s), Ag/AgBr(s), (Hg/HgY 2- ).

Methods: Electrodes of the Second kind Another examples : Ag/AgCl(s), Ag/AgBr(s), (Hg/HgY 2 - ). Where:

Where:

Methods: Electrodes of the Second kind Another examples : Ag/AgCl(s), Ag/AgBr(s), (Hg/HgY 2 - ). Where:
Methods: Electrodes of the Second kind Another examples : Ag/AgCl(s), Ag/AgBr(s), (Hg/HgY 2 - ). Where:

47

Potentiometric Methods: Electrodes of the Second kind
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 H 3 O + (pH).

Ex:

metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3
metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3

Ex:

metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3
metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3
metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3
metal-metal oxide electrodes Ex: Ti, Pb, Nb, Sb, W when passivated chemically responses to H 3
Potentiometric Methods: Electrodes of the third kind
Potentiometric Methods: Electrodes of the third kind

Electrode of the third kind responds to the activity of another Cation in specific 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. Ex:

such as a solubility reaction (involving more than two reactions) an electrode of the third kind
such as a solubility reaction (involving more than two reactions) an electrode of the third kind
such as a solubility reaction (involving more than two reactions) an electrode of the third kind
such as a solubility reaction (involving more than two reactions) an electrode of the third kind

Where :

such as a solubility reaction (involving more than two reactions) an electrode of the third kind
Electrode Membranes
Electrode Membranes
Electrode Membranes 50

50

Origin of a membrane potential

Origin of a membrane potential If the smaller ions are able to diffuse through the membrane
Origin of a membrane potential If the smaller ions are able to diffuse through the membrane

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.

5151

52
52
52

52

Potentiometric Methods: Membrane potential
Potentiometric Methods: Membrane potential

A

electrode.

typical

potentiometric

electrochemical

cell

equipped

with

an

ion-selective

electrochemical cell equipped with an ion-selective The electrochemical cell includes two reference electrodes:

The electrochemical cell includes two reference

electrodes: one immersed in the ion-selective

electrode’s internal solution and one in the

sample. The cell potential, therefore, is:

Variable

in the sample . The cell potential, therefore, is: Variable K- Constant The analyte ’s interaction
in the sample . The cell potential, therefore, is: Variable K- Constant The analyte ’s interaction

K- Constant

The analyte’s interaction with the membrane generates a membrane potential if

Potentiometric Methods: Glass Selective Electrodes

Fritz Haber (1901): discovered that there is a change in potential across a glass membrane when its two sides are in solutions of different acidity.

Harber & Klemensiewicz (1909): First glass electrode + Nernst equation;

Mc-Innes & Dole (1930): Corning 015 (commercial);

Lengyel & Blum (1934): Na + electrode;

electrodes ;

Nikolsky

&

Eisenman

(1960-1975):

Alkaline

and

alkaline-earth

54

Potentiometric Methods: pH Glass Electrode
Potentiometric Methods: pH Glass Electrode
Reference electrolyte Inner solution
Reference
electrolyte
Inner
solution

Sample l E 1 = Outer potential of the glass membrane (a 1 ); E 2 = Asymmetry potential:

so u

ti

on

glass thickness;

asymmetry;

wearing; E 3 = Inner potential of the membrane (a 1 ‘); E 4 = Inner reference electrode potential (a Cl ); E 5 = Outer reference electrode potential; E 6 = Junction potential;

-

electrode potential; E 6 = Junction potential; - Glass membrane (0.2-0.5 mm) Gel layer (10 -
electrode potential; E 6 = Junction potential; - Glass membrane (0.2-0.5 mm) Gel layer (10 -
electrode potential; E 6 = Junction potential; - Glass membrane (0.2-0.5 mm) Gel layer (10 -

Glass membrane (0.2-0.5 mm) Gel layer (10 -4 mm)

55

Potentiometric Methods: Glass Selective Electrodes
Potentiometric Methods: Glass Selective Electrodes
Potentiometric Methods: Glass Selective Electrodes Schematic representation of the reactions in a glass membrane aq =

Schematic representation of the reactions in a glass membrane

aq = aqueous solution;

sg = surface gel ; g = gel layer; v = dry glass layer.

56
56
Potentiometric Methods: Glass Selective Electrodes
Potentiometric Methods: Glass Selective Electrodes
Potentiometric Methods: Glass Selective Electrodes Schematic representation of the atomic structure of (a) soda silica

Schematic representation of the atomic structure of (a) soda silica glass; (b) soda aluminosilica glass

57

Potentiometric Methods: Combined pH Glass Electrode
Potentiometric Methods: Combined pH Glass Electrode
Potentiometric Methods: Combined pH Glass Electrode Screw Cap Filling port Connectin g p lu g Reference

Screw Cap

Filling port

Connecting plug

Reference element Lead-off electrode Reference electrolyte

Diaphragm Internal buffer Membrane

58

An early Beckman pHmeter

An early Beckman pHmeter k (1934 -1939) A ld B rno ec man 59

k (1934 -1939)

A

ld B

rno

ec man

An early Beckman pHmeter k (1934 -1939) A ld B rno ec man 59

59

Potentiometric Methods: Glass Selective Electrode
Potentiometric Methods: Glass Selective Electrode

Asymmetry potential and pHmeter calibration

Potentiometric Methods: Glass Selective Electrode Asymmetry potential and pHmeter calibration 61

61

Potentiometric Methods: Glass Selective Electrodes
Potentiometric Methods: Glass Selective Electrodes

pHmeter calibration

Dependence of the factor pre-Nernstian with T

Electrodes pHmeter calibration Dependence of the factor pre-Nernstian with T 62 K is found using buffer
Electrodes pHmeter calibration Dependence of the factor pre-Nernstian with T 62 K is found using buffer
Electrodes pHmeter calibration Dependence of the factor pre-Nernstian with T 62 K is found using buffer

62

K is found using buffer solutions

Electrodes pHmeter calibration Dependence of the factor pre-Nernstian with T 62 K is found using buffer
Electrodes pHmeter calibration Dependence of the factor pre-Nernstian with T 62 K is found using buffer
63
64

64

65
Potentiometric Methods: Glass Ion-Selective Electrodes
Potentiometric Methods: Glass Ion-Selective Electrodes

Corning 015 (first commercial) = 22% Na 2 O, 6% CaO and 72% SiO 2 . When immersed in an aqueous solution for 7 h, the outer approximately 10 nm of the membrane’s surface becomes hydrated, resulting in negatively charged sites, —SiO–. Na + , serve as counter ions. H + displace the Na + , giving rise to the membrane’s selectivity for H+.

+ , giving rise to the membrane’s selectivity for H+. Corning 015 obeys the following equation:

Corning 015 obeys the following equation:

for H+. Corning 015 obeys the following equation: Ideal application: a pH range of approximately 0.5

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, such as Na + and K + (alkaline error).

66

Potentiometric Methods: Selectivity of Membranes
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 membrane’s active sites.

ion that interacts with the membrane’s active sites . z A and z I = charges

z A and z I = charges of the analyte and the interferent;

K

= selectivity coefficient.

A,I

and the interferent ; K = selectivity coefficient . A,I (a A ) e and (a

(a A ) e and (a I ) e = activities of analyte and interferent; If K A,I is 1.0, the membrane responds equally to the analyte and the interferent; If a membrane shows good selectivity, K A,I << 1.0.

67

68

68

Nikolskys equation:

Nikolsky ’ s equat i on: NAS 11-18 from Na + Na 2 O Al 2

NAS 11-18 from Na +

Na 2 O

Al 2 O 3 18%

11% (mol)

SiO 2

71%

NAS 27-4 from K +

Na 2 O

Al 2 O 3 4%

27% (mol)

SiO 2

69%

Seletividade:

pH > 7 K Na,K = 10 -3

pH = 7 K Na,K = 3.3.10 -3

pH < 7

K Na,H > 1

Seletividade:

H +

+

> Ag

> K

+

+

= NH 4

+

> Na >Li

+

2+

>> Ca

Potentiometric Titration

Potentiometric Titration

Solid-based graphite-epoxy electrodes for potentiometric

measurements of pH and acid-base titration

Graphite-epoxy

pH range

Slope / mV pH -1

Lifetime /

Ref.

composite

mon (det)

40% m/m PbO 2

1.0 – 11

-58.7 + 0.3

> 8 (> 1200)

1

30% m/m silica gel

2.0

– 13

-40.5 + 0.4

> 12 (> 6000)

2

30% m/m λ-MnO 2

2.0

– 13

-53.6 + 0.5

> 4 (1500)

3

30% m/m Fe 2 O 3

1.7

– 12.5

-39.7 + 0.6

> 6 (2000)

4-6

20% magnesium silicate

1.0

– 12.0

-39.2 + 0.3

> 8 (1500)

7

Cu/Cu 2 S film

acid-base

-59.0 + 0.5

> 3 (400)

8

titrations

74

Potentiometric Methods: Liquid-Based Selective Electrodes
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 Ca 2+ , which uses a porous plastic membrane saturated with the cation exchanger di-(n-decyl) phosphate.

75

Potentiometric Methods: Kind of ionic exchangers
Potentiometric Methods: Kind of ionic exchangers

Cationic exchangers:

Calcium di-(n-decyl) phosphate: (Ca[PO 2 (CH 3 (CH 2 ) 9 O) 2 ]; Sodium tetraphenylborate: (NaBØ );

4

Anionic exchangers:

Tricaprylylmethylammonium chloride (Aliquat 336) : CH 3 N[(CH 2 ) 7 CH 3 ] 3 Cl ;

Protonated tertiary amine (tri-n-octylamine);

Tri-n-benzylamine; Tetraphenylarsonium chloride ((AsPh )Cl)

4

Neutral exchangers:

Valinomycin;

Crown ether.

76

Preparation of the ionic pair and polimeric membrane

Preparation of the active material

a)Cationic Species:

a)Anionic Species:

ti ve ma t er ial a) Cationic S p ecies: a)Anionic Species: Ionic Pair Ionic

Ionic Pair

er ial a) Cationic S p ecies: a)Anionic Species: Ionic Pair Ionic Pair Preparation of the

Ionic Pair

Preparation of the polimeric membrane with the active material

2 - 10 % (m/m) of ionic pair; 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
Potentiometric Methods: Liquid-Based Selective Electrodes
Potentiometric Methods: Liquid-Based Selective Electrodes First L-ISE selective to Ca 2 + develo p ed b

First L-ISE selective to Ca 2+ developed by Ross (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 Ca 2+ and a Ag/AgCl reference electrode.

78

79
Potentiometric Methods: PVC membrane electrode
Potentiometric Methods: PVC membrane electrode

PVC membrane electrode developed by Moody et al (Analyst, 95, 910 (1970).

t ro de developed by Moody et al (Analyst, 95, 910 (1970). Electric conection Silicone rubbe

Electric conection

Silicone rubber

Glass junction

Ag/AgCl electrode

0.1 mol L -1 CaCl solution

PVC tube

PVC membrane

80

Potentiometric Methods: Polymeric membrane
Potentiometric Methods: Polymeric membrane
Potentiometric Methods: Polymeric membrane Experimental arrangement for casting PVC membrane 81

Experimental arrangement for casting PVC membrane

81

82
83
83
84

84

Potentiometric Methods: Polymeric membrane with ionic exchanger
Potentiometric Methods: Polymeric membrane with ionic exchanger

First Coated-wire PVC ion-selective electrode

Coaxial cable Outer conductor Inner insulation Inner conductor Paraffin
Coaxial cable
Outer conductor
Inner insulation
Inner conductor
Paraffin

Polymeric membrane with ionic exchanger

Cattrall, R. W. & Freiser, H.; Anal. Chem.; 43, 1905 (1971).

85

Coated graphite ion-selective electrode

Coated graphite ion-selective electrode

Coated graphite ion-selective electrode

Coated graphite ion-selective electrode
88

88

Potentiometric Methods: Tubular electrode
Potentiometric Methods: Tubular electrode

Tubular electrode made of

ra hite-e ox

g

p

p

y

with a PVC film

electrode made of ra hite - e ox g p p y with a PVC film

Preparation of the tubular electrode. A = acrylic mold with 8 and 10 mm of 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 channel where it was deposited the PVC membrane.

8989

Potentiometric Methods: Tubular electrode
Potentiometric Methods: Tubular electrode
acrylic mold copper plate Shielded Connector
acrylic mold
copper
plate
Shielded Connector

coaxial cable

graphite-epoxy paste

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

of the tubular electrode based on graphite-epoxy PVC film A = View of the support; B

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 = coaxial cable, 5 = polyethylene tubes (input and output of fluid).

9090

Potentiometric determination of saccharin using coated-carbon rod ISEs and a graphite-epoxy ISE

using coate d -carbon rod ISEs and a graphite-epoxy ISE H 3 C H 2 N
using coate d -carbon rod ISEs and a graphite-epoxy ISE H 3 C H 2 N

H

3

C

H 2 N

N S
N
S

N + (CH 3 ) 2

ISE H 3 C H 2 N N S N + (CH 3 ) 2 O
ISE H 3 C H 2 N N S N + (CH 3 ) 2 O
ISE H 3 C H 2 N N S N + (CH 3 ) 2 O
O N - SO 2
O
N -
SO 2
ISE H 3 C H 2 N N S N + (CH 3 ) 2 O

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

1 1 2 3 4 5 0 5 cm . 2 cm 6 cm
1
1
2
3
4
5
0 5 cm
.
2 cm
6 cm
ion- pair:DBPh:PVC 1 1 2 3 4 5 0 5 cm . 2 cm 6 cm

2

3

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

91

FI-Potentiometric determination of saccharin using a tubular ISE

C

S

pH R RE W 6 mm L TISE W coating
pH
R
RE
W
6 mm
L
TISE
W
coating
3 2
3
2
tubular ISE C S pH R RE W 6 mm L TISE W coating 3 2
tubular ISE C S pH R RE W 6 mm L TISE W coating 3 2

2-3 cm

1

1 mm

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

92

Transient potentiometric signals for saccharin determination

mol L DL= 8.0 x 10 -5 mol L -1 Slope= 53.1 + 0.4 mV
mol L
DL= 8.0 x 10 -5 mol L -1
Slope= 53.1 + 0.4 mV dec -1
Sampling frequency = 40 h -1
1.0 x 10
-2
– 1.0 x 10
-4
-1
,

Fatibello-Filho, O.; Aniceto, C. Lab. Rob. and Autom., 11, 234 (1999).

Eletrodo para gases (Severinghaus e Bradley)

Eletrodo para gases (Severinghaus e Bradley) 9494
Eletrodo para gases (Severinghaus e Bradley) 9494

9494