Diss. ETHNo.

14209

Ion-Selective

Polymeric

Membrane Electrodes for

Potentiometrie Trace Level Measurements

A dissertation submitted to the

SWISS FEDERAL INSTITUTE OF TECHNOLOGY

ZURICH

For the

of

degree

DOCTOR OF NATURAL SCIENCES

Presented

by

Alan Ceresa

Dipl.
born

on

Chem. ETH

November

from Gnosca

Accepted

on

(TI)

the recommendation of

Prof. Dr. E.
Prof. Dr. E.

8, 1973

Pretsch, examiner

Bakker, co-examiner

Prof. Dr. L.

Sigg,

co-examiner

Zrich 2001

Seite Leer /
Blank leaf

Acknowledgments

I would like to thank:

Prof. Dr. Ern Pretsch for the

for the

numerous

Dr.

Tomek

electrodes

beginning

for

of this

always enjoy

having

Sigg

innumerable times he

work in his group,

me

into

with

his

the research

the

field

ideas

work;

of ion-selective

and

helps

the

to

accepting

the co-examination of this doctoral thesis

collaborations and

accepting

suggestions;

the co-examination of this doctoral

his know-how

on

ion-selective electrodes

thesis;

during

the

thesis, for the several interesting discussions, and for the

helped

Wegmann

Chiara Marinolli and

Monia

for

sharing

first two years of the

Dr. Dorothe

to

me

ideas, for his motivating spirit and

conducting

contributed

interesting

and for the many

Titus Zwickl for

he gave

work;

Prof. Dr. Eric Bakker for

Prof. Dr. Laura

in

introducing

for

Sokalski

and

discussions and

helpful

for the freedom I could

opportunity

for

Liya

me;

correcting

the papers that

Muslinkina for

preceded

proof-reading

this

this

thesis;

manuscript;

Fibbioli, Tams Vigassy, Martin Pntener, Patrick Reichmuth and

everyone

in

atmosphere

Pretsch

in the

group

laboratory.

for

their

help, friendship,

and

for

the

nice

Seite Leer /
Blank leaf

Part of this work is described in the

following publications:

Sokalski, T.; Ceresa, A.; Zwickl, T.; Pretsch,

E. J. Am.

Chem. Soc. 1997,

119, 11347-11348, Large Improvement of the Lower Detection Limit of IonSelective

Polymer

Membrane Electrodes.

Sokalski, T.; Ceresa, A.; Zwickl, T.; Fibbioli, M.; Bakker, E.; Pretsch,
Anal. Chem. 1999, 71, 1210-1214,

Polymeric

A.;

Electrolyte
Pretsch,

Composition

of

Sample

Solution.

E.

Determination of Formal

Ionophores

the Detection Limit of Solvent

Ion-Selective Electrodes. 2. Influence of

and Internal

Ceresa,

Lowering

E.

Anal.

Chim.

Complex

Acta

1999,

Formation

395

(1-2),

41-52,

of Various

Constant

Pb

in the Sensor Membrane Phase.

Ceresa, A.; Bakker, E.; Pretsch,

Potentiometrie Information

on

E. Anal. Chem.

2000, 72, 2050-2054, Direct

Total Ionic Concentrations.

Ceresa, A.; Sokalski, T.; Pretsch,

E. J. Electroanal. Chem.

70-76, Influence of Key Parameters

on

2001, 501 (1-2),

the Lower Detection

Limit

and

Response Function of Solvent Polymeric Ion-Selective Electrodes.

Ceresa, A.; Bakker, E.; Gnther, D.; Hattendorf, B.; Pretsch, E. Anal. Chem.
2001,

73, 343-351, Potentiometrie Polymeric Membrane Electrodes

Measurements of Environmental

for Selectivities and

Samples

Measuring Protocols,

at Trace

and

Levels: New

Comparison

for

Requirements

with ICPMS.

Seite Leer /
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TABLE OF CONTENTS

1. SUMMARY

11

2. ZUSAMMENFASSUNG

13

3. ION-SELECTIVE ELECTRODES

15
15

3.1 Introduction
3.2

Components

Polymeric

of the

ion-selective membrane

or

16

plasticizer

16

ion

17

Ionophore
Lipophilic

16
16

matrix

Membrane solvent

Lipophilic

polymeric

salt

17

Mechanism

17

3.3

Response

3.4

Selectivity

22
25

3.5 Detection Limits

4. DETERMINATION OF FORMAL COMPLEX FORMATION

CONSTANTS AND STOICHIOMETRIES OF VARIOUS

Pb2+

lONOPHORES IN THE PLASTICIZED MEMBRANE PHASE

27

4.1 Introduction
4.2

31

Theory

4.3 Determination of the

27

selectivity coefficients

35

4.4 Determination of the stoichiometrics

42

4.5 Determination of the formal formation constants

45

4.6 Ion-selective bulk

4.7

47

optodes

49

Experimental

5. INFLUENCE OF KEY PARAMETERS ON THE LOWER DETECTION

LIMIT AND RESPONSE FUNCTION OF SOLVENT POLYMERIC

53

MEMBRANE ION SELECTIVE ELECTRODES

53

5.1 Introduction

5.2

Theory

ion-exchange, coextraction,

of

and diffusion in

solvent-polymeric
55

ion-selective membranes

Ion-exchange

55

Coextraction

57

Diffusion

58

5.3

Leaching

and

depletion

at the

sample/membrane

5.4 Influence of membrane parameters, inner

composition

on

the response function of

filling

60

interface

solution and

sample

Ca2+-ISEs

63

The flow-through cell

64

Influence of the

inner filling solution

66

Influence of the

concentration

of interfering

Influence of the

concentration

of lipophilic

ions in the

sample

68

ionic sites in the membrane.

69

thickness

Influence of the

thickness and the

Response

70

of the Nernstian-layer

Influence of the

viscosity of the

71

membrane

73

times

75

Conclusions
5.5

Pb2+-ISEs with strong leaching, strong depletion and with

response function down to 5

Leaching ofPb2+
Pb2+-ISE with

Depletion

at

linear

10"9 M

75

ions from the membrane into the

Nernstian response down to 5

the outer membrane

surface:

ISE G

sample:

109

ISE E

M: ISE F

76
76
77

Response
5.6

78

times

79

Experimental

6. ION-SELECTIVE POLYMERIC MEMBRANE ELECTRODES FOR

POTENTIOMETRIC MEASUREMENT OF

Pb2+ IN ENVIRONMENTAL
83

SAMPLES AT TRACE LEVELS

6.1 Lead in the environment and in the human

Distribution

of lead

83

body

83

in the environment

Lead in

aquatic systems

Uptake

and distribution

84

of lead

in the human

84

body

86

Toxicity
6.2

Requirements

6.3

Optimization

for low detection limit and

of the

87

selectivity

experimental technique

for trace level measurements

ofPb2+

90

Membrane and inner filling solution

91

Conditioning solution

92

Measuring procedure

92

6.4 Proton interference at low

6.5 Measurements of

6.6

Speciation

Pb2+ concentrations

Pb2+ in environmental samples

of low total Pb2+ concentrations in

6.7 Diffusion of NTA

complexes through

6.8 Silver interference

6.9

Long

term

95

potential stability

drinking

97
water

the ISE membrane

100
103
105
107

Section

109

7. EXPERIMENTAL PART

113

6.10

7.1

Experimental

Reagents

113

7.2 Structures

114

Plasticizers

114

Lipophilic

anionic sites

114

Lipophilic

salt

115

Ionophores

115

Chromoionophores

117

7.3

Compositions

of the membranes

118

118

Membranes

of chapter

Membranes

of Chapter

120

Membranes

of Chapter

120

7.4 Electrodes and ZsMF-measurements

120

8. GLOSSARY

123

PREFERENCES

127

11

1.

SUMMARY

The

present thesis describes methods

membrane

polymer
through

ion-selective

electrodes

values

selectivity

are

processes have been

on

investigated

and

membrane

phase.

It

far better than the

ionophores

many

ones

on

cations

by

in

studied

polymeric

the

were

amide

publications. Surprisingly,

the latter exhibit better selectivities toward alkali and

Hg2+, Ag+, Cu2+

the best

possessing

series of available

Pb2+ complexes than the respective thioamides, but

hand, thioamides suffer from

and

calix[4]arene

functionalized

thioamide

has been

listed in earlier

alkaline earth metals. On the other

interferences

available

found that most of the determined selectivities

was

form stronger

membranes based

based

were

commercially

work, the complex formation of

Pb2+ ionophores with

which

ionic sites.

lipophilic

In the first part of the

can now

The fundamental membrane

membranes and

plasticized poly(vinyl chloride)

ionophores

analysis.

that ISEs

so

Pb2+- and Ca2+-ISEs,

with

of

biases

By avoiding

(ISEs).

massively improved

be used for environmental trace metal

performance

fluxes, both the lower detection

uncontrolled transmembrane ion

limit and the

the

improve

to

selectivity

for

influence

of

Cd2+.
was

Based

on

selected

Pb2+, especially

over

as

these

severe

studies,

ionophore

the

alkali and alkaline

earth metals.

Subsequently,

the

membrane parameters,
ionic sites

predict
the

on

the

inner

filling

including thickness, viscosity,

the ISE response has been

of the

sample

in the

can

and

Theoretical models

considerably

sensed Nernstian

ISEs.

It

has

and,

been

at

least

qualitatively,

demonstrated

that

with

confirmed for

influence

layer and,

consequence, the lower detection limit of the ISEs. The model

have been verified

various

and concentration of

investigated.

that zero-current transmembrane ion-fluxes

composition

solution

Ca2+-

as

predictions
and

Pb2+-

appropriate compositions

of

12

Chapter

membrane and inner

can

filling solution,

the extent of transmembrane ion fluxes

be reduced to obtain lower detection limits that are, with

least three orders of magnitude better than the earlier

In the last part of this

optimized
values that

achieve

at least 10

Environmental Protection

concentrations

from

in

natural water

10"8

assessed for

ISE response is dictated

results

applicable

clearly

analytical

to

Pb2+.

environmental

by H+
for the

demonstrate that

tools

for

samples

or

samples, containing

10"10 M,

were

acidified to

total

pH

speciation analysis

polymer

membrane

heavy

nanomolar levels.

metal

10"9

sensors

of lead.

The

electrodes
ion

Pb2+

4 and

10"9 M,

For lead concentrations above

Cu2+ interference. The

Potentiometrie
at

were

large

drinking water).

the values compare well with ICPMS measurements. Below

shown to be

values.

with lower detection limit

sensors

Agency (15 \igfL

spiked

varying

rugged

at

times smaller than the action level of the U.S.

number of native and

potentiometrically

10"9 M, by

work, the Pb2+-ISE and the measuring procedure

in order to
are

reported

Pb2+,
are

the
also

obtained

are

useful

determination

in

13

2. ZUSAMMENFASSUNG

Die

des

Arbeit beschreibt verschiedene Methoden

vorliegende

Ansprechverhaltens

wird
der

gezeigt,

Verbesserung

zur

Flssigmembranelektroden (ISE).

ionenselektiver

Es

dass durch die Reduktion unkontrollierter Ionenflsse innerhalb

Membran

sowohl

die

auch

als

Nachweisgrenze

untere

das

Selektivittsverhalten der ISE verbessert werden knnen. Die beschriebenen

Methoden

Schwermetallionen

von

wurden dabei mit Hilfe

Membranen

Ionophoren
Im

und

der

entsprechenden
basierend auf

Arbeit
mit

Membranprozesse

ISE

untersucht, deren

Weichmachern

kuflichen

und

zahlreicher

Komplexbildung

verschiedenen

Kationen
dass

die

in

Pb2+-

Membranphase

der

Selektivitten

meisten

sind, als die Werte, die bisher in der Literatur beschrieben

bedeutend

Pb2+-Komplexe

strkere

Thioamidverbindungen.

Ionophoren

mit

Einerseits

Thioamidgruppen

Ionophore

dass

festgestellt,

wurde

bilden

die

Membranen

zeigten

zwar

als

mit

bessere Selektivitten

Alkali- und Erdalkalimetallionen. Andererseits wurden aber fr

Interferenzen durch

starke

Thioamid-Calix[4]aren

Experimente

von

diesen

als

untersuchte

Pb2+-Ionophor

Additive auf das

fr

whlte

die

man

weiteren

gegenber

Alkali- und

und

zahlreicher

zeigte.

zudem

Membranparameter

Hg2+, Ag+, Cu2+

Untersuchungen,

aus, welches die besten Selektivitten

Erdalkalimetallionen
Man

mit

die

wurde

Cd2+ beobachtet. Ausgehend

dasjenige

Die

Bestimmung

zur

Salzen basierten.

thioamidhaltigen Liganden

und

Umweltanalytik.

Pb2+- und Ca2+-selektiven

berraschenderweise

Amidfunktionen

gegenber

der

Experimente zeigten,

Diese

bedeutend besser
wurden.

von

lipophilen

Liganden

untersucht.

in

Poly(vinylchlorid)

auf

Teil

ersten

selektiver

die

damit den Einsatz dieser Sensoren

ermglichten

wie

den

Einfluss

der

Innenlsung

Dicke, Viskositt und Konzentration der anionischen

Ansprechverhalten

der ISE.

Theoretische Modelle sagten

14

Chapter

zudem

voraus,

einen

Zustand)
Schicht

an

der

dass

Ionenflsse

wichtigen

innerhalb

Einfluss auf die

der

Nachweisgrenze

der ISE beeinflussten. Diese

und mindestens

qualitativ

und

Membran als auch der

zeigten.

bislang

Voraussagen

Innenlsung

Diese Werte

lagen

untere

optimiert.

Umweltproben

kleiner

waren,

Trinkwasser- und

10"8-10~10

untere

als

vorgeschlagene

um

etwa

drei

der

Es wurden ISE

geprft

besttigt.

10"9

von

Grssenordnungen

Es

M und

unter

Pb2+-selektiven

hergestellt,

den

der

von

in

von

Messresultaten, die mittels

Konzentration unterhalb

von

fr die

werden knnen.

10"9

ICPMS

M eine gute

ermittelt

10"9 M, zeigten

Interferenz. Die erzielten Resultate

eingesetzt

im

Bereich

von

angesuert (pH 4) und anschliessend mit ISE bezglich

Pb2+-Konzentration analysiert. Dabei zeigten die mit

entwickelten ISE

Zahlreiche

Trinkwasser).

Umweltproben mit Bleikonzentrationen

M wurden

Messungen

Umweltschutzbehrde

Amerikanischen

ug/L

(15

Grenzwert

die bei

ISE und

die mindestens zehnmal

Nachweisgrenzen zeigten,

Pb2+-Konzentrationen oberhalb
den

untere

beobachteten Detektionslimiten.

das Messverfahren

der

wurden

ISE

Nachweisgrenzen

Im letzten Teil der Arbeit wurden die entwickelten

von

die

auch

folglich

Pb2+-selektive

wssrigen

der

beobachtet, dass ISE mit optimierter Zusammensetzung sowohl der

wurde

tiefer

Ca2+-

stromlosen

(im

Zusammensetzung

haben und

Membrangrenzflche

fr

Membran

zeigen eindeutig,

Schwermetallbestimmung

gemessenen

bereinstimmung

wurden.

die ISE

ISE

mit

Lag die Pb2+-

dagegen H+-

bzw.

Cu2+-

dass die in dieser Arbeit

in der

Umweltanalytik

15

3. ION-SELECTIVE ELECTRODES

Ion-selective electrodes

(ISEs)

are

electrochemical

Potentiometrie determination of the activity of an

of other

kinds

ionic

sensors

that allow the

species

in the presence

of ions [1].

3.1 Introduction

A chemical

sensor

be

can

defined

as

transformation of chemical information into

can

on

be

processed by

an

instrument. ISEs

ion-selective membranes.

whose

logarithmic

value is

proportional

an

are

They respond
to

small

device

optical

electrical

or

Potentiometrie

to the

allows the

that

activity

ion

sensors

of the

Several kinds of ion-selective

membrane

including glass [2], plasticized polymers [3],

known

materials.

crystalline

electrode wich is still

However,

at

The

ionophore.

one

present, the

organic polymeric
species.

The

best known

most

matrix

standard

pH glass

the

probably

various

or

devices.

laboratory

versatile ion-selective membrane consists of

containig

lipophilic ligand

of the membrane

key components

is

example

important

of the most

based

potential

the membrane electrical

reference electrode.

that

analyte ion,

measured relative to
are

signal

The former guarantees the

are

operation

the

and

lipophilic

lipophilic

of the ISE

an

ionic

ion and the

by keeping

the

total amount of measuring ions inside the membrane constant, while the latter
assures a

selective response of the ISE to the target ion.

Ion-selective

electrodes

are

cheap

and

miniaturized, allow on-line and in-situ

speciation

information.

Ideally

they

do not need

measurement and

usually

applied, especially

in clinical

analysis.

simple

devices

measurements
consume

no

that

and

can

may

analyte

sample preparation. They

provide

during
are

be

the

widely

16

Chapter

of the

Components

3.2

The

ion-sensitive

immiscible

liquid

Polymeric

matrix

The

polymeric

cases

Polymeric

solvent

of high

matrix

it is inert

polymeric

ion-selective membrane

viscosity containing

has

no

ISE-membranes

are

chemical

water-

the components listed below.

stability

mechanical

ideally

is

membrane

polymeric

provides

and

to the

interaction

commonly prepared

membrane. In ideal

with

with

sensed

the

ions.

poly(vinyl chloride)

(PVC).

Membrane solvent

or

plasticizer

The membrane solvent reduces the

mobility
the

and

ensures

of the membrane constituents. In order to

provide

organic phase

and acts
can

as a

membranes
ether

Lipophilic

ions

are

(ions

selectivity.

on

relatively high

The

of

homogeneity

with the other membrane components

its

polarity

and dielectric constant, it

characteristics of the membrane

ion-exchanger

bis(2-ethylhexyl)

plasticizers

sebacate

that

are

usually

(DOS, apolar)

or

and,

as

used in ISE-

ortho-nitrophenyl

(o-NPOE, polar) [4].

ion

prerequisite

significant

compatible

plasticizer. Depending

consequence, the

The

it must be

influence the

octyl

viscosity

for

of

amount

with

theoretical Nernstian response of the ISE is that

primary

ions may be coextracted

opposite charge sign

into the membrane

for ions with the

phase.

same

characteristic is called

This

of the

means

charge sign

measuring ion)

or

measuring

with counter

from the

that the membrane is

of the

permselectivity

together

no

sample

permeable only

ion. This membrane

Donnan exclusion. The presence in

17

the

membrane

operation
the

of the ISE

membrane

of

phase

Cation-selective

the total concentration of

by keeping

much

higher

the

than

garantees the

measuring

coextracted amount,

contain

ISE-membranes

tetraphenylborate derivate,

ions

non-exchangeable lipophilic

normally

anion-selective membranes

as

i.e.

ions in

constant.

site

lipophilic

tetraalkylammonium

salt.

Ionophore

The

ionophore,

and reversible

ion-exchange

between

the

as

low

as

ligand,
ideally

has the main influence

forms

with the target

and

its

so

leaching

rate

no

no

interference,

contain

must

structure

selective

that in the membrane

interfering ions, i.e.,

ionophore
keep

ion,

relatively strong,

the

on

numerous

from the membrane to the

possible.

salt

Lipophilic

The addition of

resistance

the

Response

salt without

lipophilic

selective membrane

increasing

or

measuring

groups in order to

sample phase

electrical

carrier,

complexes only

Additionally,

lipophilic

3.3

ion

of the ISE membrane. It

selectivity

occurs.

or

of the
more

membrane.

ion-exchanger properties
Additionally,

selective for divalent

ionic-strength

in the membrane

it

reduces the

renders

the

ion-

monovalent

ions, by

consists of two

galvanic

over

[5].

Mechanism

The electrochemical

measuring

cell

(Figure 3.1)

half-cells: the ion selective electrode and the reference electrode

[1].

18

Chapter

ISE

reference

EMF

electrode

inner reference half cell

inner reference half cell

(AglAgCl)

(AglAgCl)
reference

ISE

electrolyte

solution

body

diaphragm
inner

filling
bridge electrolyte

solution

solution
ion-selective

diaphragm, capillary

membrane

teflon sleeve

Ag | AgCl |

Figure

KCl 3 M

I bridge electrolyte | sample ||

3.1. Schematic

The total

potential

difference

potential differences, arising

that

only

electrode, EDk{,

expressed

as a

inner

filling

(electromotive force, EMF)

constant

at each

potential, EM,

the membrane

reference

EMF

||

solution

are

electrodes

two

is

measured under

the

electrochemical interface.
and the

Considering

potential ED ref originates

the

boundary

electrolyte

between

of

be

high

of the

liquid junction potential

sample dependent,

the other terms

can

be

contribution, ECOBSt [6] :

The

can

of local

sum

(3.1)

Econst +EM+ Def

electrode. It

| AgCl | Ag

representation of an ISE measuring-cell assembly.

conditions between the

zero-current

membrane

or

kept

from the different mobilities of ionic

sample

and

bridge electrolyte

small and constant

concentration

(e.g.,

by using

1 M

an

of

the

species

at

reference

equitransferent bridge

KCl, NH4N03

or

LiOAc),

or

by

19

using samples
ED ref

can

be estimated

RT

^D.ref

with constant ionic

~TT
F

If necessary, the

to the Henderson formalism

according

X^-Kref -<*hs)
XT'

strength.

magnitude

of

[7, 8] :

Zzf"i,,S

^^."iKref-^sj

(3-2)

ZAMAref

with:

(8.314

i?

molar gas constant

absolute temperature

Faraday

zl

charge

ux

absolute

ax

activity [mol l"1]

The

mol"1)

of the ion i
of the ion i

mobility

electrolyte
can

mol"1)

[K]

(96487

constant

K"1

mol

[cm

of the ion i in the

s"1

sample (S)

solution of the reference electrode

be calculated

membrane

by

potential,

EM,

phase boundary potential

The inner
diffusion

be

can

potential

arises from

the contribution of

showing

EDM

Nernstian

and

one

at

phase boundary potential

divided
at

lipophilic

kind

membrane, they

of
are

to

the

into

three

separate

the membrane/inner

filling

is

membrane/sample interface, EPB, [6].

usually independent

charge separations

the different mobilities of ionic

than

The ionic activities

interface, EPB, the diffusion potential within the membrane, EDM,

solution

primary

(ref).

bridge

and in the

Debye-Hiickel approximation [9, 10].

the

contributions, i.e., the phase boundary potential

and the

J"1]

EM

response

ions of

species.
can

In most

contain

only

cases

of

practical relevance,
since membranes

homogeneously

opposite charge sign. Moreover,

exchangeable

ion

are

The

within the membrane due to

neglected [11-14]

be

sample.

of the

distributed

even

simultaneously present

usually quantitatively complexed by

the

if

more

in

the

ionophore, and,

20

Chapter

therefore, have the

membrane

^M

potential

^M,const

mobility.

same

as

It is

difference arises from

non-uniform distribution of ionic

potential contributions,

can

i+ZiF(/)

where zY and ax

free energy,

be formulated

charge separation,

between the

organic

membrane

potential fi\

for the

primary

the

charge

fJLx the chemical

fii,u,

boundary potential

and

(3.4)

activity

potential

as:

Ltj

1\1

&\

Z\r

alM

LLl

and

sample, /iIS,

is obtained

\A

^j0

of the ion /;

the electrochemical

and in the

the

electric

potential

are

is its standard

equal,

potential.

so

that

the

subscripts

membrane

phase, respectively.

energy of

transfer),

can

be

The free energy

replaced by

phase

(3.5)

S and M indicate the aqueous

where the

At

of the ion / in the

pB' =0m-0s=^^r~ + ;ln^Z{r

ion /

as:

f+RT\nal+zlF(t)

are

due

into account chemical and electrical

the electrochemical

thermodynamic equilibrium
membrane,

species

sample phase. Taking

and the aqueous

solution

describe the

(3-3)

to

to

^TB'

phase boundary potential

in

consequently possible

[6] :

The
a

the

so

and the

sample

difference,
called

single

organic

fiM (free

ion distribution

coefficient, kl:

i=~expKs-XM}

(3-6)

21

The parameter

kx

is not

of the ion

measure

lipophilicity.

and membrane

Ku

It

can

ion-exchange

an

equilibrium

uncomplexed

of the two

but it is

constant

ions between

||||||^|

sample phase

membrane

Ic+S'
T

Js

^H

IM+

HBHHH
HHHi

equilibrium

sample

membrane

of the

equilibria

solution. The

iL

are

and the

for the

RM"

involved when

cation-selective membrane is

ionophore

and the

complexes IL+

and J

L and R~ indicate the

the formation constants for the

primary, t,

TT

~->

"^

^M

symbols

ion-exchange

equation (3.8)

measuring

for the

and

of two

interfering, J*, respectively; Ku

uncomplexed

ions between

membrane-depending potential

cell is obtained from

ions inside the membrane

constant:

ILa

is the

sample

and

phase.

The Nernst

of the

and

ionophore

constant

gm
"^-

RM*

3.2. Schematic view of the

between the

XM

lipophilic anion; \L

phase

rm'

rm"

M^

Ac-LS

sample

(3.7)

k\

in contact with

Ku

(cf. Figure 3.2):

[^

Figure

combined with the

however be

ion, J, in

for another

corresponding values, k},

that describes the

thermodynamic equilibrium constant,

are

equations

difference

3.1 and 3.5 if the activities

sample independent and, therefore,

22

El

Chapter

EMF

El

where

is

to

(3.8)

log aI>s

5,

of

consisting

changes

differences in the

measuring

ISE response function

ISE; s

(59.16/ zI

sum

corresponds

cell and

lnlO/?77(zjF)

mV at

ISE

an

of all constant

the

intercept

is the Nernstian

an

ideal

that

only

potential

of the linear
of the

slope

25C).

Selectivity

Selectivity
determines

together

is

when the

sensitivity

its

with the

characteristics of

important

of the most

one

contains

sample

/. The response of

primary ions,

presence of several kinds of ions is related to the

exchange
aqueous

reactions of

potential

selectivity

coefficients

selectivity

membrane to

can

be

primary

an

equation

3.2

interfering

and Section

exactly

and

primary

an

an

J,

ISE membrane in the

constants

ions between the

5.2). However,

any

it

as

interfering ions,

equilibrium

described with the

ISE,

help

of

equilibrium

of the

organic

the

and

resulting

Potentiometrie

constants.

be defined from the linear part of the response

can

interfering

for

and

[15], without knowing

coefficient

functions of the

Nernst

primary

phase (cf. Figure

membrane

The

to

of

difference

reference electrodes and

E represents the

in als;

response function of the

3.4

membrane-depending potential

the

cell

measuring
responds

EDref

interfering

ion

ions. The response function of

is defined in

complete analogy

to

the

ion:

DT

E}=Ef+:\nahS

where
the

E}

and

interfering

Ef

(3.9)

have

ion

analogous meaning
is described

of

by using

El

and E. If the response to

the standard

potential E

of

23

equation

?o

3.8 the

following equation

T70

K'

77O-

E}=E? +(j -E?)

The

hF

difference,

functions of the

and

primary

(3.10)

lnaJS

also known

selectivity coefficient,

the EMF

is obtained:

E),

as

Nikolsky coefficient,

the

at

interfering

intercept

of the

is related to

linear

response

ions:

^ot=exp{^(-,<>)}
The

magnitude

formation

(3.11)

K^1 depends

of

between

constants

of the ions under

lipophilicity

determination of
calculate the

Kff

are

selectivity

following equations

can

on

ligand
study.

the
and

membrane

composition,

on

the

and

on

the

investigated ions,

The three factors and the

discussed in detail

in

Chapter

4.

experimental
In

order

to

coefficients from the measured EMF values the

be used:

(e -E)
log KJX=

(3.12)

si

or

\ogK[f ~^^ + \ogal(l)-^\ogaJ(J)

where

ax{l)

only

salt of the

potentials Ex
is

given

in

and

a^J)

and

Figure

are

primary

Ei.
3.3.

(3.13)

the activities of two different

and

solutions, containing

interfering ion, respectively,

graphical representation

of the

and

inducing

selectivity

the

coefficient

24

Chapter

350

300

aj2+(I)

250
>
E

UJ

200

^^^

aj2+(I)

lg KU

log Kitj

150

SI

si
100

,'

50

aj2+(J)
-

aj+(J) /'
i

-3

-2

-2-1

log

3.3. Determination of the

Potentiometrie selectivity

primary

ions at

log

separately

coefficients

separate solution method (SSM). The selectivity coefficient

vertical distance between the

-3

-1

log

interfering

^^

Figure

y^-""

"/

When

^^^

K^

according

the

primary

and

0, divided by the theoretical slope of the response function of the

ion.

more

than two ionic

species

are

simultaneously present

their contributions to the mixed response of the

according

to

the

ISE, Exl,

semi-empirical Nikolsky-Eisenman

in the

can

formalism

Unfortunately,

this

[16, 17]:

different

charges,

incorrect

the

same

i.e.,

charge.

When

correct

primary

Nicolsky-Eisenman equation

description

response range,

(3.14)

simple equation provides

involved ions have the

of the observed membrane

in the

region

where

sample,

be estimated

Eu-^+^logLs+^JfV^

an

to

corresponds

measured linear response functions for

to the

and

results

only

interfering

if

all

ions have

is inconsistent and leads to

potential

in the mixed-ion

deviation from the linear response

25

by

Morf et al.

[1],

self-consistent models for two ions of any

charge [18]

and

of the ISE is observed. This has been

but

only recently

for any number of ions of any

3.15 describes the

containing

previously

charge [15]

Potentiometrie

observed

published. Equation

have been

response of

an

ISE in

sample

solution

and divalent ions:

mono-

Eu =E? +-TTln

AI.'(1)

^pot

.(i),s

1/Z|
a.

(i),s

AI,.(2)

21H
a

i(2),S

(3.15)

where the indexes

i(i)

and

i(2)

indicate monovalent and divalent

interfering ions, respectively (Kff

primary

or

1).

3.5 Detection Limits

Deviations of the electrode function from the linear response

observed at

high

and low activities of the

IUP AC recommendations

limits

are

defined

of the calibration

by

the

curve

[25], the corresponding

cross

the

to

increasing

aY

into
s

the

upper and lower detection

linear segments

by

the loss of membrane

permselectivity,

primary

membrane.

As

ion

together

with

consequence,

and the EMF difference is smaller than

equation (cf. equations

the

(Figure 3.4).

the coextraction of the

sample

to

extrapolated

section of the two

The upper detection limit is caused

owing

normally

According

ion.

measuring

are

3.5 and 3.8 and Section

a,

counterion from
increases with

expected by

5.2) [19-23].

the Nernst

26

Chapter

The lower detection limit

-

the interference of

detection limit

can

be dictated

competing

j(DL)

by

two processes:

ion present in the

is related to the

sample.

Nikolsky equation

In this

case

3.14 and is

the

given

by:

al(m,)

the

Kffaf'Zi

leaching

surface

of

(3.16)

primary

ions from the membrane

This process is treated in detail in

layer.

phase

Chapters

into the aqueous

5 and 6.

>

lower

upper

detection

detection

limit

limit

log

Figure

3.4. The detection limits of

IUP AC recommendations

of the calibration

curve.

[25] by

an

the

ion-selective electrode

cross

section of the two

are

defined

according

extrapolated

to the

linear segments

27

OF

4. DETERMINATION

CONSTANTS

FORMAL

Pb2+

VARIOUS

OF

STOICHIOMETRIES

AND

FORMATION

COMPLEX

IONOPHORES IN THE PLASTICIZED MEMBRANE PHASE

The

formal complex formation

ionophore complexes
the

respective

selectivity of

constant

in the membrane phase,

ions and the

carrier-based

knowledge

These parameters

sensors.

the

allows

to

one

are

the

structure-selectivity

required for

fundamental thermodynamic properties

composition for

together with the lipophilicity of

composition of the membrane, determines

Potentiometrie

correlations. Moreover, their

the ion-

stoichiometry of

and the

optimize the membrane

specific application.

4.1 Introduction

characteristic of

important

The most

is, therefore,

not

Potentiometrie

astonishing

ion

sensors

complexing agents

[3,

as

chemical

has been invested in

24].

Such

developing

by measuring

the relevant parameters. If

Nernstian, the

composition [6].
formation

Their

constants

ionophore complexes
by

the

under

ionophore

selectivity.

Kff

values

magnitude

(equation 4.4)

are

It

within the membrane

correctly determined, i.e.,

constant

the

been

for

under

investigated activity
a

given

membrane

by

the

complex

stoichiometrics

of

the

phase,

and sites concentrations and

study (cf. equation 3.7).

lipophilic

Potentiometrie selectivity

the

is above all

and

selective

traditionally

have

ionophores

conditions where the response to each of the ions in the

range is

is its

sensor

that much of the research work in the field of

characterized in I SE membranes
coefficients

by

dictated

but
the

also, in

ion-

minor extent,

lipophilicity

of the ions

28

Chapter

For

fixed interference

or

method, FIM) proposed by IUP AC [25]

coefficients

determining Potentiometrie selectivity

because of
but

experimental

only recently

allowed

one

an

artifacts. This

experimental procedure proposed by prof.

obtain unbiased

to

this

selectivity

method, calibration

taken before any contact of the membrane with the

a

Nernstian electrode

calculated from the measured

method

[25]. Later, it

was

also obtained with ISEs

primary
The

interfering

stoichiometry
selectivity
in

ions of any
of the

ion-ionophore complex,

To establish

directly interpreted

structure-selectivity

optimize

membrane

fundamental

Formal

phase

complex

were

usual

values

in terms of

compositions

it

are

optode

components,

chromoionophore (C),

an

and the

without L, but otherwise of the

of

possible
same

to

any kind of

the

predict

the

to

components but

quantities

relative

only

one

knowing

formation constants.

view to

ionophore design

is, therefore, desirable

ionophores

optical

membranes

i.e.,

are

[30].

without

complex
a

are

to

know the

the stoichiometrics and

in the membrane.

complexes

formation constants of

responses of two bulk

the

Kff

correlations with

first determined with

leaching

containing

it is not

thermodynamic parameters, i.e.,

formation constants of the

coefficients

ISE membrane lets

given

charge [15, 18]. However,

proportion. Moreover,

and cannot be

more

solution

behavior of another ISE membrane with the

different

and to

values of

that

coefficients

inner solutions that prevent

sample

so

the separate solution

selectivity

shown that unbiased

Kj^1

to

its exact response function in mixed solutions

predict
of

of true

Bakker

primary ion,

selectivity

The

slope.

ions from the membrane into the

knowledge

curves

potentials according

having

E.

for discriminated ions

are

to

[26-28],

coefficients for any discriminated

[29]. According

gives

biased values

yield

realized many years ago

was

ion

each ion

(separate solution

discriminated ions, the conventional methods

strongly

Method, SSM
for

the

same

method

(see

organic

membrane

[31], by comparing the

Section

ionophore

lipophilic

in the

4.6),

(L),

ionic site

the

(RT),

composition [32].

one

containing

FT-selective

and the

other

The ratio of the

29

corresponding

of

constants

between

sample

complex

formation constant

assumption
In

and

that the

for the

equilibrium

phase correspond

membrane

of H

exchange

This method relies

(Equation 4.9).

/Z|

ion-ionophore

the

to

and

the basic

on

does not bind other ions than H+.

chromoionophore

ISEs, theoretically, the difference between the phase boundary potentials

of two

permselective membranes,

measured in the

complexation

in the membrane

respond

ions in the membrane

Since

however, the

of the

membrane,

complex

phase.

In

changes

to

phase,

same

no

if the

without

one

in the

in the

occurs

phase boundary potential

ionophore

of the presence of the

kept

is

sample

is be observed. For

potential change

membrane

and

ionophore.

of solid-contact

use

inner

at

both sides

determining
must be

in the membrane.

potential

systems

available

depend

not

are

still

the

on

not

simple techniques

incorporated
well

perfectly
to

manufacture

[33].

Another

possibility

and without

formal

is to choose

ionophore)

complex

Potentiometrie
under

not

are

kept

electrodes, since the potential between

should

those

Unfortunately,

understood, and there

them

electrode

ion-

constant.

The easiest way to eliminate the influence of the inner membrane

would be the

of ion

uncomplexed

of the

potential change simultaneously

net

degree

equation 3.5,

to

activity

ionophore,

an

reflects the

fact, according

activity

formation constants, the inner

independent

with and

sample solution, directly

same

selective membranes

one

reference ion that in both membranes

induces the

same

formation constants

responses of

investigation

assumption

that the

and

pair

can

potential.

It has been shown that

be determined

of ISE membranes

by comparing

charged

(with

chromoionophore

and without

point. Consequently,

with the

the

ligand

H+ selective ionophore [34, 35]. Until the basic

does not bind other ions than H+ is

valid, the potential induced by the hydrogen ion is the

membranes

(with

ionophore)

the ratio of the

and it

selectivity

can

values

same

be used

Kf*

as

in

both

reference

of the membranes

30

Chapter

with and without

recently,

a new

been introduced
this
a

is

function of the formal

solved

case

[36].

method based
The

by using

problem
two

on

sandwich membranes has

segmented

of the inner membrane

layer membrane,

that made

potential

possible

membrane with the inner and outher surfaces of different

has been shown that the initial

sandwich

two-layer

contacted with the

ion

complexation

the

ionophore

potential
depends
as

the

is

on

membrane-potential

membrane,

same

one

solution

across

obtained with

saving time,

the

the

two

complex
single

experimental

It

such

ionophore,

reaching

the

equilibrium,

distributed in both membrane

homogeneously

obtain

to

sides, directly reflects the degree of

both

in the membrane. After

the EMFs of the sandwich and

constants

difference

that the measured

so

membranes.

individual

formation constant

are

i.e. after

layers,

the

potential only

the other contributions of the cell. It therefore has the

ones

same

For

value

practical

calculated from

membranes measured under the

same

conditions.

of this

topic

on

in

was

composition.

with and the other without

the membrane is zero,

across

purposes of

The

formation

complex

of ILZl.

constant

More

ionophore

of various

the last 20 years

[3]) and

the

drinking

water

is the determination of formal

chapter

Pb2+-selective ionophores

more

possible

than 20 of such

use

of

some

in the membrane

ionophores

phase.

Over

have been described

of them in view of

has been demonstrated with

formation

complex

the

monitoring

optodes [37]. However,

so

(cf.

quality
far,

no

system has been achieved with optimal response times, signal stability and
selectivities
of ISEs

[38].

The recent relevant

[39] (cf. Chapters

alternative

for

this

task.

5 and

The

constants and stoichiometries is

membrane and inner solution

the

sensor

design

6)

improvement

make

Potentiometrie

knowledge
required

of lower detection limits

of

formal

for the rational

composition

for

sensors a

promising

complex

formation

optimization

of the

given application. Otherwise,

remains at the level of a trial and

error

process.

31

the

Unfortunately,

of FT

concurrence

Potentiometrie

method based

done,

and,

disadvantage
In this

on

with

that

membrane is

a new

the

required

work, tetramethylammonium ion

a

with those of the

method is

generally applicable

^7tma

varues

information

Finally

the

on

the results

varying

the

validated

by

it

investigated
as

was

has

the

ion.

the reference

membrane

are

membrane. It is shown that this

ionophores

ionophores,

occurs.

The

concentration

ionophore

of the

to

solutions

after this work

is chosen

in order to characterize

stoichiometry

are

for each

(TMA+)

ionophore-based

between TMA+ und

upon

published

ligand-free ion-exchanger-based

compared

complexation

directly applied

procedure presented below,

compared

the

on

pHs. On the other hand, the

soluble at low

only

sandwich membranes has been

ion and the selectivities of

no

[34] is based

measuring procedure requires

because the

whereas lead is

high pH,

far

so

IZ{ in the membrane, and cannot be

an

Pb2+-selective ionophores
of

method used

complexes

long

as

changes

also

as

in

provide

formed in the membrane.

reference measurements with bulk

optodes

[32, 38].

4.2

Theory

The

Potentiometrie
with

ionophore, L,
obtained

with

determination of the

an

two

ion, IZl, is based

ISE

membranes,

complex

formation constant of

the

of

on

one

comparison

with

characterized and the other without. The reference

the

Kff

ionophore

ion, /Zj,

must not

an

values
to

be

interact

with L.

The model is based

in

on

the

following assumption,

that have

already

been listed

[32] and [18]:

The

solvent

organic phase
solution.

polymeric

membrane

and its surface is in

phase

behaves

equilibrium

like

with the

homogeneous

contacting

aqueous

32

Chapter

The membrane response is

sample/membrane interface,
is
-

phase boundary potential

the

governed by

and the diffusion

potential

at the

within the membrane

neglected.
The

ionophores

and the anionic additives

confined to the membrane

are

phase.
Ion

pairs

either

equal

between the
for all ions

Ionophores

ionic additives and their counterions

lipophilic

negligible.

or

form stable

are

complexes

of not

more

than

one

stoichiometry

at

time.
-

The

species

equilibrium

constants

in the membrane

Since the model

neglects

phase

assumes

According

to

related to concentrations of the

are

pairs,

can

be used in the membrane and

the obtained values

are

complex

formal

only.
phase boundary potential

the

phase.

and to activities in the aqueous

that concentrations

the formation of ion

formation constants

determined

Potentiometrie selectivity coefficient,

K^\

model

of

(equation 3.5),

cation-selective ISE,

related to the concentration of the

uncomplexed cations, 7Z'

membrane surface

[6] :

layer

as

follows

the

and

7Zj,

is

in the

|yZjj
This

simple equality

assuming

aIM

can

be derived from

equations (3.5-3.9)

and

(3.11) by

that:

~[/Zl ] and aiM [> ]

The concentrations
measurements

(4.2a, 4.2b)

IZl

and

7Zj

under conditions

in

equation

ensuring

4.1

refer

that in each

case

to

two

only

one

different

kind of

33

cation is present in the membrane. This is easy to

because it is the

prerequisite

verify by experiment

of Nernstian response of the ISE to

If the ISE membrane contains

an

that forms

ionophore

ion.

an

complex

with the stoichiometric factor nx, its concentration in the membrane

be

expressed

Mwith

can

as:

(4.3)

AL[i]"'

lL

as

/Zj,

as

the formation constant of the

is valid for /Zj

lipophilic

if it also forms

complex 7Ln'

From the

by

the

of the

(4.4)

membranes,
L

one

is

sites, RT :

Kf^MA(lE)

coefficients

selectivity

containing

analogous

complex. If, however, TMA+

its concentration in the membrane is defined

anionic

An

[TMA+]=/?T

two

phase

ii

equation
used

with IZl

based

one

on

an

ion

A^ma(L),

obtained with

exchanger only (IE)

and the other

also, the complex formation

and

for /LZl

constant

can

be calculated

accordingly:

*t?ma(ie)
ILni

^iP?ma(L)K

Equation

4.5 is

if strong

complexes

[lLzn\]~ RT / z,

"

closely
are

and

,*r

(4 5)

^i]n'

related to those described in

formed, i.e. for lL

[L]*^

-/it/?T

[L]n|

/z,)

[34, 40]

1,

so

and is valid

only

that:

(4.6a, 4.6b)

34

Chapter

where

is the total

Lj

concentration. When

ionophore

have been calculated in relation to

this

work, they

must

one

selected

be recalculated since

selectivity coefficients

primary ion,

equation

such

Pb

in

TMA+

as

as

4.5 holds for

7ZJ:

log KffMA

Equation

|(log tfgTMA

4.5 is based

formed under the

ionophores

for

independent
the

shape

log KZ

(4-7)

well-defined

evidence is available. In

some

of the response function of bulk

ionophore

Kf^

concentration.

TMA+, according

to

the

that

conditions. Its

experimental

that build

assumption

the

on

nx is determined from the

their

only

This

(2)

can

membrane with

Figure 4.4).
comparison

solved

supposed

optodes [38, 41, 42].

that L

The

from

A^^l)

does not

corresponds

complex

selectivity

to:

for nx

(cf.

factor

nx

experimental

Table

predict A^Pjl(2)

of another membrane with

coefficients obtained with the two

iteratively

in

differing only

(4.8)

stoichiometric

of calculated and

from

work,

In this

and 4.6 the ratio of the

be used with different values of nx to

Z^(2)

if

or

gathered

cases, it has been

Again, assuming
4.1

be

cavity (e.g. valinomycin)

values of two membranes

equations

can

is

complex

1^(1)-nyRT Izx

equation

selectivity

kind of

stoichiometry

coefficients obtained with ISE membranes 1 and 2

^pot

one

4.2).

can

be

values.

for

^(1) (cf.

through

the

Alternatively, using

the

estimated

membranes, equation 4.8

can

be

35

4.3 Determination of the

Seven

out

literature

of

more

[3, 43-47]

(Figure 4.1).

than

20

Pb2+-selective ionophores described in the

have been selected for the

(I, IV-VII)

Five of them

ionophores. Compound
(A":

(ETH 322)

sample anion) polymeric

5428) [37]

has the

coefficients

selectivity

used in the first

was

membrane ISE

The

respect
from

improved Pb2+ selectivity

to alkali and alkaline earth

Hg2+, Ag+, Cu2+

and

metal

reported Pb2+/PbA+

as

I, but

of the two amide oxygens

sulfur atoms leads to the dithioamide IV

an

optode

in

recently,

More

which

(ETH 5435),

ions, but suffered

Cd2+ [37].

lead

lipophilicity

of II

shown to have

as

(ETH

similar

replacement

available

II

aliphatic

lengths.

in this work

[44]. lonophore

different

by

chain

commercially

are

central unit and

same

investigation

was

membranes with
severe

the

interference

corresponding

monothioamide III

this

respect, while

and

(ETH 5439) [38] showed some improvement in

maintaining sufficient Pb2+ selectivities in relation to alkali

alkaline earth metal ions. The series II-IV allows

best

coordinating

replacement
VI

atom for

of amide O

[47] currently

that interference

seems

by
to

by Ag+

Finally, although

VII

Pb2+ by evaluating the

S

on

the

severely

still

for

Ag+

measurements.

to

check wich is the

influence of

formation constants.

ionophore

for

recent

as

lead

studies

[29]

stepwise

Compound

Pb2+ in spite of the fact

underestimated in the

offered

agreement with other independent

adequate

complex

be the best

was

is

one

selective

original

work.

ionophore,

it is shown to be

in

only

36

Chapter

C3H7\ /C3H7
N

Cl2H25\ ^Ci2H25

Cl2H25\ /C12H25

.0

ETH 5493

ETH 5428

ETH 322

"o
.0

C18H37

C18H37

.0

.0

III

II

Cl2H25\ /C12H25

*N

C12H25

C12H25

C12H25

C12H25

/C7H15

0
O
ETH 5435

ETH 295

,N,

C12H25

,N,

C12H25

C7H1J
VI

IV

MDBiBDTC

VII

Figure

4.1. Structural formulas of the Pb

-selective

ionophores investigated.

37

To determine the

cation

[25]

but

exchanger, NaTFPB,

has been extended

/Zl

of

background

until

(Figure 4.2, right side).

determining ion,
checked

Figure

the ISE

The

diluting

(left side) show,

4.2

primary ion,

given

are

point /z'

unbiased

obtaining

constant

potential

is the

Kf^1

values, is then

the solution with pure water. As the

in

is obtained for all

slope

Nernstian

nearly

plots

recalculated for

Pb2+

as

in Table 4.1.

-J

11

//

-3

-4

-10

-8

-9

Figure

calibration

membrane
curve was

curves

was

the

obtained

by

(NaTFPB, DOS, PVC)

taken

by diluting

study (right side). Then,

that Iz'

-5

-6

-2

-3

-4

log aTtm+

4.2. EMF response

exchanger

-7

g a,

under

that at this

corresponding Kff values,

cations. The

investigated

assumption

FIM

potential change

shows any

longer

no

which is essential for

further

by

First, TMA+ is diluted in

follows.

as

originally proposed

the

ionophore,

no

the

containing

coefficients of the I SE membrane

selectivity

basis for

TM A+ with

the solution

potential determining

as

the extended FIM

ion

was

on

determining

constant

an

ISE with

Kf'j(lE).

background

an

ion-

First, the

of the ion, /"',

further diluted with pure water to confirm

(left side).

38

Chapter

Table

4.1.

Potentiometrie

membranes based

on

logKff,

selectivity coefficients,

the ion

obtained

DOS/PVC

with

exchanger NaTFPB3 or ionophore I-VIIb.

NaTFPB3

Ion

II

IV

VI

vn

N(CH3)4+

7.0

-6.3

-6.0

^1.9

-3.9

-1.0

-6.5

6.7

H+

5.4

-3.1

-3.0

-4.8

-5.8

2.5

-7.5

4.4

Na+

3.8

-2.4

-2.1

-4.5

-5.6

-1.0

-7.5

3.5

K+

4.7

-3.0

-2.8

-AA

-6.5

-1.1

-6.9

4.5

Ag+

3.8

-0.3

-0.1

15.0

22.0e

Mg2+

-0.6

-6.0

-6.2

-9.1

-11.6

-3.2

-13.9

-1.7

Ca2+

-0.5

-0.7

-0.9

-5.8

-10.9

-1.2

-13.1

-1.1

Cu2+

-0.5

-3.5

-3.6

-2.7

-0.4

-2.5

-4.0

0.3

Cd2+

-0.6

-0.7

-1.0

0.7

-1.0

-2.5

-6.3

-0.3

aExtended FIM;

mean

bSSM;

mean

total of nine measurements

different concentrations between 5

aAg

10"6

dObtained

The

aPb

with o-NPOE

response with DOS

selectivity

10"2

as

on

and 5

membranes, each

three

10"4 M; standard deviations:

three ISE membranes at aAg

by

was

possible

not

to

obtain

ionophores

or

cationic

I-VII have

the SSM. For each ion, the Nernstian response

ionophores).

condition in that at

Of the cations

higher activities,
This

S-containing ionophores.

formation of too strong

complexes inducing

counterion

(Donnan failure). Except

horizontal

(activity independent)

for

is

Figure 4.3b-d).

The

corresponding

did

were

consequence of the

coextraction of

in

Ag+

studied, only

Ag+

VI, which exhibited

response,

tested

was

anionic responses

EDTA-buffered

cationic responses have been obtained in the range of

shown in

(III)

membranes).

obtained with the

(not

0.1-0.2.

10"5

at three

M.

plasticizer [30] (it

4.3a-d for four

not fulfil this

10"2

on

coefficients for ISE membranes with

been determined

(see Figures

measurements

(IV) and

21.8e

values from measurements with six ISE; standard deviations: 0.1-0.2.

values from

Mean values from

9.5d

0.9

10"4-10"8

EMF values

and its

nearly

solutions

M free

were

Ag+

used for

39

K^A

calculating
mean

coefficients in Table 4.1

values from three ISE at three concentrations between 5

10"4

M of

primary

In contrast to the

ionophore [44],
the

probably

known that
effect

selectivity

All other

on

an

of

lipophilic

to

Pb2+

is

M. Lerchi

(I)

is observed here for

strength

of divalent
in

ETH 322

as a

and

over

agreement

PbA+ selective

Pb2+. The

anionic sites in this work. It

increased ionic

selectivity

performed by

slope

10"2

cation.

describing

paper

Nernstian

the

response

interfering

original

use

or

represent

is, in fact,

in the membrane has

monovalent ions

with

earlier

reason

is

well

beneficial

[5]. The obtained

optodes

measurements

[37].

600
500

Ionophore

400

II

300

a 2oo

|-

100
o

-100

-200

-300

N(CH3)4+

i_

-4

log

Figures

4.3a.

(ETH 5428)

Response

to the

of ISE membranes

cations under

study.

a!

(DOS/PVC/NaTFPB)

based

on

the

ionophore

II

40

Chapter

The
its

ligand

ETH 5428

binding properties

aliphatic

chains. As

discriminated

by

S. If the

not

influenced

length

the

by

alkali and alkaline earth metal ions

are

so

worsens

assumption

when the amide O in the

that the

ionophores

ligand

used do not

is

that

of the

strongly

S-containing ionophores. Interestingly, however,

discrimination of TMA+

by

apparently

expected,

all

very similar selectivities to ETH 322

(II) yields
are

the

replaced

complex TMA+

holds, this indicates that the Pb2+ complexes become weaker (see Section

4.5).

600

Ionophore

500

III

400
300

S 200

100

u.

0
Na+; K+

N(CH3)4+

-100
-200
-300

log

Figures
III

4.3b.

Response

(ETH 5493)

to the

of ISE membranes

cations under

study.

-1

-2

-3

-4

a.

(DOS/PVC/NaTFPB)

based

on

the

ionophore

41

The
to

coefficients obtained with the ISEs based

selectivity

8 orders of magnitude better than the

that,

turns out

selective

so

selectivity

new

ligand

literature values

VI

[47],

are

up

and it

far, the calix[4]arene derivate is the best available Pb2+-

ionophore.

due to the

original

on

It is

important

realize that the

to

measuring procedure

coefficients described in

for

the

improvement

is

only

of unbiased

determination

[48].

600
500
400

IonophoreIV

300

a 2oo

100

N(CH3)4+

K+
Na+

-100

-200
-300

_.

-4

-2

-3

log

Figure
IV

4.3c.

Response of

(ETH 5435)

The

Pb2+
VII

ISE membranes

the cations under

to

application

of VI in

in environmental water
was

found to be

published

data

a!

(DOS/PVC/NaTFPB)

based

on

the

ionophores

study.

Potentiometrie
samples

sensor

for the measurements of

is discussed in

only Ag+ selective,

[29, 42].

-1

Chapter

6.

Compound

in agreement with other

recently

42

Chapter

600
500

400

Ionophore

300

200

100

VI
Pb2+

N(CH3)4+
K+
Na+

-100
-200
-300

-I

-3

-4

log

Figure

4.3d.

of ISE membranes

Response

VI to the cations under

L_

-2

-1

ai

(DOS/PVC/NaTFPB)

based

on

the

ionophores

study.

4.4 Determination of the stoichiometrics

With the
of

an

experiments

ionophore

activity
calculate

on

the

above, the influence that have the presence

selectivity

of the

membrane, i.e.

on

free

formation constants, the

ionophore complex

must

publications discussing

also be known

stoichiometry,

n{,

(cf. equation 4.5).

of the
In

the determination of formation constant in

few cases, determined

by optode

measurements.

to

ion-

previous
polymeric

membranes, the stoichiometric coefficients have always been assumed,

a

cation

membrane, could be evaluated. However, in order

within the

complex

described

or, in

43

50 mV

30.9 mmol

kg"1

Lj(1)=

10.3 mmol

kg"

LT(2)

Pb2+

Ca2+

30.9 mmol

kg-V

LT(1)=

10.3 mmol

kg"1

LT(2)

N(CH3)4H

---LT(2)

30.9 mmol

kg"1

-LT(1)

10.3 mmol

kg"1

-2

-3

log a,z+

4.4.

Figure

Responses (normalized

NaTFPB) differing only

responses of

lower

one

TMA+)

higher ionophore

coefficient of ISE membranes

As shown

such two membranes

of

ionophore III,

(normalized

Lr(l)
is

kept

for

are

Lj.{2),

(DOS/PVC/

lines:

III. Dotted

concentration

Z^(2)

constant

ligand

concentration

in their

differing only

by equation 4.8,

predicted

from that with

on

the

ionophore

selectivity

concentration

are

complex

the ratios of the selectivities of

related to the stoichiometric coefficient. In the

calibration

the

TMA+)

10.3 and
at

ionophore

membranes

in order to collect information about the

investigated,

stoichiometry.

ISE

for three different stoichiometrics, nb

In this work the influence of the total

have been

of two

in their concentration of

membrane with

Lp{\),

to

shown in

30.9

value

obtained

curves

Figure

Ca2+

and

4.4 with ISE membranes

mmol/kg (RT,
of 3

for

and thus the ionic

mmol/kg).

The

dotted

case

Pb2+

having

strength [5],

lines

give

the

44

Chapter

theoretical

of the

response

1^(1}

response of those with

cations, nx

been

Z^(2)

membranes with

for three different nx values.

number of selected cases,

determined

with

membranes

two

4.8

mostly

either

by

the

simultaneous
or

4.3

nCd

[38].

were

nCu

one

In the

estimated
=

one

does not

ionophore

complexes,

cases

not

hold, the obtained values

explained

complexes

of

different

underlying assumption (e.g.,

no

figuring

learned

where the

be

of

occurrence

of the

different

number. This

integer

two

obtained earlier from the

as

calculated and

coefficients

guess,

nPb, and that all nx values

shape

in Table

of the

the

ion

optode

pairs
of HI

response

4.2, the nx values of table

by assuming

e.g.,

are

can

Pb2+ complex

violated. The value determined for the

considered) being
agrees with the

by

1)

for both

by iteratively solving

for weak

Except

little above the nearest

stoichiometrics

function

(lL [L]"1

involved

approximation
are

in Table 4.2.

given

are

Evidently,

selectivity

of

concentrations. The stoichiometric factors calculated

equation

the

calculated from

reasonable agreement between the

data. For

experimental
have

gives

same

that

for I and II

nM

<,nCei,

(for VII,

cf.

[41]).

Table

4.2.

Stoichiometric

factors

calculated with

equation

for

4.8

various

ion-ligand

complexes.
II

Ion

(DOS)

H+

1.08

Na+

1.26

K+

II

(o-NPOE)

III

(DOS)

IV

(DOS)

VI

(DOS)

(1.05)

(0.38)

1.17

(0.46)

0.89

1.04

0.99

(0.46)

(0.76)

Ag+

1.13

2.21

Ca2+

1.39

1.43

2.15

(1.38)

(0.96)

Pb2+

2.33

2.34

2.27

2.14

0.94

Values in
in

parentheses

equation

refer to weak

4.8 does not hold.

1.31

complexes (cf.

Table

4.3) for which the approximations

45

4.5 Determination of the formal formation constants

The formal

given

above

complex

optodes FT

made for

were

Pb2+ (see Figure 4.5).

instead of TMA+ is used

with the two methods

that TMA+ does not

with

interact

the

agreement of the data obtained with both

of the

ionophores

conditions in ISE

steady-state
out

in

situation of

Table 4.3a. Formal

obtained with

Ion

is not influenced

by

spite

kinetic

the

Obviously,

assumption

Moreover, the

holds.

ionophores
sensor

of the fact that in

types shows that the response

limitations, since contrary

membranes, optode

measurements

are

carried

formation constants,

complex
I

log/3n,

for

IL~n'

and

stoichiometrics,

IV in DOS/PVC membranes.

log/3

IV

II

'Ogfin

login

logln

H+

lb

4.3

4.2

2.6

<3

Na+

lb

5.5

5.4

3.7

<3

K+

lb

4.7

4.6

3.3

la

<3

Ag+

lb

6.5

6.4

19.0

Mg2+

lb

9.7

9.1

2a

Ca2+

lb

14.9

Pb2+

2b

17.2

17.4C

15.9
7.2

la

<3

14.3

10.5

<3

16.8

15.7

14.7

17.2

15.7

14.6

Cu2+

2b

14.2

2a

13.7

2a

13.5

2a

14.8

Cd2+

2b

17.1

2a

16.5

2a

17.1

2a

16.4

Standard deviations

<

0.2

(for II-Pb2+: 0.27);

b Assumed values
c

From

optode

to

equilibrium.

ionophores

In

ion, the values determined

reference

as a

in excellent agreement.

are

results, bulk optode

To validate the

listed in Table 4.3.

are

measurements

formation constants calculated with the stoichiometrics

measurements

9.

n,

46

Chapter

Table

4.3b. Formal

obtained with

formation constants,

complex

ionophores

Ion

H+

la

Na+

la

3.2

K+

la

4.2

Ag+

la

6.0

Mg2+

2a

8.6

Ca2+

2a

Pb2+

2a

log/3,

for

lb

<3

lb

<3

lb

<3

2b

12.6

<3

lb

<3

10.5

<3

lb

<3

11.4

15.9

lb

<3

<3

<3
3.1
1

<3

15.2

9.1

12.1

lb

<3

Cd2+

2a

9.3

10.0

lb

<3

<

0.2

n,

2a

Standard deviations

stoichiometrics,

vn

Cu2+

and

VII in DOS/PVC membranes.

vi

11.5

7L'

(for II-Pb2+: 0.27);

9.

b Assumed values
c

From

The
IV

optode

measurements

comparison

surprisingly

induces
about

order of

consequence of
one

surprising
analogy

complex

stability

magnitude.

The

interfering

result is that the

of the

Further

that

Ca2+

an

amide O

II-

by

of

is not the

stoichiometry

are

of the
in

Ca2+-II (and,

DOS/PVC

Pb2+ complex is

results obtained with other

tends to form

investigations

alkali and alkaline-earth metal ions. Another

Ca2+-I) complex

previous

corresponding Pb2+ complex by

selectivity improvement, thus,

membranes is 1:1, whereas that of the

is in contrast with

of

replacement

ionophores

stronger complexation of Pb2+ with the ligand, but of

of the

reasons,

showing

formation constants of

shows that each successive

reduction in the

one

weaker

of the formal

complexes

necessary to

and
1:2

o-NPOE/PVC

(Table 4.2).

This

Ca2+ ionophores [28],

of stoichiometries

explain

for structure-

higher

the contradiction.

than 1.

47

4.6 Ion-selective bulk

optodes

Since ion-selective bulk

introduction is

given

optodes

are

not

topic

here. The measurements with

assumption

ionophores.

More detailed informations about

spectral properties

The thin membrane

optode

membranes the

additive. The

or

primary

ion in the

by

be found in the

is the

constant of

an

on

are

that

ionophore

and

the cation

an

changes

spectrophotometrically.

lipophilized glass plate,

ionophore

an

of

contains in

lipophilic

anionic

exchange equilibrium
phases.

of

Activities

accessible, if the sample pH is measured

The response

curve

of

an

optode

membrane is

following equation:

K -(-a)cA

)ZI

zY

cast onto

sample

by buffering.

the

__(vIx

where

here

investigated

protonation

ion and H+ between the aqueous and membrane

constant

described

(2-4 |i,m),

optode signal depends

primary

kept

can

of

degree

is measured

protonation,

upon

chromoionophore,

addition to the

of the

optodes presented

optodes

incorporated tT-selective chromoionophore, i.e.,

the

brief

[31, 49-51].

In ion-selective bulk

its

work, only

that TMA+ does not interact with the

validate the

references

of this

degree

of

equilibrium
and

membrane

phase

The other

symbols

LT

--{RT -(l-a)CT|

deprotonation

for the

CT

of the

exchange

chromoionophore,

of H+ and 7Z'

between

is the total concentration of the

have the

same

meaning

as

in the

Klexch

is the

sample

and

chromoionophore.

equations

for ISE

(see

above).
The

complex

exchange

formation constant

constants

exchanger)

was

obtained from the ratio of the two

determined for membranes with

cation-selective

ionophore:

(L)

and without

(IE,

ion-

48

Chapter

^exchlW

Au.

(4.10)

^exch(lE)

"'

Without
IV

III

0.0

ionophore

(ETH 5435)

(ETH 295)

(ETH 5493)

-12

-10

-8

-6

i_

_l_

l_

-4-2024

10

log apb2+

Figure
and

4.5.

Responses

to

Pb2+ (normalized

to

chromoionophore

pH 4.7) of six DOS/PVC optode membranes based

indicated

points

(cf. Figure 4.1)

were

fitted with

and the

chromoionophore

equation (4.9) using

on

the

ETH

5418; pKa 9.0 [51]

Pb2+-selective ionophores

ETH 5418

or

as

ETH 5315. The data

the stoichiometrics from Table 4.3.

49

4.7

Experimental

sebacate

Reagents. Poly(vinyl chloride) (PVC), bis(2-ethylhexyl)

sodium

(NaTFPB),

tetrakis-[3,5-bis(trifluoromethyl)phenyl]borate

Methylene-bis-7V,A^-diisobutyldithiocarbamate (MBDiBDTC,

VII),

butyl-calix[4]arene-tetrakis(AyV-dimethylthioacetamide)
tetrahydrofuran (THF)
ionophores

(cf.

were

Figure

from

Fluka

4-tert-

and

(VI),

(CH-8071

AG

(DOS),

Buchs).

The

7V,A^-diheptyl-7V,iV,6,6-tetramethyl-4,8-

1),

dioxaundecanediamide) (ETH 295, V), Af,iV-dioctadecyl-J/V',iV,-dipropyl-3,6dioxaoctanediamide)

(ETH

322,

I),

N,AyV\yV-tetradodecyl-3,6-

dioxaoctanediamide)

(ETH

5428,

II),

AWV,7V-tetradodecyl-3,6-

dioxaoctane-l-thio-8-oxodiamide)

(ETH

5493,

and

III),

NJJfJfwell

tetradodecyl-3,6-dioxaoctanedithioamide) (ETH 5435, IV)

as

chromoionophores,

5315)

4-(octadecylamino)azobenzene

(ETH

as

the

and

9-

dimethylamino-5-[4-(l 5-butyl-1,13-dioxo-2,14-dioanonadecyl)phenylimino]-

5//-benzo[cc]phenoxazine (ETH 5418)

ca.

solution of

ca.

2.5 mL of THF, into

ion-exchanger
DOS

(66.15

ionophore

our

laboratory

as

were

obtained

by

in

[37, 38, 52].

ISE membranes. Membranes of

pouring

synthesized

ca.

200 \im thickness

250 mg of the membrane components, dissolved in

a

glass ring (28

mm

i.d.)

membrane contained NaTFPB

wt%),

had the

and

same

PVC

amount

on a

(0.45 wt%,

(33.40 wt%).
of NaTFPB

fixed

The

(5.00

glass plate.
5.00

mmol/kg),

The

mmol/kg),

membranes

65-wt%plasiczer,nd32ofPVC.Ih:ETH19(m/kg);4807MBDxbuNFOS

described in

were

with

an

50

Chapter

and PVC
under

respectively)

owing

to its

and 4.32

used. These

were

were

in DOS,

solubility

mmol/kg, respectively),

0.04 wt%

membranes und
mm

filling

(Ag|AgCl,
10"3

with

glued

i.d. Three ISEs

internal

with

they
a

prepared

were

solutions

in

were

KCl) through

3 M

tetraacetic

ethylenediamine

for those with

carried out at

Hg|Hg2Cl2|3

Measuring

KC1|1

with

solutions

were

10"3

The

chloride of the

sample

was

10"3

10"

ISEs

were

M chloride

All measurements

LiOAc|sample||membrane||inner filling solution|

saturated calomel reference

electrode

[53].

successive automatic 5-fold dilution of

711 and two Dosinos 700

(FIM)

as

values

ion under

ion constant, the

not

were

follows: The ISEs

sample containing 10"2

each, until further dilution did

the

with

10"1

(Metrohm AG,

CH-

with 50-mL burettes.

interfering

interfering

TMA+).

The

consisted of

ion-exchanger-based
a

of

half-cell

and of

(Na2EDTA)

or

tubing

composition.

ionophore,

salt

(Na+

ion-exchanger membranes, ^j^j

10 min in the initial

PVC

reference

the

TMAC1, the others in

from the master

punched

bridge electrolyte. They

disodium

prepared by

fixed interference method

of the

(1.58

temperature (ca. 21C) with cells of the type

Liquino

Herisau) equipped

For the

ionophore VI,

plasticized

for ISEs without

free-flowing

stock solutions with

9101

to

with

contact

ionophore.

room

were

for each membrane

solution of the most discriminated cation

AgCl|Ag,

mmol/kg,

concentration of

constant NaTFPB

slurry

1 M KCl

acid

conditioned for about 12 h in

were

10 and 30

0.17 and 0.46 wt%

were

diameter

mm

THF/PVC

N(CH3)4C1 (TMAC1)

Pb(N03)2

(ca.

(0.47 mmol/kg).

EMF measurements. Disks of 5

0.9 and 2.6 wt%

for ETH 5428, ETH 5493, and ETH 5435. For

limited

ionophore

but two different concentrations of the

(32-33 wt%)

study

were

give

any

the

equilibrated

for

10"3

M TMAC1 and 2

study. Then, keeping

sample

by

determined

was

the concentration

successively

diluted 5 times

potential change.

At this

point,

diluted twice 5-fold with pure water to ascertain that the ISEs

51

responded

the

to

ion. After each dilution step, the

interfering

potential

was

obtained with

the

measured for 3 min.

For

ionophore-based membranes, A^AJ

method described in

10"2-10"4

[29], measuring

M for each

values

the response

boundary potential
solution

(10~3

was

kept

by using

constant

M, those of Pb(N03)2,

around 0.1 mV in most

measurements.

mmol/kg (1.00 wt%)

(I-VI),

9.2

and

cases

film had the

same

films of 2-3

urn

thickness

UV-vis spectra

10"2

M with

time, drifts

of

period

of the

optode

chromoionophore

were

remaining

films

were

10.8

was

of

ionophore

5418, 65-66

ETH

prepared

were

and

determined with
Orion 91-57 BN

(Guidener
with the

pH

meter

Werner

thermostat

solutions

The

of

spin-on

measuring

were

Haake

device

using

values

KG,

were

Berlin,

buffered with 2.5

were

pH triode electrode

Abtwil).

cells

by

controlled

[55]. The pH

cell

CH-9030

Zrich)

peristaltic

Meyer AG, CH-6000 Luzern)

(Gebrder

(O^-IO"6 M)

help

optode

UVIKON Model 810 double-

Orion Model 290 A

(Hgli-Labortec AG,
Perpex II,

CH-8010

flow-through

flow-through system.

of

Pb(N03)2

Vario

using

with the

measured with

were

constituents. The membrane

dissolved in 1.5 mL of THF and

spectrophotometer (Kontron AG,

Macintosh SE

means

10"2

were

mmol/kg (1.1-2.3 wt%)

of the

of the

amounts

components totalling 150 mg

beam

AgN03

were

above 0.5 mV.

never

of NaTFPB, 26.3

mmol/kg (0.65 wt%)

samples

DOS, and 32-33 wt% of PVC. The corresponding ionophore-free

wt% of

[54].

"7-1-

After each dilution step, the

this

During

composition

The

in the

and

(pH 4.70).

M HO Ac

measured for 5 min.

was

Optode

Cu(N03)2, Cd(N03)2,

10"3

M NaOAc and

potential

Pb

EDTA-buffered

an

Na2EDTA, 10"5 M Pb(N03)2). Initial concentrations of HCl,

NaCl, KCl, Ca(N03)2, Mg(N03)2, and TMAC1

10"3

work, the internal phase

with the most discriminated ion. In this

starting

in the range of 5

curve

increasing selectivity coefficients,

sequence of

ion, in

were

kept

was

used

at 25 C

Germany).
10-3

pump

by

The

Mg(OAc)2

52

and 5

Chapter

10"3

M HO Ac to

membrane, unbuffered
activities

taking

were

calculated

into account the

[56, 57].

pH
10"1

4.70. For measurements with the

M

Pb(N03)2

according

complex

to

the

was

used

ionophore-free

(pH 3.90).

Sample

Debye-Hckel approximation

formation of

and

Pb2+ with AcO", NO3" and OH"

53

5. INFLUENCE
DETECTION

LIMIT

RESPONSE

AND

ON

PARAMETERS

KEY

OF

LOWER

THE

OF

FUNCTION

SOLVENT

POLYMERIC MEMBRANE ION-SELECTIVE ELECTRODES

The lower detection limit

electrodes in diluted

samples

given by

is

phase.

the membrane into the aqueous

inner solutions

membrane ion-selective

of conventional polymeric
the release

It

can

of measuring

ions

from

greatly improved by using

be

of appropriate composition [30, 39, 58].

5.1 Introduction

In most

described

cases

ion-selective membrane electrodes

polymeric

[3, 24]. Significantly

micromolar range

analyte

far, the lower detection limits of solvent

so

ion activities

were

kept

lower values

the aqueous surface

layer,

to

significantly [1, 59-61],

ion buffers

was

this field has

explicitly

not

only

started

the

origin

more

recently,

sensors, whose response mechanism is

much better lower detection limits

when it

closely

lie in

more

found when the

sample

and the

that

release of primary ions from the

This
of

for

causes

10"6

even

strongly

cases

their
in

activity
highly

sensing

recent years, it became

diluted

samples.

biased

membrane into the

in the sensed aqueous Nernst

The

layer

by

fact, they

are

based

on

to

heavily

continuous

sample

solution.

be of the order

reported selectivity

discriminated ions obtained with conventional ISEs

biased too. In

optical

[6], had

evident that the achievable lower detection limits of ISEs had been
are

bulk

intensive research in

related to that of ISEs

underrated. Their values in conventional systems

[26,

concentrations in

recognized

was

[42, 62]. Only in

the

improvements by using

of the

traced at that time. A

to

of ion buffers

analyte

responds,

which the I SE

may differ

were

help

under control with the

Even if it has been known for decades that the

28].

reported

were

coefficients
are

in most

EMF values measured in solutions

54

Chapter

containing only

the

activity

primary

of the

ions released from the inner solution

and may be

At present, there

ones.

to obtain unbiased

that

was never

for

curve

various

are

selectivity

in contact with

discriminated

by

many orders of
means

to

reduce

coefficients. For

primary

through

the

are

too

than the true

magnitude

avoid such effects and

or

example,

ions before

interfering ion,

the

coefficients thus obtained

selectivity

worse

to

responding

but with the ISE still

interfering ions,

membrane. The values of the

pessimistic

ISE membrane

an

the calibration

recording

exhibits Nernstian

slope

to

the latter

and, therefore, provides unbiased thermodynamic selectivity coefficients [29,

48, 63]. The

primary

same

results

can

ions from the inner

be obtained with ISEs in wich the release of

filling

solution to the

is

sample

prevented [30,

39].
The

primary

ion release from the membrane is

ion fluxes that have their

their counterions

exchanges

at the

from

origin
the

an

appropriate
the

lowering

in the coextraction

choice of the inner

analyte activity

detection limits

can

effects

filling

can

the

has
a

too

high

negative

primary

ion

concentration of

influence

uptake

on

many orders of

activity,

sample

on

are

not

an

high,

by

appropriate
the lower

magnitude [39, 65].

be

must

carefully adjusted.

the inner membrane side

limits,

too

low value induces

into the membrane. The

large super-Nernstian step

below which the ISEs

processes,

by

ions

primary

the lower detection

from the

response functions show

through

concentration

However, the composition of the inner solution

While

[30, 58].

solution. It has been shown that

interfering-ion

ion

efficiently compensated by

be

in the inner compartment

improved by

be

[64] of primary ions and

inner solution into the membrane and/or

exchange

buffer, while keeping

ion

consequence of zero-current

and inner solution-membrane interface

sample-

Both coextraction and ion

sensitive to the

at

primary

corresponding

critical
ion

sample

[30].

Both

i.e., ion release and ion uptake, have been successfully described

theoretical model worked out for the

The influence of the

composition

steady-state

of the

inner

situation

[58, 66, 67].

solution and

of various

55

membrane parameters

on

the response function of ISEs has been

with this model and verified

5.2

polymeric

ion-exchange, coextraction,

of

Theory

shown in this

by experiments

chapter [30, 68].

in

diffusion

solvent-

ion-selective membranes

In recent years, several models have been

the response function of ISEs in diluted

consider the influence of

coextraction from the
zero-current

ion-exchange

sample

ion-fluxes

the

Section

those processes

are

developed

for the

between

sample

membrane

only

prediction

of

samples [58, 66, 67, 69]. They

inner solution into the

or

through

In this

boundary layer.
describing

and

predicted

the

basic

and

membrane, of

and

membrane, and of
the

aqueous

equilibria

and

phase

equations

explained.

Ion-exchange

Uncomplexed interfering
membrane interface

^-JZJ(S)

where

(S)

IZ'(M)

and

respectively.

according

(M)

The

ions

refer to

exchange
to

the

with the

primary

ones

\alM>\als)

the

sample-

following ion-exchange equilibrium:

^-JZj(M)

species

Iz'(S)

in the

sample

(5.1)

and membrane

equilibrium constant, Ku (cf. equation 3.7)

*U=MM

at

is

phase,

given by:

(5-2)

56

Chapter

the

By considering
membrane

complexation

(cf. equations

(\zi'zj

The

exchange

constant

calculated without

between the ions and the

4.1/4.2 and

constant is obtained

equilibrium

as

follows

the

The

of

are

Ku

coefficient and
and

of the

Ku

equation

Zi

\rt)

above

the

appropriate

At

equilibrium,

mass

(Lj.

charge

and

balances

the concentrations

combining equation

als

5.3 with the

[ /L*1 ]
and

(54)

equations

a}S

following

[ 7LJ ]

in

the

mass

4.1 and 4.3

4.6a and

(equations

and

be

known:

/ZiY1

be obtained from

can

calculated if the activities

(equation 5.6)

-niRT

can

stabilitiy

RY(^',^'(L<-n]R1lzs^',I

1
_

^exch

selectivity

magnitude

constants, if all the membrane parameters

(cf. Figure 3.2):

is related to the

knowing

ion-exchange

izi/zi

^exch

the overall

Figure 3.2),

in the

ionophore

by inserting

4.6b).

in the membrane

samples

are

(equation 5.5)

can

be

known, by
and

charge

balances:

L=LY-nl[lLl]-ni[jLl]

(5.5)

^T=^.[^Zn,I]+2j[^nJJ]

(5-6)

The

equation system

Zj

Zj

and nx

has
n}

an

1.

analytical

solution

only

for the

This has been used for the

simple

case

description

where
of the

57

response function of

fluxes

under

ionophore-based

zero-current

ISEs

Section

If

[58].

conditions

stoichiometrics have other values than 1, the

numerically (cf.

by considering steady-state

charges

the

equation system

or

ionthe

has to be solved

5.4).

Coextraction

The word coextraction is used to describe the

cation

analyte

membrane

together

with

counter

"I

YZX

X'x

thermodynamic equilibrium

coextraction constant,

K\x

ion

of the

between the

uncomplexd

sample

of this

(M)

F1

process

is

described

ai,s

(kj"z*
is

primary

ax,s

same

to

measuring

ion

/ and

The overall coextraction constant

kx.

process, when the

complexation

kx

is defined in

Kcoex

between

is used to

ionophore

and

ion is considered:

^coex

the

Klx [19]:

counter-ion of the

complete analogy
the

with

(5.8)

\Z|/Zv

quantify

the

(5.7)

(M)

where X

and

phase.

^-XZx(S) + Iz,(S)
The

partitioning

PlLn

ni(^x)ZlX

i,sMni

The influence of the coextraction

is treated in detail in references

*_}

-z,/zx

(5.9)

V X,S /

on

the theoretical response function of I SE

[19, 58, 64, 66].

58

Chapter

Diffusion

transfer

Mass

in

transport in

given by

J.(x)

'

of

because

diffusion and
A

gradient

migration)

or

in

the

because of
of the ion

general description

electrochemical cell at constant pressure and temperature, is

the Nernst-Planck

'v

-D.

occur

(i.e., by convection).

reasons

an

can

potential fi (i.e., by

electrochemical

hydrodynamic

solution

--*

dx

D.c.-^'

RT

equation [70] :

'

cMx)

(5.10)

'

diffusion

d(x)

convection

migration

with:

J\ (x)

rate

of transfer of the

species

coordinate, flux [mol cm"2

cl

concentration of the

Z),

diffusion coefficient for the

0(jt)

electrical

-Jl(x)

migration

perpendicularly

[cm]

to the section

diffusing species

in x-coordinate

Nernst-Planck flux

diffusion if the

x-

[cm2 s"1]

in x-coordinate

v(x) hydrodynamic velocity

general

of the section in the

diffusing species [mol cm"3]

space coordinate measured

The

area

s"1]

jc

potential

/ per unit

equation

[cm

s"1]

reduces

and convection terms

can

to

be

Fick's

first

law

of

neglected:

Dl^

(5.11)

dx

Diffusion is defined

as

the natural movement in

the electric field. The flux of

substance /,

solution, without effect of

Jx(x), represents

the number of

59

moles of / that pass at

given

the direction of diffusion

For

the

y,

one-dimensional

cm2 of

location per second and

area

[70].

steady-state system,

the differential

equation

5.11 has

solution:

simple

A^

normal to

(5.12)

Ajc

gradient

is the concentration

/ Ax

of the

species

where

Ac,

means

that the concentration of the ion / at the coordinate

i.
x

Steady-state
is not time

dependent.
The

equation

above

can

be used for

modeling

the ISE response, if the laws of mass and

and if the ionic concentrations in the

boundary layer
-

the law of

mass

the Nernstian

<5S

layer

and of the

the law of

sample

conservation

are

on

considered,

bulk and in the inner membrane

[58, 66, 67]:

requires equal

and the membrane

fluxes of the

species

/ in both

phase:

(5-13)

M denoting

and

with

conservation

layer

AC!,S-T-= Ac,,M

charge

assumed to be constant

are

the influence of ion-fluxes

the thickness of the aqueous Nernstian

boundary

membrane, respectively;

charge

conservation for zero-current measurements forbids

net

charge-transport:

2V,U)

Such system of

explicit

(5.14)

equations

solutions

exist

can

only

usually
for

be solved

only numerically. Simple

special systems considering only

two

60

Chapter

monovalent ions. Simulations of the ISE response that takes into account

migration

also

are

reported

in the

literature, but they need

much

more

complicated approach [71, 72].

5.3

Leaching

Depending
of

gradients

depletion

and

on

the

at the

compositions
and/or

primary

of

sample

interfering

is

accompanied by

counterflux of

Aci

PB

bulk of the

interfering

ci

bulk

sample,

'

c{

ions

unstirred Nernstian

one

layer

primary

ions

across

ion

fluxes

on

and in the sensed surface

through

cause

between the concentration of the

bulk,

direction

same

the membrane

the membrane

by

ion-

difference,

primary

layer

an

or

ion in the

the membrane,

near

the lower detection limit of ISEs is

represented

in

5.1.

Usually,

in

samples

with

10"6 M, the magnitude of Aq

primary
s

ion concentration

is much smaller than cl

function of the ISE is not influenced

activities the

higher

adjacent

entering

concomitant

The

cIPB. Their influence

Figure

induced toward either

that of coextracted counterions in the

process.

ci

are

solution, concentration

sample.

Under zero-current conditions, the flux of

exchange

and inner

ions

side of the ISE membrane and within the

of the aqueous

interface

sample/membrane

or

function.

analyte

concentration at the

lower than that of the

by

ion-fluxes.

higher

bulk

and the response

Only

phase boundary

than about

can

at

be

lower bulk

substantially

bulk, leading biased, non-linear response

61

SAMPLE

INNER SOLUTION

ISE MEMBRANE

cJ,bulk

RT
CI,PB

cI,inner

"pL+

cJ,inner

cI,bulk

cJ,inner

RT
cI,bulk

PL+

cJ,bulk

CI, inner
CI.PB

Figure

5.1. Schematic

representation

of an ISE, which is based

and

interfering (/*")

layer (s)

either

by

on an

of the processes

ionophore (L)

ions. Concentration

influencing

that forms

gradients

are

the lower detection limit

complexes

generated

with the

primary (t)

in the aqueous Nernstian

coextraction of t and the counterionX from the inner solution

by partial ion-exchange

at

the

sample

and inner membrane sides

(B

and

C).

(A),

or

62

Chapter

When the flux of

ions is directed from the membrane to the

schemes A and

(Figure 5.1,
Ac,
'I,S

primary

since at low bulk concentrations

the

relatively

concentrated inner solution

sample

negligible.

situation where

In the

may

are

anions

Scheme A

c,

u,,^

'I,PBDn

"-I.bulk

coextracted

transported through

the

from

the membrane

interfering

gradients

the

by

ions at both membrane surfaces.

of the

layer

induced

are

sample

depleted

is

of the

ions since their concentration in the membrane decreases toward the

at

C).

In

an

bulk concentration of the

concentration

cipb <<cibuik' and

me

gradient

observed

the concentration cIbulk. As

potential

phase boundary

primary ion,

cl

bulk.

approaches

AcIS

successive

with

experiment

the concentration in the aqueous

given

the

activity

scheme

(Figure 5.1,

sample dilutions,

At

and

primary

and

concentration

case, the Nernstian

inner solution

abruptly

cations

c,

when coextraction from the inner solution is

even

In this case, the

reverse

primary

an

DD

by

Scheme B shows that ion fluxes in direction of

sample.

occur

between

exchange

has

c,
I,PB

and reach the dilute

sample

the lower detection limit is determined

B),

describes

the

decreases

At this bulk

since

cIbulk,

is much lower than

for

expected

consequence, the response function of the I SE

apparently super-Nernstian slope.

the

steady-state,

between both

concentration difference

membrane, AcIM, and of the Nernstian layer, AcIS, is related

coefficients, DlM and DIS, of the primary ion in the
thickness of the

respective potential determining

two

diffusion

sides

of the

to the diffusion

phases

and to the

layers M

and

(cf. equation 5.13):

Aci,s

A,nA
=

Aci,m

D,SM

r,

<?

The diffusion coefficients of cations in water

example,

for

complexes

Ca2+it

(5.15)

is 8

10"6 cm2

in the membrane

are

s"1) [73],

are

about

10"5 cm2 s"1 (for

while those of the

in the order of

ionophore

10"8 cm2 s"1 [74]. Since

63

lipophilic

ionic sites

and,

as

concentrations in the membrane

see

Section

much

5.4)

the overall

than the

higher

one

rather

are

ion-transport
in

measuring

consequence, the

in the

the smaller diffusion coefficients in the membrane

ionic
can

concentrations,

influence

the

so

that the slow ion release

of the

composition

diffusion coefficient in water is much

of

5.4 Influence

membrane

sample composition

The

steady-state

coextraction

[58, 66, 67],

was

to

layer,

inner

of the inner

composition

sample,

the concentration of

flow-through cell,
membrane
function

of

solutions

(A

membrane

D)

Ca2+-ISEs

how various parameters of

predict

inner

membrane

(80%

of

as

Ca2+

long
is

convenience, the

sample

anions in the

lipophilic

experimentally.

solution

generates
as no

polymer
Their

replaced by Na+

(10"3

the

content

influence
four

same

an

I SE

ISE-response

curves

Ca2+)

coefficients of the different ISEs

ion

at the inner
are

shifted

coincide.
are

the

on

of

ISE C with

kg"1,

occurs

on

side of the
so

The

that

of

of the

response

inner

different

concentration

exchange

use

(viscosity)

filling

conventional

RT: 4.5 mmol

is used for direct

Figures)

significant

significant

response

on

membrane, the

thickness: 150 ^im, LT: 13.1 mmol

with full circles in

solution

effects

solution, the presence of interfering ions in the

reported, whereby

(membrane

kg"1; represented
Its

is

and

solution

gradient generating

as

Ca2+-selelctive electrodes with

to

the

though

above, which considers ion exchange and

and the thickness and

studied

are

the membrane

even

filling

influence its response function. In this Section the effects

the

be

higher.

parameters,

model outlined

applied

can

consequence,

uptake by

or

Nernstian

both sides of the membrane

on

As

kg"1,

compensated by higher

are

the response function of

on

5 mmol

ca.

membrane, AclMDlM,

sample, AcISDIs.

diluted

high (typically

ion

interfering

or

comparison.
in

the

sample

side

membrane).

For

gradient
the

potentials

in the first

Potentiometrie selectivity

summarized in Table 5.1. Since

quasi-

64

Chapter

Nernstian responses
coefficients
them for
the

obtained for all

were

correspond

to

thermodynamic

calculating equilibrium

adjacent

membrane surface

Selectivity

Table 5.1.

PVC and NaTFPB

membrane surface

values

[67],

layer

that it is safe to

use

distributions between the inner solution and

layer (cf.

Section 5.2,

coefficients of of various membranes

(i?T)

so

selectivity

the

investigated ions,

Ion-exchange).

containing

different amounts of

Ca2+ replaced by Na+

and calculated percentage of

for the inner solutions A, B, C and D. The ratio

Z,T

in the inner

Rj is 3

1 for

all the membranes.

PVC

IVj"

[mmol kg"1]

wt%

% of

log^H

log ^Ca.Na

Ca2+ replaced by Na+

membrane surface

in the inner

layer

<0.1

1.7

79.8

>99.9

4.6

32.2

-4.7

-2.5

4.6

20.8

-5.1

-2.7

65.0

4.6

49.5

-5.6

-3.3

46.0

0.45

32.2

-3.7

-1.2

97.2

0.04

32.2

-1.5

1.0

99.8

The flow-through cell

The

influence

of the

various

membrane

response function of the ISEs has been

and

sample parameters

investigated using

are

in the

flow-through system,

conditions
in the

beaker.

two motivations for this choice:

thickness of the Nernstian

the

flow-through

system (Figure 5.2) instead of the conventional stirred solutions in

There

on

are

the geometry of the

layer

exactly

defined

cell and the

that the

experimental

so

perfectly reproducible;

flow-through system,

membrane is

are

measuring

the

continuously renewed,

sample
so

that

solution
even

at

contacting

low

Ca2+

with

the

activities the

65

bulk

concentration

membrane

or

illustrated

by

affected

not

beaker wall and

the

contains 5 mmol

only

is

10% of its

following.

sample.

kg"1 lipophilic
Ca2+

content is

will be contaminated with 3

by

typical

ion-exchange

The

of this

importance

membrane has

processes

anionic sites and thus 1.5

exchanged by Na+,

10"8

mass

50 ml

between

precaution

is

of 3 mg and

10"8 mol Ca2+. If

sample

solution

Ca2+.

Ion-selective

Reference

electrode

electrode

Ag/AgCl

Bridge
electrolyte

3 M KCL
1 M HN03
Pt wire

Internal

Ion-selective

electrolyte

membrane
6

65

Figure

5.2. Schematic

representation

To reduce the noise caused

diffusion

potentials

that

electrode and the ISE

by

can

were

of the

the

mm

flow-through

pulsation

cell.

of the

arise in the small

placed

mm

peristaltic

pump and

by

flow-channel, the reference

in front of each other in the

flow-through

66

Chapter

cell

and the

potentials

measured

were

reference and counter Pt

(working ISE,

Influence of the

composition

function of the ISEs is shown in

MNaCl)

0.1

membrane

was

Nevertheless,
due to the

use

B, C, and

some

Ca2+

rather

of the

on

good

of the inner

Figure

the

side

sample

concentration

cell

(cf. [75]).

10"7

Ca2+

of the membrane. From the

in the membrane

and sites

was

calculated

containing
as

lower detection limit of

The fluxes

surface
that

10"8

10"8

generated by replacing

layer

of ISE C

cause a

Ca2+.

Below this

Ca2+

at

the

in the inner
of the inner

the amount of Ca

1.7, 79.8, and >99.9% (ISE B, C and

to

theoretical response

M is obtained with the inner solution B.

79.8% of

depletion

of the

Ca2+

in the inner membrane

sample

at low

concentration, the potential does

sample

predicted by theory,

abrupt changes

this

diminishes.

conventional amounts of PVC,

side of the membrane is

Na+ (cf. Response times). The steep EMF change

the

solutions

Ca2+ activity

so

strong (super-Nernstian) EMF change is observed in the range of 10"7-

aca,buik, and

was

filling

composition

D, respectively; cf. Table 5.1 and Figure 5.3). A close

a

obtained,

gradually

Potentiometrie selectivity coefficients,

solution and the

and

is

exchanged by Na+

phase boundary layer

are

gradient

Ca2+

In the inner

in the inner solution

of

(1

investigated samples.

all

for

lower detection limit of

flow-through

the response

on

into the conventional

Ca(N03)2

amounts

with

assembly

5.3. With the inner solution A

Therefore, increasing

ionophore

solution

filling

This generates

Ca2+ activity

D the

replaced by Na+

electrode

three

electrode, cf. Figure 5.2).

coextraction of

expected [64].

release of

steady

with

inner filling solution

The influence of the

Ca(N03)2,

possibility
region.

than those

of

activity

but earlier

at

experimental

presented here,
measurements

not

depend

on

slowly exchanged by

the critical

Ca2+ activity

[30]

showed less

results

and could have

with increased

wrongly

indicated

sensitivity (slope)

in

67

In ner

solution:

>

jf

&1/T

_e-

m
50 mV

--*

o^^
i,i,

-9

-10

-7

-8

-6

-3

-4

-5

log aCa2+

Figure

5.3.

Response of four Ca2+

conventional membrane
M

NaCl; (B) 10"3

pH 5.4; (D) 10~3

In the present

corresponding
h),

of

the

composition

CaCl2,

CaCl2,

0.1 M

Na2EDTA, pH

of

occurs

exceeds that of ISE C

the

with

ISE

potential

by

that

so

already

at

pair

of

recorded for

larger

inner

with

such

Ca(N03)2,
M

0.1

Na2EDTA,

C.

it

as

longer

time

(2

In the inner surface

solution

D,

is

Ca

gradients

are

Therefore, the super-

was

and the EMF step

proposed

to

monitor

ISEs C and D to obtain

strong signal in the critical activity range between the

MF-steps [76].

10"2

concentrations

Recently,

sensors

1 M

obtained because at the

higher Ca2+ activity

about 50 mV.

difference of

was

are

the

than in the membrane of ISE

Nernstian response

(A)

9.

curves

potential

quantitatively replaced by Na+,

generated

ETH 5234 with identical

h"1 (cf. Response times).

10 mV

membrane

ionophore

but different inner solutions:

concentrations the
was <

the

NaCl, pH 5.7; (C) 10"3 M CaCl2, 5

10"2

on

work, steeper response

until the drift

layer

ISE based

two

super-Nernstian

68

Chapter

Influence of the

concentration

ions in the

of interfering

affected

by

background,

the
a

ionic

lower detection limit of 1.6

close to the value

traditional

of the

background

(static)

(tfNaaJa

model

With

sample.
10"7

from the Na+

expected

of ISE

function

5.4 demonstrates that the response

Figure

Ca2+

is

0.1

strongly

M NaCl

as

is obtained. This is

interference

10"7,

sample

cf. Table

according

to

the

5.1) [25]. On the

contrary, with 10"3 and 10"5 M NaCl and without Na+ background, the lower
detection limits
fluxes
the

by

Ca2+

the

are

introduced

formalism. The observed differences in

Nikolsky-Eisenmann

responses at activities

<

10"7

model

dynamic selectivity

in the absence of ion

predicted

than the values

higher

be

can

explained by

recently

[77, 78] (cf. Chapter 6).

Background
electrolyte:

10"1

M NaCl

>

10-3 M NaCl
IQ"5

No

50 mV
M NaCl

background

-10

-9

-8

-7

-6

-5

-4

i_

-3

log aCa2+

Figure

5.4. Influence of changes in the

response

expected

activity

function of the ISE with inner

from the

of the

filling

interfering Na+

C. Much

Nicolsky-Eisenman equation, except

in the

in the

sample

on

the

smaller influences would be

case

with 0.1 M Na+.

69

The
at

exchange

10"8

Ca2+

respectively)
reduces the

Figure

of

on

uptake

5.4 the

reduced with

only

the

(Figure 5.4)

lipophilic

primary

increasing

surface

6% and 1 %

10"5

and

layer.

NaCl,

gradients

and

As shown in

is

uptake,

ion

successively

ionic sites in the membrane

of lipophilic

in the inner

(Figure 5.3)

and outer

membrane, but also the concentration of

ionic sites define the extent of concentration

exchanger, RT,

(ca.

of interfering ions.

of the

layers

expected

membrane. It is therefore
ion

containing 10"3

ion-exchange

of

ions from the Nernstian

amounts

concentration

degree

or

side of the membrane modifies the

sample
of

pH

super-Nernstian slope, i.e., primary

Influence of the

Not

in solutions of
the

by Na+

minor amounts of Ca

only

that

gradients

within the

decrease in the concentration of the

will reduce ion fluxes in either direction

[66].

Concentrations of
NaTFPB

[mmol

(Rt)

kg"l

>

Rj 0.05

ta

50 mV

_i

-10

-9

-8

-7

-6

-5

-4

i_

-3

log aCa2+

Figure

5.5. Influence of 1 Ofold

changes

in the concentration of ionic sites

of the ISE with inner solution C. The concentration ratio of

Lj/Rj,

is the

same

for all membranes.

ionophore

on

to

the response

ion

exchanger,

70

Chapter

In the
to

shown in

experiments

ion-exchanger, RT/LT,

concentrations

Figures

5.3 and

10"9

Ca2+. However,

5.4),

kept

and

with

(full circles,

lOfold reduction of RT and LT, the

further

lower detection limit increases. This

explained by

be

can

the

H+ selectivity of this membrane (see Table 5.1). As

divalent to monovalent ion
of the membrane
of

selectivity

ion-exchanger

was

non-exchanging lipophilic

salt

amount

logA^lH

(K^a^

to reduce

only

For

increase the coextraction of

other hand will

positively

Influence of the

The essential

thickness

problem

limited ion fluxes

lipophilic

ions at

influence the

through

theoretical

experiments

shown in

primary

C, which shows
range when

probably

is

on

can

the

keeping
hand

one

but

on

the

Figure

of the

layer

of

since

primary ions,

predictions

are

5.6. The response

flow-through

ion

uptake,

cell is

sample.

the
A

decrease of

ion-transport (cf. equation 5.12)

are

in the

ion-transport through

fully

curves

by

confirmed

the
the

obtained with ISE A,

ions leach from the membrane into the

significant

are

is beneficial to the detection limit of

and thus reduces the influence of the

These

for which

or

increase of the net

membrane.

it

kg"1,

by FT

defined

mainly

high concentrations,

the unstirred Nernstian

uptake

layer

0.05 mmol

of submicromolar measurements with ISEs

membranes, both with release

aqueous

of the Nernstian-layer

layer

an

reduced

selectivity of the membrane.

reduction of the thickness of this

s implies

the

strength

anionic sites, while

This

ionophore.

primary

is

reduced

the addition of

practical applications,

the amount of

concentration of the

constant the

due to

by

[5]. Nevertheless, with RT

10"9).

ionic

decreasing

counterbalanced

partly

strongly

general rule,

selectivity

is +1.0 and the lower detection limit

interference

expedient

declines with

In this case, the loss of

[1].

in

as

same

Nernstian electrode function is obtained till

nearly

their

lOfold reduction in

constant.

the response of ISE

improves

ionophore

5.5 the concentration ratio of

Figure

was

Nernstian in

applied (solid lines)

sample,
a

and with

wider

activity

than in unstirred

71

samples (dotted lines).

were

Similar

observed earlier with

wall-jet system by

Lindner et al.

[75].

F low-through system

of the lower detection limits

improvements

A-

Unstirred

sample

<&?

-A-''\^p

_^^*/:

/
/

50 mV

''"'

-^

f****

-10

-9

-8

-7

-4

-5

-6

-3

log aCa2+

Figure

5.6.

ion

primary

samples

Response
release)

and in the

Influence of the

of

Ca2+

and C

ISEs with inner

as

primary

ion

through

the membrane has the

their increase in the aqueous Nernstian

magnitude

of ion fluxes

through

varying

its thickness and/or the diffusion coefficient of the

A reduction of the concentration

gradients by

nearly

5.7).

beneficial

transported

activities

it is

by

ions.

4fold increase of the thickness

ideal response of ISE C down to

Ca2+. On the other hand, its reduction by

higher

same

the ISE membrane

to

Nernstian response step to

in unstirred

layer. Experimentally

possible

of the membrane leads to

uptake)

with strong

viscosity of the membrane

thickness and the

control the

(membrane

cell.

A decrease of the ion fluxes

effect

with moderate

(membrane

flow-through

solution A

filling

10"9

factor of two shifts the super-

on

one

logarithmic

unit

(Figure

72

Chapter

Membrane
thickness

>
E
fa

600

um

150

um

75

um

j&

50 mV

,i,i

-10

-9

-7

-8

-6

-4

-5

-3

log aCa2+

Figure
inner

5.7. Influence of the thickness of the membrane

filling

concentration ratio of

polymer

to

can

be

widely

varied

plasticizer [79, 80].

by changing

the

An increase of the

content of the membrane of ISE C from the usual value of 33% to

50% also leads to

(Figure 5.8).
response to

gradients

the response of the ISE with

solution C.

Diffusion coefficients in the membrane

polymer

on

an

On the

almost ideal response down to the nanomolar range

other

higher Ca2+

are

hand, its decrease shifts the super-Nernstian

activities in

spite

of the fact that the concentration

smaller in this membrane than in the others because of its

improved Na+ selectivity (see

Table

5.1).

73

PVC

^^

3.7

50 mV

/
%^*

1:2
1

DOS

e^

<

-10

-8

-9

-6

-7

-5

-3

-4

log aCa2+

Figure
inner

5.8. Influence of the

filling

times

All calibration

curves

lower concentrated

one

in

of two ISEs

without

samples

(B)

were

measured from the

(10"9 M Ca2+)

are

in

represented

with concentrations

higher (10~3

with

one

Figures

higher

from

small

membrane, that leads

sensed

H+).

layer (in 10"8

exchange
to

to

the

than

stable

ratio of

small flux of

Ca2+ solution

at

and

5.9a and 5.9b. The response times

10"6

potential

For the ISE without super nernstian response the

originate

Ca2+)

super-Nernstian step (C)

Ca2+were

were

pH

more

at

diluted

considerably longer.

long equilibration

Ca2+ by H+
Ca2+

of the order of

whereas in

investigated ISEs,

the times needed to reach

solutions. The time traces of the calibration

(cf. Figure 5.3),

seconds for both kinds of the

samples

the response of the ISE with

on

solution C.

Response

curves

of the membrane

viscosity

the

sample

time

can

side of the

ions from the membrane to the

5 0.6 % of

Ca2+

is

exchanged by

74

Chapter

50

>
e
0

i___^

\
^^

-50

20

40

~^____
,

80

60

120

100

time / min

Figure

5.9a. Time traces of the response of ISE B.

100

time / min

Figure

5.9b. Time traces of the response of ISE C.

The ISE

with

strong gradient had

concentration where the

drifts
ion

were

between

very

super-Nernstian step

still of about -10 mV

exchange

Ca2+

h"1).

and Na+

long

occurred

response

(after

time

2 h the

At this bulk concentration

or

at

the

potential
complete

H+ takes place, since the Ca2+

75

concentration in the sensed

the concentration

is lower than

layer

within the membrane

gradient

steady

state

(after

10 h for

ca.

'

J. Consequently

changes, leading

only

drifts that reduce to the conventional values

reached the

Kf^Ha^j

potential

to

when the membrane has

PVC content of

ca.

[74]).

33%

Conclusions

While the variation of membrane thickness and

valuable
must

means

be

optimizing

in mind that

kept

with

slowly

when

high polymer

ISEs for

steady

content

and

practical

polymer
trace

will be

content

level

applications,

state

situation is reached much

large

thickness

[80].

more

example,

For

it

the

diffusion coefficient is about 10 times smaller when the PVC:DOS ratio is

increased from 1:2 to 1:1
times

[33] and the time needed

when the membrane has

longer

influence of other measures, i.e.

efficient

stirring

exploited

first.

5.5

Pb2+-ISEs

the

or

use

previous Section,

with

dilute

has been

and with

fully

linear

through

may

key parameters

on

systematically investigated.

induce

in the aqueous Nernst diffusion

polarizations

should be

the influence of various

samples,

state is 16

Therefore, the

thickness.

flow-through system

been shown that zero-current ion fluxes

contact

steady

the reduction of site concentration and

10"9

Ca2+-ISEs

response function of

4fold

reach

leaching, strong depletion

with strong

response function down to 5

In the

of

to

the

It has

ion-selective membranes in
concentration

significant

layer, leading

to

non-ideal

response of the ISEs. On the basis of the theoretical models and the obtained

results, it is
to obtain

now

higher

any kind of

possible

or

to

carefully adjust

lower detection

polymer

limits,

the various parameters in order

or a

super-Nernstian

membrane ISE. Three kind of ISEs

(E, F,

response with

and

G)

based

76

on

Chapter

the Pb

examples.

-selective

conditioned in the
in the

together

VI described in

ionophore

Their responses in water solution

CaCl2 and 10"4

same

containing

shown in

are

Figure

solution and the calibration

used here

are

background
All

5.10.

of

ISEs

as

10"3

were

measured all

curves were

samples.

same

Leaching ofPb

HN03

Chapter

ions from the membrane into the

sample:

ISE E

The ion-selective membrane of ISE E contained the conventional amounts of

lipophilic
10"'

sites and

Pb(N03)2

inner

as

lower detection limit of

of

by

Pb(N03)2
the

high

ca.

thickness of about 150

solution and o-NPOE

filling

10"6

M is dictated

side, due

at the inner membrane

diffusion coefficient of ionic

with o-NPOE

Pb2+-ISE

and had

ionophore,

with

Nernstian response down to 5

reproducible

selective membrane of ISE F

calibration

was

modified

DOS instead of o-NPOE and the content of

was

Additionally,
constant
at

about 20 times smaller

the

value of

10"9

ca.

were

not

M with NTA

and,

strong enough

This membrane is the

drinking

of N03", and

in membranes

10'9

plasticized

curve

as

M: ISE F

down to

10"9

follows. The

lipophilic

compared

same

and natural water

used in

samples.

as

as

to

ion

buffer,

Pb2+-

plasticizer

with the

so

M the

ionic sites

Pb2+ activity of the inner filling solution

the inner membrane surface

membrane

The

the strong coextraction

lipophilicity

to the

species

plasticizer.

as

[74].

In order to obtain

ionophore

by

It had

u,m.

as

well

previous
was

that the

was

kept

as

one.

at

ion-exchange

consequence, the ion fluxes in the

bias the response function of the ISE.

Chapter

6 for the measurements of Pb

in

77

Depletion

at

the

The membrane

outer

surface:

of ISE G

composition

solution

filling

membrane

contained

the

was

membrane surface

This caused

Pb2+

and

and,

Nernstian response of the ISE between the

Pb2+ concentrations

10"7

M. At

in the

sample

activities below 5

membrane-contacting

the EMF

on

aqueous

in the inner

1 (H

layer

as

as

M, virtually

by

shown

no

super-

consequence,

10"8 and

independence

the

Pb2+ is present
of

aPb2+.

ISE F

400

^^^^"^

350

300

Na+

strong Pb2+ gradient in the membrane

directed toward the inner compartment

higher

Pb2+ by Na+

of

complete exchange
a

of ISE E, but the inner

same

lower

sufficiently

concentration to induce

layer.

ISE G

ISE G

^^^^^1^^^^^

^^^^

m^^^*^

>

S 250

u.

200

150

100

^^^
50

I_i

ISE E

^^"^^^^

*
"

^^

-7

-6

1_

-3

-5

log aPb2+

Figure

5.10.

Response

functions of ISEs

oflO'3MCaCl2andpH4.

E, F, and G in Pb2+ solutions with

background

78

Chapter

Response

Pb2+

The

times

measurements

calibration

curves was

done in

were

measured from lower to

5.11 shows that measurements at trace levels

of

the response of the ISE is

higher

fast.

reasonably

Only

10"8

This is due to

M.

contacting

the

sample,

with

ion

an

exchange

in the presence

even

ISE G has

10"7

of the ion

in the

gradients

membrane.

5
400

5
5

350

10

10-5(

10

10

5xl(H

300

5
250

10

ISE F

fa.

200

ISE G

,'

150

100

ISEE
50 h

10

15

20

25

30

35

40

45

50

time / min

Figure

5.11. Time traces of the responses of ISEs E,

F, and G.

55

60

65

to

surface

membrane

the

long

very

from 5

changes

at

change

concomitant

Figure

CaCl2, pH 4), and that

response time when the concentration of the solution

5

concentrations.

possible

are

background ( 10"3

concentration of ionic

high

beaker and the

polypropylene

500 ml

70

79

5.6

Experimental

Reagents. Polyvinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS),

nitrophenyl

ether

octyl

bis(trifluoromethyl)phenyl]borate
tetrakis(4-chlorophenyl)borate

tetradodecylammonium

(NaTFPB),

Ca2+-ionophore

the

500),

(ETH

tetrakis[3,5-

sodium

(o-NPOE),

dicyclohexyl-7V,A^-dioctadecyl-3-oxapentanediamide (ETH 5234),

Fluka AG
with
a

and

tetrahydrofuran (THF)

(CH-9470 Buchs, Switzerland). Aqueous

freshly

deionized water

(specific resistance,

NANOpure reagent-grade

Switzerland).

from Merck

(1.0 wt.%,

(66.4 wt.%),

DOS

Until not

acid

ca.

and PVC

150, 600

(dissolved

in

glass plate.

but

Membranes

same

NaTFPB

were

u.m

thickness

1600 mg

in their

differing

amounts

i.d. gave membranes of

procedure

as

nitric

acid

ca.

160

u.m

(LT)

the conventional

kg"1),

thickness of about 150

were

with this membrane.

by casting

obtained

of the membrane components

viscosity

poured

i.d. fixed

mm

on

from the conventional

PVC/DOS ratio of 1:3.7 for the softer and 1:1

same

disodium

4.5 mmol

(0.4 wt.%,

of ETH 5234 and NaTFPB

lower concentrations of ETH 5234

the

Basel,

CH-4009

membranes contained

performed

solutions of 180 mg of membrane components

mm

prepared

obtained with

p.a.),

3, 5, 16 mL of THF) into glass rings of 45

contained the

ones

kg1),

(32.2 wt.%) and had

solutions of 200, 400,

Ca2+-selective

Conventional

respective

ca.

cm)

from

(Darmstadt, Germany).

13.1 mmol

75,

Pb2+

Fluka, NaCl and CaCl2

from

were

were

(Microselect),
(puriss

(Na2EDTA)

specified experiments

Membranes of

solutions

18.1 MQ

(NTA)

acid

the

Selectophore

(Barnstead,

system

CaCl2 (puriss. p.a.)

ISE Membranes.

ETH 5234

um.

tetraacetic
and

(Traceselect)
(Suprapur)

water

Nitrilotriacetic

ethylendiamine

Ca2+

were

N,N-

dimethylamide)

acid

ionophore 4-ter?-butylcalix[4]arene-tetrakis(thioacetic
(lead ionophore IV),

2-

as

the

others,

for the harder ones;

into

glass rings

of 28

thickness. The two membranes with

and NaTFPB
ones

but

(RT)

were

additionally

prepared by

contained ETH

80

Chapter

kg"1),

5.6 mmol

(0.6 wt.%,

500

either to 0.11 and 0.04 wt.%

wt.%

and 0.05 mmol

(0.14

Ca2+

mm

1 M

Ca(N03)2, 10"1
(inner

5.7

pH

5.4 with

10"2

A, B, C, D

10"4 M,

respectively.
NaCl)

based

were

solution.

the

on

to

10"2

used.

were

10"2

and

10"3

M NaOH

10-12

was

10"1

M NaCl
a

as

10"3

solution with

conditioned for

15 d.

to

10"2

CaCl2, 5

10"3-10"9 M) with

fixed ionic

Ca2+,

of

aCa2+, were 4

A, B, C, and D,

(Ag|AgCl
were

M NaCl and

or

10"7 M), the

EMF

was

super-Nernstian

recorded for 2

h,

at

10'5

50 wt.% PVC

or

10"5

was

were

(concentration

M NaCl and

response

10"1

in

conditioned

HNO3. The measuring time for sample concentrations above 10"6

min. At concentrations at which

D). ISE
and the

membrane

CaCl2, 10"5

background

solution

(inner

solutions consisted of CaCl2

Sample

consisted of

Na2EDTA, adjusted

The ISEs

HN03. Those with membranes of 600 \im thickness

of

CaCl2, 0.1 M NaCl,

M for ISEs

bridge electrolyte.

tubing

PVC

They

Between internal solution and inner half-cell

for at least 4 d in

range

conventional

from the master

plasticized

A), 10"3

C),

same

10"8 M, and

and 0.004

to 0.01

or

punched

were

solutions

CaCl2,

9.0 with 6

pH

kg1)

inner solutions. The calculated activities of free

respective
10"' M,

to

slurry

solution

(inner

(inner

M NaOH

diameter

mm

filling

10"3

B),

and 0.45 mmol

THF/PVC

M NaCl

solution

Na2EDTA, adjusted

with

glued

respectively, corresponding

and RT,

LT

kg1).

i.d. Four different inner

pH

(1.38

Measurements. Disks of 5

membranes and
4

with

10"5

10

was

observed

( 10"6

lower concentrations for 30

min.
Potentials
at

room

were

measured with

custom-made 16-channel electrode monitor

temperature (20-21 C) in

unstirred solutions. The

junction free-flowing
All EMF values
Henderson

flow-through

reference electrode

was

cell

corrected for the

The

selectivity

(see Figure 5.2)

in both

calomel electrode with 1 M KCl

were

equation.

as

cases

or

double-

bridge electrolyte.

liquid-junction potential using

coefficients

given

in

in Table

5.1

the

were

81

determined

[29]. Activity coefficients

in

the method described

by

were

calculated

according

Pb2+ ISE

Membranes. The membranes for LDL ISE contained 0.07 wt %

(0.70

kg1)

mmol

lead

ionophore IV,

mmol

(10.74

1.23 wt %

[9].

to

kg1)

ETH

kg"1 Pb(NC>3)2.

and 0.17 mmol

500, 61.66

kg"1)

0.44 wt %

(4.94

32.82 wt%

PVC, and 0.17 mmol

cocktail

as

50

aqueous

the cocktail has to be

the solution into

kg"1 Pb(N03)2.

one

was

Pb2+

solutions

half of the borate

Electrodes. A disk of 4

selective membrane and

slurry.

The

internal

conventional), 10"4

filling

cm

to

i.d.)

ca.

150

fixed

solutions
M

limit),

10"1

NTA, 2.1

10"5

and

wt %

o-NPOE,
were

in mol in

amount

This membrane solution

obtained

by casting

glass plate.

from the above ion-

punched

PVC

were

ionophore IV,

added to the membrane

urn was

on a

was

plasticized

Pb(N03)2, 10"3

PVC,

wt %

(except Pb(N03)2)

(the Pb2+

amount).

diameter

mm

glued

NaTFPB,

The parent membranes

successively

Pb(NC>3)2

glass ring (7.0

lead

500, 65.65

ETH

no

stirred for about 1 h. A membrane of

was

DOS, 37.00

kg"1)

mmol

(10.37

NaTFPB,

lead salt

The

^iL of

wt %

kg1)

mmol

-450 mg of membrane components

prepared by dissolving
in ~5 mL THF.

(0.35

The membranes for conventional and super

nernstian ISE contained 1.09 wt %

mmol

0.03 wt %

with

tubing

THF/PVC

Pb(N03)2 (ISE

M
x

10"3

E,

NaOH, pH 7,

10"1

Pb(N03)2,

(ISE F, optimal

low

Na2EDTA, 10"1

NaOH, pH 7.5, (ISE G, with super-Nernstian response). A

of

bridge electrolyte
the

separated

(Ag/AgCl,
M

inner

3M

KCl).

Pb(N03)2, 10"3

3 ISEs of the

Pb2+

same

detection

10"'

M NaCl

filling

solution

The electrodes

electrode

E and ISE

the

from

were

G)

or

inner

10"3

ca.

M NaCl

half cell

reference

conditioned for

CaCl2, 10"4 M HN03. All

20 h in 5

measurements

were

10"9

done with

composition.

measurements. Calibration

concentrations at

(ISE

pH

(adjusted

(Metrohm AG,

curves

were

with 0.1 M

CH-9010

taken from lower to

HN03 using

Herisau)

in

Metrohm

polyethylene

higher

pH glass

beakers which

82

Chapter

were

pretreated

custom

with 0.1 M

HNO3 overnight. Potentials

made 16-channel electrode monitor at

in stirred solutions. For each

drifts

were

1 M

(10

super-Nernstian step),

The reference electrode

room

solution, potentials

smaller than 1 mV/min

where ISE 3 has

had

NH4NO3 bridge electrolyte.

measured until the

10"7 M,

and 5 min at
in 3 M

measured with

temperature (20-21 C)

were

min below

(Metrohm Ag/AgCl

were

higher

40 min at

10"6

concentrations.

KCl, type 6.0729.100)

83

6. ION-SELECTIVE POLYMERIC MEMBRANE ELECTRODES FOR

POTENTIOMETRIC

Pb2+

OF

MEASUREMENT

ENVIRON

IN

MENTAL SAMPLES AT TRACE LEVELS

Potentiometrie polymeric membrane electrodes based

ionophores
water

be used for the determination

can

samples

at

of heavy

It

can

be found in all parts of

used for the

and for

protection

major origin
use

of

production

in

good

of

body

and

mainly

burning

as a

result of human

of fossil fuels.

as

Lead is

batteries, ammunition, pipes and pigments,

X-ray radiations.

In the last

of lead emission has been motor vehicle exhaust

tetraethyllead

"anti-knock" agent

begun

[81]. Only in

decrease, due

to

to the

decades, the

resulting

from

very recent years

diminished

use

of

petrol.

Distribution

Lead, the

of lead in

most

such

as

the environment

abundant natural

the earth's crust. Its

Pb(II)

are

in small amounts in the earth's crust.

environment

from gamma and

the level of lead in the air has

lead in

our

mining, manufacturing

widely

the

occuring

metal

bluish-gray

activities like

metal ions in natural

measurements.

6.1 Lead in the environment and in the human

neutral

electrically

nanomolar concentration. The obtained results

agreement with ICPMS

Lead is

on

primary

heavy

metal

element, is widely distributed in

forms in nature

are

insoluble salts

PbS, Pb02, PbC03 and PbS04 [82]. The

the ecosystem is

mainly

due to

anthropogenic

sources

or

oxides of

presence of lead in

like

mining,

industrial

emission, automobile exhaust and burning of fossil fuels. This leads

to

the

84

Chapter

strong deviations in the environmental lead concentrations between urban

of

region

Lead in

With

high

industrial

exception

of lead

carbonate

and

pH

hydrated Pb2+
the

ion is

absence

The chemical
is

joints

higher

in the

concentration

only slightly

predominant only

as

in

soluble in water.
lead

main

and

systems

of

in

Pb(II)

Figure

In

6.1.

usually

with

very

the

uptake

in rainwater in

The free

7)

and

high

CI"

<

is PbCl+.

water,

[83],

the

but it

or

lead-soldered

from the

air, the lead

from metallic tubes

to

in

natural water

seriously polluted

not

uptake

quite high

species

between 50 and 0.5 nmol/L

plumbing system. Owing

also be

(pH

typical organic-free

found

PbSO40.

under acidic conditions

In

Depending

species

estuaries and seawater, the dominant

in tap water due to

can

the

ligands.

organic

concentration of total lead is

may be

without industrial sites.

PbCO30, PbOH+, PbHC03+,

speciation

shown

or

concentration,

are

of

concentrations, such

system

regions

chlorate, Perchlorate, nitrate, and acetate, inorganic

insoluble

are

environmental water

in

and rural

aquatic systems

Pb(II) compounds
on

density

regions

of

high

industrial

density.

Uptake

and distribution

The main
and food
a

sources

[83].

of lead

Lead

can

diameter below 0.5

absorbed

through

of lead

in the human

uptake by

humans

body

are

inhaled

air, drinking water,

be inhaled from air in form of PbBrCl

mm

the skin

or

by

as

alkyllead

formation of

acid and amino acids in sweat

[84].

vapor, but it

can

particles

also be

lipid-soluble complexes

with

rapidly

with lactic

85

100

Pb2

PbCO,0
PbOH+

80

60

PbHCO
o

40

20

12

L_

10

13

12

11

pH

Figure
solution

The

6.1. Distribution of the various

containing only Pb2+

are

curves

obtained

1062, PbHco3

concentrations:

PbC03

[Pb2+]tot

10"y, [C(VMtot

1.0

pKa values for

2.9

103, PbCI

10"j, [S04]tot

the dissociation of carbonic acid

The average lead content in ambient air

m"3

in remote

working

areas

more

environments

glassworks,

etc.

lead intake. The

occurs

to

in the

substances.

Tobacco

uptake

[83]

such

as

can

1.55

can

m"3

example, iron,

and

can

calcium

in

1063, Pbs04

pK^

1.25

and

1027,

10"4. The

10.25.

industrial

storage

slightly

of lead from the diet

tract

sample

[56, 57, 85]

10"4, [Cl"]tot

6.35 and

in

vary from less than 0.04 nmol

mines,
also

pH

CI", OH", and S04".

constants

1016, PbOH

pKal

than 50 nmol

smoking

gastrointestinal

For

are

function of

C032", HC03",

formation

following

the

as

anions

inorganic

and the

with

Pb2+ species

battery

(drinking

phosphate

water

by

daily
food)

and

other

reduce

and

factories,

contribute to the

be influenced

and

regions

dietary

the

lead

86

Chapter

absorption,
it. The

(World

Health

lack of zinc, ascorbic acid

by

an

(PTWI)

adult human

being

has been established

it is transferred to the

and urine

into

WHO

and within few minutes

slowly (with

remains

(6%)

small amount

half-time of 2-3

tissues, teeth and skeleton [81, 83]. More than

the

[86]. Indicators of

(recent exposure),

plasma
a

lead is stored in the

released back

intoxication

from where it is

to the soft

body

90% of the total

slowly

erythrocytes. Only

plasma,

weeks) distributed

the blood

to

by

kg"1 week"1 [83].

to be 0.24 mmol

intake, lead is transported

drinking

of lead from

intake

Organisation)

dissolved in the

citric acid in diet enhance

or

weekly

tolerable

provisional

and diets

water

After

whereas

skeleton, from where it

with

blood

the

human exposure

consequence

can

be

of chronic

the lead levels in blood

are

(long-term exposure).

and in bones and teeth

Toxicity

Lead is

non-essential element with toxic effects

biochemical level lead is

haem

pathway

and disturb the

effective

substitute

processes

[81].

The toxic effects

poisoning,

capable

which

for

on

humans

usually

and

can

the human health. At

inhibit enzymes at several steps in the

to

porphyrin

calcium

on

Moreover, it is

metabolism.

influences

many

be both acute

arises from the accidental

or

an

calcium-dependent

chronic.

ingestion

lead

Acute

of a soluble lead

salt, is initially associated with anorexia, abdominal pain and vomiting,

followed

eventually

or

development
peripheral

skin
of

absorption,

damage, encephalitis

may

cause

system

damages

with
are

in

possible,

abnormal lead exposure has terminated

coma.

Chronic

quantities by inhalation,

Long-term

paralysis

also

and

anemia, weakness, headache and the

black line in the gums.

nervous

Irreversible renal

renal

due to accumulation of small

poisoning, usually
ingestion

by

[81, 83].

the
even

exposure
more

can

affect the

advanced

long

cases.

time after

the

87

6.2

Requirements

drinking

water

demands that total lead

Agency (EPA)

The U.S. Environmental Protection

in

selectivity

for low detection limit and

ppb (7.2

should not exceed 15

10"8

[87]; action limit).

expected

is

Since the detection limit of a reliable

analytical technique

least ten times lower than the action

limit, conventional ISE with

10"6

limit of about

analysis

of

heavy

M have

liquid samples

drinking

metal ions in

widely

Until now, the most

were

used

graphite

been considered to

never

samples.

for the determination of lead in

hydride generation

or

detection

suitable for the

be

and environmental water

techniques

furnace

be at

to

atomic

absorption

spectroscopy (GF-AAS and HG-AAS), inductively coupled plasma combined

with

mass

spectrometry (ICPMS)

AES) [88-91], and several voltammetric methods

stripping voltammetry (ASV),

and square

become

an

by

many

interesting

orders

with other methods. For

expensive,

can

be

limit,

not

the

investigated

example, they

the

membrane

solely

concentration of
an

through

boundary region
limit,

advantages

they

may

fact, with the

in

comparison
are

not

require sample preparation

and

cases

the

of

speciation

of

the membrane and the sensed aqueous

lower

defined

dictated

interfering

ion is lost when it is

detection

methods. In

allow in many

they

that

so

ions.

thermodynamically
is

stripping voltammetry

allow in situ measurements,

do not

easily miniaturized,

In absence of the ion fluxes

layer,

analytical

ISEs have various

redox-sensitive. Moreover,

are

anodic

anodic

polarography,

magnitude [30, 39],

alternative to other

of the detection

exception

of

wave

as

the lower detection limit of ISEs have

(SWASV) [85, 92-95]. Only recently,

been lowered

(ICP-

atomic emission spectrometry

or

by

the

ions in the

selectivity

sample.

completely replaced by
the

membrane.

^(DL,static),

is

detection

The

limit

coefficients

In this case, the

an

interfering

corresponding

given by equation

of

ISE

an

and

the

sensitivity

to

ion in the

phase

so-called

static

3.16. It is obvious that

88

Chapter

trace

environmental

with

selective

highly

river and

samples (lake,

and K+ concentrations

Pb2+ concentrations

are

are

at least five

submicromolar

or

detection limits

predicted by equation

an

exchange

sample interfering
induces

flux of

consequence, the

of just

leads

ions

primary

higher

equation

has been derived

to

by

3.16

are

too

concentration

slight

the

sample. Here,

detection limit and the

just

one

interfering

primary

and

bulk.

(dynamic

logCl(DL)

divalent

Recently,

primary

logc^DL)

ion of chosen

Ui

Na

static

analyte

detection

detection

coefficient

to

limits).

limit

are

as

given

same

sample.

The

As

layer

the

required

equation

function

interfering

can

of

be
the

ions in

between the

for systems

containing

(6.1)

interfering

ilogoff ^clsqRT| j

simple implicit

predict

that

charge:

and monovalent

ions with

valency:

ion have the

_i_

lower

polarization

rather

[78, 96]

hog(-Kffc}SqRT)
2

since in dilute

only simplified explicit relationships

selectivity

interfering

the

optimistic,

concentration of any number of monovalent and divalent

the

of

case

six orders of magnitude lower.

Prof. E. Bakker

expected

are

10"3 M, while the

and

small fraction of membrane

sample

selectivities in such situations

the

10"4

the

where the Ca

ions from the membrane into the

than in the

calculate

between

is

concentration in the sensed aqueous surface

analyte

becomes

to

drinking water)

analyte concentrations,

at

solutions

This

membranes.

normally

Unfortunately,

used

backgrounds

level determinations in the presence of millimolar ionic

only possible

Mg+,

ion:

(6.2)

89

The coefficient q

analyte

ion in both membrane and

respective

the ratio of the diffusion coefficients of the

incorporates

diffusion

layer

and

sample phases (DM

and

(<5M

thicknesses

and the

Ds)

<5S)

From

(6.3)

equations

6.1 and 6.2 it is

ionic sites should be

phase,

and

Table

6.1

according

preferably low,

to

ions should diffuse

in the

slowly

organic

coefficients must be small to reach low detection limits.

selectivity
shows

evident that the concentration of

immediately

the

measured

both the static and the

detection limit of 7.2

10"9

and

dynamic

Pb2+.

coefficients

required selectivity

the

model in order to obtain

A value of

0.001 is

thereby used,

which is obtained with the diffusion coefficient of

Pb2+

10"6 cm2 s"1 [73])

ionophore complex

membrane

layer

(DM

those obtained

equations

process is

of the

i.e.

are

only

based
a

on

coefficients

the

the value calculated

on

one

important
that the

are

order of

the basis of equation 3.16.

in the

to the

new

much smaller than

analyte

Therefore, they

lower detection limit is at least

are

assumption

few percent of the

ions in the membrane.

9.5

thickness of the diffusion

the basis of the static model. It is

6.1 and 6.2

( Ds

in water

organic phases. Evidently, according

required selectivity

incomplete;

by interfering
predicted

the

on

one

10"8 cm2 s"1 [74]), and equal

in the aqueous and

dynamic model,

that

and the estimated

lower

ions

only

to

remember

ion-exchange
are

displaced

valid when the

magnitude higher

than

90

Required Selectivity

Table 6.1.

detection limit in Zurich

Chapter

coefficients for

drinking

water

log^Pbj
Ion J

cone.

/ M

and

lead ISE to achieve

1.5

comparison with experimental

required

measured

static

dynamic

eq. 3.16

eq. 6.1-6.2

ppb (7.2 nM)

values.

Expected CPb ( DL)

I M

log<j

static

dynamic

Na+

3.5

xlO4

-1.2

-3.9

-6.3

0.2

6xl0"14

lxlO"9

K+

3.8

xlO"5

+0.7

-1.9

-6.3 0.1

7xl0"16

H+

1.8

xlO"8

+7.3

+4.7

-3.5

0.3

lu"19

9xl0"12

1.0

xlO"4

-0.1

-2.8

-3.5

0.3

10'12

4xl0"9

Ca2+

1.6

xlO"3

-5.3

-6.6

-12.3

0.1

10"16

lxlO"11

Mg2+

4.9

xlO4

-4.8

-6.1

-12.4

0.2

2xl0"16

10"12

Cu2+

4.7

10-8

-0.8

-2.1

-3.7

0.2

9xl0"12

10'9

Cd2+

8.9

xlO"10

+0.9

-0.4

-5.4

0.1

6.3

of

Optimization

measurements of

In the

the

filling

previous

two

chapters,

possible

lower

of

if very selective

polymeric

on

samples containing
Ca2+.

ionophores

solvent

high background

membrane ISEs have been

Potentiometrie
are

are

measurements

at

trace

available and if the inner

carefully adjusted.

polymeric

the routine determination of nanomolar

or

for

the relevant effects that dictate the

solution and the membrane parameters

H+, Na+

2x10-"

level

selectivity

demonstrated that ISEs based

as

technique

10"15

10-10

trace

experimental

considered. It has been shown that

are

Pb2+

detection limits and the

levels

membrane

concentrations

concentration of

of

can

Now it is

be used for

Pb2+,

even

interfering ions,

in

such

91

Membrane and inner filling solution

First, the compositions of the ISE membrane and the inner electrolyte

optimized

in order to minimize ion fluxes

of the ISE any

perfect performance
only

induce

interface.

an

the

sample composition

Here, for practical

sample
the

this could

that in each

composition

required

inner compartment

buffer.

(cf.

With the

at the

(ca.

6.8).

Section

sample/membrane

the
an

but

sample,

filling

membrane

Its

10"9

activity
Pb2+.

possible

to

10"9 M)

was

kept

in Section

was

chosen to be close to

by using

constant

not

changed

membrane.

membrane

The

anionic sites

reduction

selectivities

that

of

the

were

larger

necessary, it is

improve

possible

by increasing only

to

NTA

is

be calculated

can

replaced by Na+

6.1 and

6.2, it

membranes that contain

thickness

or

exhibit

at

the

in

gradients

equations

to

In the

anionic
as

smaller

present application, only

times of the

conditioning

concentration

good

adequate
the

an

reduced but the other parameters

was

not

Pb2+

concentration

in order to not increase the

but still

sites.

ionophore.

composition (cf. Chapter 4)

fluxes

the

by preparing

sites, have

diffusion coefficient of the lead

lipophilic

of

stability

5.2, the membrane weighing

Additionally, according

small concentration of ionic

were

that

so

minimize the ion fluxes

the amount of

unfortunately

To increase the

solution less than 5% of

surface,

membrane remain small.

is

electrolyte

solution is used for all

filling

parameters, and the selectivity coefficients (Table 6.1), it

the inner

inner

side, the low activity of the free Pb"+ in the

inner

1.3

inner

same

equations given

that with this inner

should

sample composition

across

for

is variable and not known before the measurement.

detection limit of 7.2

potential

membrane

in the

matches the

perfectly

case

Ideally,

the membrane.

be achieved with

only

reasons, the

concentrations

change

flux of lead ions

insignificant

Generally,

across

were

as

with

the

for the present

selectivity

the concentration of the

sites

without

ionophore

yielded

unmodified

application.
enhancing

If

ion

but not of the

92

solution

Conditioning

Before use, the ISE membranes

Pb2+ solution of pH

level,

lead ions

amount of

too

exchange

the counter ions

avoided

in

(Na+)

minimize

PbCC>3 and Pb(OH)2 crystals

with this

5.3-5.6 and

on

CaCl2. A

required

lipophilic

right

with this

quantitatively

to

anion in the membrane. The

10"2

in

of

coextraction

Pb2+ solutions)

was

from

Pb(N03)2

the

the H+

the ISE has

the membrane surface. Calculations based

on

selectivity

the
of
on

coefficients of Table 6.1, indicate that

Ca2+ present

or

conditioning procedure

required,

the

solution less than 3% of the lead ions in the membrane

conditioning

exchanged by

such

10"9

solution into the membrane and to prevent the formation

conditioning

equations

of the

conditioning procedure (overnight

to

which is close to the target

times would be

long conditioning

order

conditioning. Otherwise,

before the

already

solution,

conventional

in

10"3

of

background

Pb2+ solution,

dilute

overnight

conditioned

because the membrane cocktails contained the

only possible

was

were

4 that contained

with such

conditioning

are

Chapter

in the aqueous

reequilibration

no

5.10

Since after

of the membrane bulk is

fast and Nernstian response in

Pb2+concentration (cf. Figures

phase.

sample having

higher

5.11).

and

Me as wring procedure

To

the

keep

overall

relatively high
in

the

concentrations

Figure 5.10,

than at lower

sample,

addition to

advantage
short,

so

measuring
x

short, calibrations

10"6-1

10"4 M).

In

fact,

were

as

made

at

demonstrated

the response of ISEs is much faster at these concentrations

ones.

the

(7

times

As shown in

five-point

shortening

Figure 6.3,

calibration

was

the measurement

after

achieving

stable EMF in

taken within few

cycle,

minutes.

In

fast calibration has the

that the contact between membrane and calibration solution is

that the coextraction of

If the membranes had

longer

Pb(N03)2

into the membrane is minimized.

contact with

these

relatively

concentrated

93

calibration

take

much

is shown in

from the last calibration solution to

changing

6.3. It is evident that

Figure

with the calibration solutions

membrane surface occur,

reequilibrate again

sample

would

time due to the release of the coextracted lead ions. The

longer

recovery time after

sample

EMF recovery with the next dilute

solutions, the

with

some

changes

even

during

in the

new

the short contact

membrane

or

the

at

that the membrane needs several minutes to

so

dilute

sample.

ionic

backgroung:

10-3MCaCl2

*
9

104MHNO3

-6.43

"

-7.13

>
E

-7.43

-8.13

t
-8.43

1
29.6 mV
-9.13

t
l

-7

-10

log apb2+

Figure

10"4

6.2. Determination of the

HN03

as

ionic

activities in

background by calibrating

concentrations. The known

numbers and

Pb2+

by the vertical

logarithmic
arrows.

samples containing 10"3

with

lead activities of the solutions

indicating the

CaCl2 and

series of lead ion solutions of

The measured values

calibration line with the horizontal line

correspond

are

indicated

to the

EMF obtained in the

higher

by

the

intersection of

sample solution.

94

Chapter

minimize

To

solutions is

measurement

usually

explained above,
differ

that the

slope

the results
the

are

despite

curves

is

reasons

the results in

6.2 show

Figure

highly reproducible,

and

can

therefore,

difference in the activities between

large

the

calibration

and calibration solutions

sample

magnitude. However,

of the calibration

of the

work, for the

In this

sample.

the concentration of the

accurate

concentration

the

close to that in the

many orders of

by

errors,

and the calibration solutions.

samples

-4.39

"4-15

-5.22^^^*1/^
-

29.6 mV

-9.13

calibration solutions
-9.13

sample

^1

solution

-6.43

sample solution

-6.43

^_

_li

10

l_

1_I

L_

40

30

20
time / min

Figure
of the

6.3. Time traces for two of the

sample

and calibration solutions

the ISE membrane after calibration is

experiments
are

shown in

indicated

longer

for the

by

more

Figure

6.2. The concentrations

the numbers. The recovery time of

dilute

sample.

95

Table 6.2. Known and found Pb

standard deviations

are

for

higher

more

sample

concentration difference between

spiked Pb2+

activities for the

found

or

activity

10"10

-9.16 0.08

7.11.4xl0-10

-8.43

3.7

xlO"9

-8.44 0.05

3.60.4xl0"10

-8.13

7.5

xlO"9

-8.13 0.02

7.40.3xl0"9

-7.43

3.7

xlO'8

-7.40

0.02

3.90.2xl0"9

-7.13

7.5

lO"8

-7.11 0.02

7.70.4xl0"8

-6.43

3.7

xlO"7

-6.46 0.01

3.50.1xl0"8

samples

carbonate

lower

of about

and that the

a

only possible

Pb2+/H+
the

Experimentally,

From

Pb(N03)2 (EPA

Figure 6.4,

by pH changes

pH

<

3 the

observed. At

the

Potentiometrie

after acidification of the

sample

to

the

pH proton is the main interfrent,

lower detection limit is about 4

exchange

the

at

dependence

of

outer

FINO3 concentration of

action

level)

and

HN03 and then slowly decreases

pH 2.3,

recovery is

the

potential

incomplete
increases

and

by

of

Pb2+-ISE

pH,

the

to
a

surface.

containing
10'3

was

CaCl2.

is not influenced

potential

the initial
net

10"9 M, due

response

solution

background

it is evident that the EMF of the

potential

membrane

Pb2+-ISE

the

between 5.0 and 3.9. At lower

after addition of
at

ion

pH

investigated by varying
KT8

Pb2+ is predominantly

(cf. Figure 6.1).

practical (dynamic)

minute

pH

hydroxide. Consequently,

or

of total lead is

concentrations

The data in Table 6.1 indicate that at this

to

amount

7.5

complexed by

pH

log activity

6.4 Proton interference at low Pb

assessment

Pb:

-9.13

In untreated natural water

larger

and calibration solutions.

activity
x

6.2. The

Figure

because of the

samples probably

dilute

amount

log activity

shown in

experiments

increases

just

potential. Only

potential

shift

can

be

about 8 mV, which is about 6

96

Chapter

mV

higher

exactly

than

predicted

with

equation

compare the two values

negative

as

possible

6.3. However, it is not

the measured

potential

had still

to

slow

drift.

2.3
200

EMFofthePb2+-ISE

150

N-

-J-

>

Sample composition:

100

10-8MPb(NO3)2

4.3

10-3MCaCl2
4.6

HNO,

4.8
5.0
50

EMFoftheglaspH-ISE
and corresponding pH
i

ii

ii

iii

ii

50

40

30

20

10

time / min

Figure
5

6.4. Time traces of the EMF response of a lead selective electrode in contact with

10"8

commercial

Figure
to

Pb2+ sample by lowering

pH glass

electrode is shown

6.4 confirms that the FT

asses

Pb2+

at

variations of the

important,

the

as

sample pH.

The

respective

because

selectivity

environmental water

do not influence the

it

is

very

samples

reference.

of the ISE-membrane is sufficient

the action limit concentration of 15

pH

time trace of

difficult

without

Pb2+
to

ppb,

and that small

measurements. This result is

precisely adjust

using highly

the

pH

concentrated buffers.

of

97

6.5 Measurements of Pb

The

were

evaluated

ICPMS. The measurement

by comparing

procedure

obtained results

are

proportional
and

to

two

bottled water

The results
to

ICPMS

value that

are

comes

Especially noteworthy
molar

excess

Potentiometrie
and

Cu2+

sample
were

was

of

10"8

as an

private

results.

of
and

7.2

water

lead, which

According

to

from tap,

lake,

Bellinzona,

of

the commercial brands Evian

sources

in

Budapest.

homes with

original

drinking

contains

sample

These last two

lead

water

plumbing
quality

more

of

ppb

than 50-fold

appear to have little influence

equations

with known concentration of

EPA action

the

in this measurement. This

lead, and ISEs

the added lead concentrations in the

10"7 (see Table 6.5, first three lines). Clearly the ISE

10"8 M;

on

6.2 and 6.3 and Table 6.1, H*

major interfering agents

accurately recovering

were

very close to the concentration assessed with ISEs.

over

indeed the

concentrations

in Table 6.3.

adequate analytical technique

Pb2+ (over

(of

sample during

the tap water of Zurich containes about 5

subsequently spiked

capable

range of

used

are

sources

The

calculations.

of the

Pb2+

(Switzerland), tap

is the fact that this

of copper

for

strength

that all the

described above, but

investigated samples ranged

presented

analysis,

as

used

and do not represent the average

place,

According
lead,

of Zurich

obtained from old

were

Budapest.

so

and tap water of different

Cristalp),

still in

change,

the activities. The

rainwater

(Switzerland),

were

not biased since the ionic

the calibration did not

samples

conditioning

the results obtained with ISE and

carried out

was

Pb2+ concentrations instead of activities

and

and

for the determination of total lead concentrations in environmental

samples

river,

samples

proposed measuring

of ISEs and the

applicability

procedures
water

in environmental

to

detect

value).

unacceptable

can

be

concentrations

98

Chapter

Table 6.3. Total lead concentrations determined

samples

and

comparison

Zurich tap

Zurich lake

Glatt river

(ZH)

Zurich rain

Bellinzona tap

Cristalp (bottle)

Evian

(bottle)

Budapest tap

Budapest tap

Other water
ISEs showed

to ICPMS

Cu-ICPMS

ppb

0.71 0.04

0.54 0.07

6.70

nM

3.4 0.2

2.6 0.3

104 1

ppb

0.78

0.23 0.01

4.35

nM

3.8 0.2

1.1 0.1

69 1

ppb

0.96 0.08

0.62

nM

4.6

3.0 0.1

93 1

ppb

5.02

5.12 0.05

40.4

nM

24.0 1.0

24.7

ppb

0.70 0.06

0.09 0.01

8.66 0.06

nM

3.4 0.3

0.72

136

ppb

1.06 0.09

0.01 0.01

nM

5.1 0.4

<

ppb

0.74

0.02 0.01

nM

3.6 0.4

<

ppb

2.30 0.8

0.92

nM

11 4.0

4.4 0.1

ppb

10.0

nM

49 5.0

0.05

0.4

0.20

0.05

1.0

never

exceeded 5

as

5.93

0.2

636

0.08

10"9

from

equation

0.02

0.10 0.01

0.9

0.03

<0.02
<0.2

45.2 0.1

<0.02

<0.2

1300 20

<0.02

20300

<0.2

300

river and rainwater. The

lake,

were

cases.

The assessed lead

in reasonable agreement

shown in Table 6.3

results

6.2.

0.2 0.1

<0.2

Pb2+. However, ICPMS values

expected

0.02 0.01

0.07

15.7 0.5

samples) according

that the ISE

0.2 0.1

<0.02

also in these

samples

0.02 0.01

0.07

1.00 0.03

712

M and

0.7 0.1

<0.2

12.5 0.1

0.07 0.01

5.3 0.2

0.02

0.08

<0.02

0.01

0.34 0.01

0.1 0.1

from Zurich included

magnitude lower, showing

interference,

0.01

0.1 0.1

2.59

acceptable performances

10"9

Cd-ICPMS

Pb-ICPMS

water and the bottled water

exceed 5

in environmental

analysis.

with ICPMS values. The next three

tap

potentiometry

Pb^-ISE

samples

concentrations

direct

by

to

the I SE

were one

are

or

biased

(Bellinzona

again
two

by

do not

order of

the proton

99

Table 6.4. Total lead concentrations determined

spiked

Zurich tap water

spiked

Pb and Cu amount

total

Pb2+

spiked

Cu2+

total

and/or

Pb2+-

Pb

ISE

0.04

sample

ppb

ppb

12.0 nM

10.5

ppb

51.0 nM
20.5

ppb

ppb

6.70

104 nM

ppb

6.70

ppb

6.70

99.0 nM

104 nM

2.5

507

ppb

12.0 nM

ppb

2.5

12.0 nM
2.5

ppb

12.0 nM

The

two

0.06

12.6

0.3 nM

0.02 nM

11.3 0.1

ppb

22.0

0.2

0.4

0.8

ppb

ppb

0.02

13.5

0.1 nM

2.80

0.02

13.5

0.1 nM

14.0

drinking

them exceeded the action limit

water

very

EPA.

high

ppb

1 nM

ppb

0.05

104

1 nM

523

952

value obtained with ICPMS.

0.1

^iM

lead

though

none

copper concentration

ISE

10"8 M, which

is twice

(2

of

is the
x

10"5

measurement.

as

6.1

predicts

high

than the

By adding the concentration predicted by the

concentration close to the value

was

ppb

Especially interesting

detection limit to the value determined with ICPMS

interference

(iM

higher

contained
even

\>M

ppb

0.1

1410

ppb

0.04

22.2

which appears to be the main interfrent in the

lower lead detection limit of 2.3

ppb

6.60

Indeed, for samples containing this Cu2+ concentration, equation

a

ppb

1 nM

15.0

samples,

ppb

0.08

8.23

0.2 nM

Budapest

imposed by

containing

ppb

2.90 0.03

from

samples

ppb

2.80

1 nM

6.70

ppb

0.08

6.70 0.08

106lnM

ppb

6.70

104

22.0

ICPMS

104

ppb

0.2 nM

concentrations than the other

M),

13.5

677nM

ppb

0.04

13.9 1.5

sample Budapest tap

analysis.

ICPMS

104

54.5

1507

water

0.3 nM

1.5 nM

474nM

tap

ppb

ppb

15.8 nM

23.7 nM

0.07

9.8

ppb

Cu

ICPMS

2.80

302nM

ppb

comparison to

55.6

6.3

7.9 nM
1007

ppb

10712nM

ppb

2.6

2.61

11.5 0.3

104 nM

and

0.54

3.40.2nM
2.5

Cu2+

in natural and

potentiometry

found Pb and Cu amount

0.71

natural

Pb2+

with

direct

by

suggested by

further evaluated

ISE

by spiking

(4.9

one

obtains

10"8 M). The

lead

copper

Zrich tap water with 2

ppb

100

Chapter

lead and various levels of copper, in order to mimic the

Table 6.4, last three

lines).

The bias in the ISE

similar to that observed with the native

line)

its

simplicity. Although

action limit

current

lead

action

substantially

give

to

copper itself has

6.6

Pb2+

of low total

Figure

carbonate

Pb2+ activity

the free

6.5. It

of the total

concentrations in

samples

in the

ions. In

of

to

pH

about 2

limits, since

the presence of

Pb2+ and Cu2+ in the sensed

complexed Pb2+
The total

bigger

at

arrow

in the

aqueous

was

plot

In

reveal

is

predominantly

pH dependence

(native water)

7.9

10"10 M,

water

of

few percent

could be

accurately

considerations of

previous

high pH

the H+ interference

by

other

is

interfering

carbonate, the effective concentration

layer

because of the

Pb2+ concentration

The vertical
ICPMS.

are

if

only

water of Zurich is shown in

that the lower detection limit is caused

addition, due

ISE

interfere

may

reliably

drinking

The measured

unspiked drinking

Pb2+ concentration, i.e.,

so

would

pH 8, Pb2+

of about

(cf. Figure 6.1).

lower detection

eliminated,

copper

above the lead action limit

determined. This result does not contradict the

dynamic

at the

exactly

water.

demonstrates that at

clearly

that

means

reading

drinking

with

adequate

concentration than the copper action limit.

In untreated natural water

complexed by

It

is

lead concentration above the

simple Potentiometrie screening

quality problem

Speciation

false lead

higher

practice, therefore,
real

10"8 M).

very

#1342], the bias in the

1999

to indicate

large enough
(7.2

limit

here

employed

was

Table 6.3, last

the copper concentration is here

(1.3 ppm) [Agency,

measurement is not

measurements

Budapest sample (see

and suggests that the interference model

despite

Budapest sample (see

is

high

buffered, and the fluxes of

carbonate concentration

measured with the

same

ISE, but

at

[97].

pH

shows the lead concentration determined

4.

by

101

Measured concentration at
3.4

Measured concentration at
2.1

pH

4.0:

10"9M Pb2+

10"10

Pb2+ (6.2

pH 7.9:

% of the total

Pb2+)
standard additions
in acidified

tap

(pH 4)

water of Zrich

29.6 mV

acidified

tap

(pH4)

water of Zrich

untreated

tap

(pH 7.9)

water of Zrich

concentration measured with ICPM S

-11

-7

-8

-10

log cPb2+tot

Figure

6.5. Potentiometrie determination of

values:

pH

by

(native pH)

7.9

and

pH

horizontal dotted lines for the

vertical

arrow

4.0

for

experimental
10

magnitude

and

by

can

be

Zrich tap water at two

Measured

potentials

are

pH

indicated

dots for the calibration solutions. The

two

different

carbonate

is corroborated

reliably specified

which shows the calculated

pH dependence
concentrations

of the

together

values. For this measurement the Zrich tap water

ppb Pb2+.

speciation

unspiked

shows the lead concentration obtained with ICPMS.

Figure 6.6,

with

in

(acidified sample).

sample

The fact that low lead activities

activity

Pb2+

free

Pb2+
the

with
was

by

spiked

Some deviations between the calculated and measured

curves can

be

caused, in addition

of the used formation constants.

and the literature source, the

to the

experimental

Depending

published complex

on

errors,

the ionic

by

the

strength

formation constants of

Pb2+

102

Chapter

with carbonate and bicarbonate deviate from each other up to

not

order of

the total concentration of carbonate

magnitude [56, 57, 85, 98]. Additionally,

varies at different

one

pHs and, therefore, during

the titration with

does

HN03

remains constant.

-1

r-

100

80

S
a

60

CL.

calculated for

TS

D.

[CO3- ]tot=

40

2.48 mmol/1

S
o
o

s
s

calculated for

20

[C03"]tot=

4.14 mmol/1

pH

Figure

6.6. Direct

ppb Pb2+
equilibria

as

of

Potentiometrie speciation

function of

Pb2+ given

theoretical

curves are

from web

sources:

the

pH

in the

given

for

of

Pb2+

in Zrich tap water

Solid lines: calculated values

experimental part (Section 6.8,

spiked

with 10

the

complex

considering

EMF

The

measurements).

maximal and minimal CO3 concentration in the water

www.WVZ.ch, Wasserversorgung Zrich). Errors bar

are

(data

the standard

deviation of measurements with 6 ISE.

The bias in the upper part of the calculated

total

SO42"

concentration.

Unfortunately,

curves

an

strongly depends

accurate

simulation of

on

the

SO42"

103

influence

depends

Pb2+ speciation

the

on

the

on

linear to the

errors,

of the

logarithm

between 1% and 10% of free

between

and

50%

inner

buffer,

of such

disadvantage
change

6.7)

Section

see

an

strength

solution

4 in

sample

cause

potential

is

the total

10'3

total

The electrode

Pb2+ and

good

are

of

EMF stabilities. After 30 min

expected

Pb2+ activities and

discriminated

at

pH

sample

4 and

spiked

between the two

the

10"9

first measured in

pH

10"3

of

NTA

CaCl2. The

Pb2+ concentration

as

in it

can

NTA and EDTA in the

pH

or

the ionic

investigated

interfering

ions

negative potential

M and the free ion

while ISE II

M and

in the

no

ion buffer.

(sample A).

A is

in

10"8

because

tap

they

water

5x10"

Both ISEs exhibit

replaced by B,

with 5

activity

(dotted lines)

sample containing

samples

(cf. Chapter 6.2). However,

solution showes

Pb(N03)2, (without

the

of the responses of two ISEs

traces

10-9 M,

10~3 CaCl2

water of Zrich acidified to

as

solutions. In the inner solution of ISE I

Pb2+ concentration of

potentials

same

the ISE membrane

Pb2+ concentration is 10"4

background

difference is

This effect is further

filling

ca.

the

pH,

these

For

mV.

shifts and drifts when the

changed.

M NTA is

at low

drifts.

potential

complexes through

in their inner

buffered with
contains

10"9

only

background

present section. Figure 6.7 shows time

(solid lines)

mV, while

exactly

was

inner solution is that the

induce

can

of the

differing only

is

H+.

and

difference

potential

the

29.6

the presence of ion buffers such

Surprisingly,
inner solution

pH

it

lead,

free

it contained 5

at

with time and may

6.7 Diffusion of NTA

Pb2+ (high pH) is

amount

that the ISE response is

must remember

one

filling

conditioning solution, i.e.,

Ca2+, Mg2+,

ions, i.e.,

activity. Therefore,

of

100%)

the

measurements

of other

concentration

Moreover, comparing the

difficult, since the free SO42"

is very

which is tap

Pb2+.

No EMF

have the

are

same

sufficiently

ISE II that has NTA in the inner

shift of about 30 mV. It is evident that

104

Chapter

the

potential

the

sample composition

of ISE II does not

so

only depend

that

Pb2+ activity,

the

on

external calibration of the

an

but also

on

is not

sensor

feasible.

Inner

250

solution without NTA

Sample

>

filling

Sample

Sample

Sample

200

S
iV

Z H tap

100 _5x
-

10"

spiked

150

3MCaCl2,

spiked with

5xlO-8MPb2+

^y

20

30

40

50

ZH tap water,

will

!v
ZHtap water, pH

pH

sp iked with

10

pH

j 5xl0"8M Pb2+

10"8MPb2+
pH4

wa ter,

5x

10_5M Pb2+

|!

60

70

>

80

100

90

110

time / min

Figure

6.7. Time traces of the response of two ISEs that differ

the inner

After

filling

Pb2+,

to

show the
more

constant

sample C,

but its
same

pH

potentials

in

sample B,

the

composition

measuring

which is also tap water of Zrich

is 8 instead of 4.

During

behavior, but then ISE

positive potential.

potential

in the

of

solution.

reaching

changed

only

II

was

with 5x10"

the first two minutes both ISE

(with NTA) begins

After 30 min both ISE responses

difference between them

spiked

solution is

higher

than

to

were

in

drift toward

stable, but the

sample

B.

These

105

experiments

indicate that the response of ISE II is somehow influenced

the

by

pH of the sample.
the EMF is recorded in acidified

Finally,
with 5

10"5

Pb2+. The

the

(83.7

be used if

can

have the

background.

values

can

and ionic

pH

be biased

by potential

the diffusion of NTA

membrane. The

use

buffering agents

II),

which

are

close

containing

If this is not the case, the measured

drifts. These drifts

ion-exchanger

B and D is

and calibration solutions

sample

are

species (e.g. PbHNTA, logAT

of

Zrich, spiked

be concluded that ISE

can

NTA in the inner solution

of

samples

for ISE I, 81.1 for ISE

value. It

theoretically expected

same

water

EMF difference between

similar with both electrodes

to

(pH 4) tap

to be

the

by
the

molecules

organic

improve

caused

[99]) through

15.2

resins instead of

may eliminate this effect and

likely

performance

as

of

the ISEs.

6.8 Silver interference

The

selectivity

the thioamide functionalized

However, ion selectivities

are

4 indicate that ISEs based

Chapter

values measured in

calix[4]arene strongly prefer Ag+

and, consequently, under steady-state conditions.

ISEs conditioned with
occurs

calibrated with
the

10"8

same

model

ISE

Pb2+

to

experiment,

solutions

no

Ag+

was

important

concentration

was

the

used to monitore the

wich

Ag+

was

expected
EMF

reached.

steady-state selectivity

the

Pb2+

(Figure 6.8, right)

stepwise

[15] (dotted line), for

response to

6.8,

was

with

predicted

In the

Pb2+

Here it is shown that

in

Pb2+ the interference of small Ag+ concentrations

much later than

(Equation 3.16).

Pb2+.

over

salt concentrations

relatively high

determined at

on

changes

to check its

potential
added.

selectivity

above

conditioned ISE

10"11
are

of

was

coefficient

to the

K^Ag

Ag+. However,
before

first

operation. Then,

sample containing

According

observed

model

steady-state
=

as seen

10"8

+13.2

in

Figure

Ag+

106

Chapter

response

Measured

to

Ag

Calculated theoretical response to

450

Ag+

Measured response to Pb2+

,__^

400

350

>
S

ta 300

"

ta

250

^^*

200
---*-*---#

'~~

//

_^J

of

150

-14

-13

-11

-12

6.8.

The ionic

The

Response

background

experimental

of the ISE to
was

10"3

ions enter the membrane

A^Pb<2pb2,

proximity
so

layer

the

-3

-4

in

sample containing

10"8

Pb2+.

4.

explained

if ion fluxes

considered. At the

sensor

through

the

interface silver

with lead ions and diffuse into the

of the membrane decreases below the values

that the ISE continues

phase boundary

abruptly.

are

be

-5

consequence the concentration of the aqueous

concentration in the bulk of the

at

can

-6

log aAg+

Ag+

by exchanging

bulk of the membrane. As

in the

to

-7

Ca(N03)2 and pH

observations

membrane and the aqueous

Ag+

Pb2+ and

-8

log an2+

Figure

-9

-10

responding

sample

become

is

to

Pb2+. Only when the Ag+

high enough (> 10"8 M) depleation

ngligeable,

and

the

potential

This behaviour is related to the so-called Hulcmicki

earlier described for anion ISEs.

given by

increases

effect [100],

107

Differently

from the situation described in the

Table

where concentration

the

6.1),

Pb2+-ISE,

performance

Ag+

lead

biased the lower detection limit of

system investigated here ion fluxes improve the

of the

Pb2+-ISE.

In

would be

solely
at

fact, in absence of ion fluxes the response

dictated

by

based

sensors

on

Miniaturised

ionophor.

smaller amounts of

carrier with the

sensors

analyte and,

as

can

same

times with the

would be useful

Long

term

only

Figure

6.9 the

stability

to

that

they

need

volumes

sample. However, they

work at

(cf.

6.2)

Section

is

expected.

membrane, the ionophore used in this work

for the detection

Ag+,

but not for low concentrations of

potential stability

The EMF of the

containing

miniaturised

trying

samples

conditions and static interference

a

that

behaviour of the

advantage

consequence, smaller

equilibrium

in

could arise when

selectivity

have the

equilibration

Consequently,

to

much lower concentrations than those meausered

and shorter

6.9

selectivity coefficient,

the

experiment. Unexpected selectivity problems

miniaturise

(cf.

Pb2+/Ag+

predicts Ag+-interference
in the

of the work

in the

Pb2+

or

gradients

previous part

1(T8

Pb2+
M

I SE have been monitored

Pb2+, 10-3

potential changes

during

CaCl2 and 1(T4

were

filling

days

in

sample

HN03. As shown in

lower than 5 mV,

of the membrane and of the inner

solution.

indicating

good

108

Chapter

time/

Figure

days
Time

in
=

days

6.9. Potential of 3 ISEs with membranes of the

a

500 ml solution

corresponds

containing

to the

10"8

unconditioned

dry

same

composition

Pb(N03)2, 10"3

membrane.

measured

CaCl2, 10"4

during

HN03.

109

Experimental

6.10

Section

Reagents. Poly(vinyl chloride) (PVC), bis(2-ethylhexyl)sebacate (DOS),

sodium

the

(lead ionophore IV),

lipophilic
and

chlorophenyl)borate (ETH 500)

AG

tetradodecylammonium tetrakis(4-

salt

tetrahydrofuran (THF)
solutions

(CH-8071 Buchs, Switzerland). Aqueous

freshly

(18.0

deionized water

NANOpure

reagent-grade

MQ

from

(Darmstadt,

Merck

and the other used salts

purity,

Fluka. The

Pb2+ standard solution

HN03

was

were

Nitrilotriacetic

Germany).

Microselect

0.001 M

MgCl2

and

Switzerland). HN03, NaCl, KCl, CaCl2

with

were

of

obtained from Fluka Trace

mmol

kg-1)

wt %

0.03

ETH

kg-1 Pb(N03)2.

500, 62.06

Pb(N03)2

cm

ca.

200

i.d.)

urn

fixed

of the

on

selectivity

puriss.

(0.68

(NTA)

p.a.

was

quality

of

l'1

in

mmol

kg"1)

lead

(11.50

wt %

PVC, and 0.15 mmol

wt %

417

mg

in 5 mL THF. The lead salt

as

62 u,L of

was

glass plate.

The

an

aqueous 10~

of
was

stirred for about 1

h. A

the solution into

glass

by casting

obtained

was

acid

prepared by dissolving

(except Pb(N03)2)

for

the

composition,

but

membrane

coefficients had the

same

used

Pb(N03)2.

Electrodes. A disk of 4

selective membrane and

slurry.

was

Suprapur grade

NaTFPB, 1.32

DOS, 36.52

solution. This membrane solution

measurements

without

kg1)

added to the membrane cocktail

membrane of

ring (7.0

mmol

wt %

membrane

The

membrane components

successively

(0.30

Basel,

CH-4009

of

analysis.

Membranes. The membranes contained 0.07 wt %

ionophore IV,

obtained with

concentration of 1000 mg

with

prepared

were

(Barnstead,

system

from Fluka

were

specific resistance)

cm

water

dimethylamide)

acid

ionophore 4-fert-butylcalix[4]arene-tetrakis(thioacetic

the

(NaTFPB),

tetrakis[3,5-bis(trifluoromethyl)phenyl]borate

The internal

mm

glued

filling

diameter
to

was

plasticized

solution

(if

not

punched
PVC

from the above ion-

tubing

with

specified otherwise)

THF/PVC

was

10'

110

NTA, 2.1

10"3

NaOH, 10'4 M Pb(N03)2, adjusted

NaOH. The calculated

log Pb.NTA

(Ag/AgCl

in 2

of

activity

11.39, pKal

10"3

NaCl).

Pb(N03)2 (1 ppb), 10"3

Pb2+

uncomplexed

1.89, pKa2

the internal

diaphragm separated

10'9

Chapter

filling
The

conditioning

was

solution

always

was

4.8

CaCl2 and 10"4 M HN03. All ISEs

[56, 57].

9.73

with

solutions from the reference half cell

conditioned for at least 24 h and used for not

measurement

1.3x10"9 M,

was

2.49, pKa3

7 with 0.1 M

pH

to

done with 4 ISEs of the

than

more

were

week. Each

one

composition

same

repeated

and

at

least two times.

Experiments

EMF measurements.

beakers, which

collected in

were

after

immediately

pretreated

were

Potentials

used.

electrode monitor at

specific
in

protocol

beaker

was

with

samples

solution). Subsequently,
but

sample,
acquired

adding

for 5 min. Four

and

was

with

with

the

following:

were

adjusted

amount of 1 M

HN03 (0.8

water);

pH buffers

no

16-channel

custom-made

the ISEs

equilibrated

were

potential

and the

sample

the target

smaller than 1 mV for

the ISE

more

500

was

Pb2+

period (ca.

10 min time

immersed into

additions

50

mL

were

of the

performed

jxL of standard) and the potential

from 8 to 4

pH-electrode.

was

Pb2+ concentration higher than the conditioning

successively changed

monitored

values

pH

of natural

for 1 min each time. For the measurements in

sample

polypropylene

4 in

HN03 overnight. The samples

required

case

pH

same

\iL of Pb2+ standard solution, and the potential

80

sample (80, 150, 250,

was

containing

observed until the drift

20 min for

in the

at

temperature (20-21 C) in stirred solutions. The

room

measurement

500 mL

the

measured

were

bottles and the

sampling by adding

sample

performed

with 0.1

polyethylene

to 3.1 mL to a 500 mL
were

were

The

Figures

was

6.4-6.6 the

by adding

ISEs

on

were

0.1

or

then

the

was

same

monitored

pH of

1 M

the

HN03

calibrated

as

described above. For this measurement the concentration of Pb2+ in the inner

filling

solution

conditioning

was

not

solution

buffered with NTA,

(see

Section

6.7).

but it

The

was

identical to the

theoretical

curves

were

Ill

by taking

calculated with Mathcad PLUS 6

following species: C032" (log ,

with the
=

2.48

KT3 M;

10.88, log 3

1.55

1.38; [Cl-]tot
=

7.20

CI"

(log j

1.25

log 2

liquid junction potential,

corrected for the

be

proportional

to

the

concentrations.

any

Pb2+. Calibration

values

EMF

and

Pb2+ activities

The

selectivity

ions and then for

interfering

ion.

obtained with
were

Pb2+ [29].

10"3

For

according

to

M solutions

were

rate

and

highest

samples.

at

were

65Cu, 1HCd

interfering

used for each

the

EMF

the Henderson

to

coefficients

not

All EMF data

experimental slope.

Canada)

were

and

was

The instrument

robust

interferences. The

measurements, Cu and Cd,

measured

initially

from

calculated

were

generation quadrupole-based

Concord,

in the water

sample uptake

was

were

were

calculated

[9].

DRC, PE/SCIEX,

spectroscopic

of three electrodes

the

using

assumed to

taken first for the

selectivity determinations, activity

the reference

quantification

set

not

were

coefficients

liquid junction potential according

ICPMS Measurements. A last

6100

new

coefficients

Selectivity

corrected for the

equation.

curves were

in 3 M

of the solutions

strength

the

pH glass

The

measured with the separate solution method with membranes

containing

log i

were

bridge electrolyte.

kept constant,

The

2.10).

C032"

1.40; [NOaltot

(Metrohm Ag/AgCl

also from Metrohm. Since the ionic

was

of

protonation

1 M NH4N03

1.70; log 2

1.17; log 2

16.35. The reference electrode

the measurements

during

1.80; log 3

[SO^Mtot

3.47;

min

6.29, log 2

3.20); HS04' (log ,

constant for the

KCl, type 6.0729.100) had

was

2.75; log 2

[CO32"]t0t,

8.85;

10"3 M); OH" (log ,

10"4 M); N03" (log ,

logarithmic equilibrium
10.33 and

1.60; log 2

10"5 M); HC03" (log j

electrode

4.14

13.94), SO42" (log ,

10"4 M);

[C032\]tot,max

6.20; log 2

of Pb

equilibria

into account the

plasma

208Pb,

abundance but to the least

were

to

to

(ELAN
metal

heavy

operated

at

minimize

elements

additionally

which

for

was

conditions

major interfering
monitored

used

ICPMS

for

the

Pb. The

low
non-

ISE-

isotopes

chosen with respect to the

potential spectroscopic

interferences

(e.g.

112

Na

Chapter

Ar

the

on

higher

of Pb

composition

were

abundant
not

Cu+).

considered to be of relevance for the accuracy

in these measurements. Due to this fact

required

isotopic

Variations in the natural

only

the most abundant

prior

to the

ICPMS measurements and included in the measurements to examine

signal

related

signal

isotope

used for

was

drift, which
variation

was

was

analysis.

10

found to be

2.5% with

^ig/L

of Tl and Bi

virtually

variation for

were

The

absent.

added

sample

periodic repetition

of

one

sample

below 0.5%.
The

instrumental

parameters under

standard

operation

mode

were

Rf-Power: 1350 W; Carrier gas flow: 0.95 L/min Ar;

following:

the

Auxiliary

gas flow: 0.9 L/min

Ar; Plasma gas flow: 14.5 L/min Ar; Nebulizer: Quartz,

concentric;

chamber:

Spray

mL/min; Autolens:
200 ms;

no.

Quartz,

cyclonic; Sample uptake

on; Measurement mode:

of sweeps: 5;

no.

of readings: 1;

of detection achieved under these conditions

for

208Pb,

formCd.

0.03

fxg/L (4.7

peak hop;
no.

of

were

10'10 M) for 65Cu and

rate:

dwell time per

replicates:

0.7

isotope:

10. The limits

0.002

(ig/L (9.7

10"12 M)

0.02

\ig/L (1.8

10"10 M)

113

7. EXPERIMENTAL PART

7.1

Reagents

Poly(vinyl chloride) (PVC),

(DOS)

potassium

and

lipophilic

sites sodium

tetrakis-[3,5-bis(trifluoromethyl)phenyl]borate

(NaTFPB,

2-nitrophenyl octyl

and

lipophilic

the

KTFPB),

ether

diisobutyldithiocarbamate

the

tetrakis(4-

tetradodecyl-ammonium

Pb2+-ionophores Methylene-bis-A^iV-

the

(MBDiBDTC,

calix[4]arene-tetrakis(thioacetic

Ca2+-ionophore

(o-NPOE),

salt

chlorophenyl)borate (ETH 500),

acid

ionophore

4-tert. -butyl-

VII),

the

dimethylamide) (ionophore VI),

A^,A^-dicyclohexyl-A^,A^-dioctadecyl-3-oxapentanediamide
tetrahydrofuran (THF)

and

(ETH 5234),

sebacate

plasticizers bis(2-ethylhexyl)

the

were

(CH-8071

from Fluka AG

Buchs).
The

Pb2+-ionophores 7V,A^-diheptyl-iV,A^,6,6-tetramethyl-4,8-dioxa-undecane-

diamide) (ETH

295,

ionophore V),

iV,A^-dioctadecyl-A^,7V-dipropyl-3,6-

dioxaoctanediamide) (ETH 322, ionophore I), A^,A^,A^,A^-tetradodecyl-3,6dioxaoctanediamide) (ETH 5428, ionophore II), #,7V,A^,7V-tetradodecyl-3,6dioxaoctane-l-thio-8-oxodiamide)

(ETH

and

III),

ionophore

5493,

A^,jV,J/V,A^-tetradodecyl-3,6-dioxaoctanedithioamide) (ETH 5435, ionophore

IV),

as

5315)

well

and

as

the

chromoionophores, 4-(octadecylamino)-azobenzene (ETH

9-dimethylamino-5-[4-(15-butyl-l,13-dioxo-2,14-dioxanonadecyl)

phenylimino]-5H-benzo[a]phenoxazine (ETH 5418)

laboratory
Aqueous

as

described

solutions

were

synthetized

in

our

[37, 38, 52].

were

prepared

freshly

with

resistance, 18.1 MQ cm) obtained with

deionized water

NANOpure

(specific

reagent-grade

water

system (Barnstead, CH-4009 Basel, Switzerland).

The salts

grade

NaCl, KCl, CaCl2 and MgCl2 and the acid HN03

from

disodium

Merck

(Darmstadt, Germany). Nitrilotriacetic

ethylendiamine

tetraacetic acid

(Na2EDTA)

of

Suprapur

acid

(NTA),

were

and all other salts

were

114

of

Chapter

puriss

The

p.a.

Pb2+

FIN03

or

quality

Microselect

standard solution with

was

from Fluka

7.2 Structures

Plasticizers

o-NPOE, C14H21N03, Mr 251.33

:h3
no2

Lipophilic

or

p.a.

quality

concentration of 1000 mg

obtained from Fluka Trace

DOS, C26H5o04,

Mr 426.69 g

anionic sites

NaTFPB, C32H12BF24Na, Mr 886.21 g

KTFPB, C32H12BF24K, Mr 902.32 g

analysis.

l"1

from Merck.
in 0.001 M

115

K+

F3C

J^jl

Lipophilic

ETH

or

Na+

tF3

salt

500, C72H1]6BC14N, Mr 1148.29

CI

Ch-V

^)-B-^^-CI

CI

lonophores

ETH

322, C48H96N2O4, Mr 793.34

ov

116

Chapter

ETH

5428, C54H108N2O4, Mr 849.45

ETH

5493, CjAgNzOaS, Mr 865.51

ETH

5435, C54H108N2O2S2, Mr 881.58

CCCOOO-^JH
ETH

295, C27H54N204, Mr 470.73

CH3

117

MBDiBDTC, C19H38N2S4, Mr 422.77

Pb2+-selective calix[4]arene derivate, C60H84N4O4S4,

er

'XT'

ETH

5234, C52H100N2O3,

Mr 801.37

Chromoionophores

ETH

5315, C30H47N3, 449.71, pKa 5.2 [51]

Mr 1054.59

118

Chapter

ETH

7.3

tx

5418, C45H57N305, Mr 719.95, pKa 9.0 [51]

Compositions

The

membrane

chapters 4, 5,

Membranes

ion-ionophore

of the membranes

compositions

and 6

are

ofchapter

Table 7.1. Membrane

name

described in the

experimental

sections

summarised in the tables below.

composition

of the ISE-membranes used for the determination of the

formation constants.

Ionoph ores
(mmol/kg)
-

NaTFPB

DOS

PVC

(mmol/kg)

(wt%)

(wt%)

5.0

32-33 %

65-66 %

ETH 322

15.5

5.0

32-33 %

65-66 %

ETH 5428

15.3

5.0

32-33 %

65-66 %

ETH 5493

16.3

5.0

32-33 %

65-66 %

ETH 5435

16.2

5.0

32-33 %

65-66 %

65-66 %

ETH 295

28.6

5.0

32-33 %

MBDiBDTC

29.3

5.0

32-33 %

65-66 %

Ionophore

14.9

5.0

32-33 %

65-66 %

VI

of

119

Table

7.2.

Membrane

stoichiometries of the

composition

ISE-membranes

used

determine

to

PVC

NaTFPB

DOS

(mmol/kg)

(wt%)

(wt%)

ETH 5428

10.7

3.3

32-33 %

65-66 %

ETH 5428

31.0

3.2

32-33 %

65-66 %

ETH 5493

10.2

3.2

32-33 %

65-66 %

ETH 5493

29.3

3.1

32-33 %

65-66 %
65-66 %

ETH 5435

10.2

3.2

32-33 %

ETH 5435

29.3

3.2

32-33 %

65-66 %

VI

1.6

0.5

32-33 %

65-66 %

VI

4.3

0.5

32-33 %

65-66 %

Ionophore
Ionophore

Table 7.3. Membrane

composition

of the

optode-membranes

used for the determination of

formation constants. The DOS and PVC amounts

the

ion-ionophore

and

32-33%, respectively, for all membranes.

name

Ionoph Dres
(mmol/kg)
-

Chromoionophores
name
(mmol/kg)

(wt%)

were

65-66%

KTFPB

(mmol/kg)

ETH 5315

9.4

11.0

ETH 322

26.1

ETH 5418

9.1

10.8

ETH 5428

26.2

ETH 5418

9.2

10.9

ETH 5493

26.6

ETH 5418

9.3

11.0
10.9

ETH 5435

26.2

ETH 5418

9.2

ETH 295

26.2

ETH 5418

9.1

11.0

MBDiBDTC

26.5

ETH 5418

9.2

10.9

Ionophore

26.4

ETH 5418

9.2

10.8

VI

the

ion-ionophore complexes.

IonophDres
(mmol/kg)

name

of the

120

Chapter

Membranes

of Chapter

Table 7.4. Membrane

composition

Ca

-ISEs.

ETH 5234

NaTFPB

ETH 500

DOS

PVC

thickness

(mmol/kg)

(mmol/kg)

(mmol/kg)

(wt%)

(wt%)

um

13.0

4.6

32-33 %

65-66 %

150

12.8

4.5

32-33 %

65-66 %

75

13.1

4.8

32-33 %

65-66 %

600

13.2

4.5

49-50 %

49-50 %

160

13.3

4.5

20-21 %

78-79 %

150

1.38

0.45

5.6

32-33 %

65-66 %

150

0.14

0.05

5.6

32-33 %

65-66 %

150

Membranes

of Chapter 6

Table 7.5. Membrane

mol%

(relative

to

composition Pb2+-ISEs.

To the membrane cocktail

were

added 50

NaTFPB) of Pb(N03)2.

Pb2+

NaTFPB

ETH 500

DOS

PVC

thickness

(mmol/kg)

(mmol/kg)

(mmol/kg)

(wt%)

(wt%)

urn

0.7

0.3

11.5

62%

36.5 %

Ionophore
VI

ca.

150

7.4 Electrodes and IsMF-measurements

The ion-selective membranes

glued

to

internal

filling

(Ag/AgCl
electrodes
custom

plasticized

in

PVC

tubing

solution of the ISE

a

were

chloride

punched

with
was

solution) by

from Methrom

made of the type free

measured with

were

from the master membrane and

THF/PVC

separated
a

(Ag/AgCl

slurry.

If necessary, the

from the reference half-cell

bridge electrolyte.
in 3 M KCl

flowing [53].

The

reference

type 6.0729.100)

The Potential differences

or

were

custom-made 16-channel electrode monitor and corrected for

121

the

liquid junction potential

Henderson formalism

of the reference electrode

[1, 70]. Activity

Debye-Hckel approximation [9].

coefficients

were

according

calculated

to

using

the
the

122

Chapter

Seite Leer /
Blank leaf

123

8. GLOSSARY

a,

activity [mol l"1]

*i(/)

activity [mol l"1]

ion

of the

in

an

sample

ideal

containing only
a

of the ion /

i,s

activity [mol l"1]

of the cation / in the

I,M

activity [mol l"1]

of the cation / in the membrane

i,S

activity [mol l"1]

of the ion i

i,ref

activity [mol l"1]

of the ion / in the

sample

of

bridge electrolyte

the reference electrode

a

j,s

a}(J)

activity [mol l"1]

activity [mol l"1]

containing only
a

of the ion / in the

of the

ion

sample
in

an

sample

ideal

X,M

activity [mol l"1]

of the anion X in the membrane

x,s

activity [mol 1"']

of the anion X in the

sample

chromoionophore

total

chromoionophore

concentration of the
Hbulk

concentration in the membrane

diffusing species

concentration of the ion / at the

DL

Detection Limit

Dl

diffusion coefficient for the

F
const

sample

phase boundary

diffusing species

[cm2 s"1]

electromotive force

contribution to EMF

sample independent potential

Diffusion

^D.ref

[mol cm"3]

concentration of the ion / in the bulk of the

CI,PB

EMF

potential

within the membrane

the

sample/reference

liquid junction potential

at

membrane-depending

potential

measuring
ISE

cell

consisting

responding only

to

of

difference

electrode
of

reference electrode and

changes

in als

the
an

124

Eu

Chapter

cell

ISE

of the

responding
E}

to

ISE

of the

EM

membrane

EM const

sum

of all

function

species

of the

ISE

of

the

difference

potential
of

reference electrode and

changes

to

linear

an

in aJS

response

of the

function

ISE

potential
membrane

sample independent

potentials

interface

phase boundary potential

filling

ionic

to several

an

to the ion J

bridge electrolyte

Em.

reference electrode and

response

consisting

responding only

intercept

the

of

the ion /

cell

responding

EPB

linear

membrane-depending
measuring

of

consisting

responding simultaneously

intercept

difference

potential

membrane-depending
measuring

the

at

ISE

membrane/inner

solution interface

phase boundary potential

at

the ISE

membrane/sample

interface

tetraacetic acid

EDTA

ethylendiamine

EPA

Environmental Protection

Faraday

constant

Kcoex

overall

coextraction

(96487

Agency

mol"1)

constant

of

membrane

with

ionophore
KSKCh

overall
with

Ku

ion-exchange equilibrium

constant

of

membrane

ionophore

ion-exchange
between

constant

sample

of the

uncomplexed

ion / and /

and membrane

Klx

coextraction constant

Kff

Potentiometrie selectivity

coefficient of the ISE for the

ions / and J

kx

"single

ion distribution coefficient" of the cation /

k}

"single

ion distribution coefficient" of the cation /

125

ion distribution coefficient" of the anion X

kx

"single

primary

(IE)

ion-exchanger membrane

IL

ion-ionophore complex

ICPMS

Inductive

I SE

ion-selective electrode

interfering

JL

ion-ionophore complex

/j(x)

rate

(L)

Lj

of the

ion

primary

Plasma Mass

Coupled

Spectrometry

cation

of transfer of the

in the
L

cation

interfering

of the

species

/ per unit

x-coordinate, flux [mol cm"2

ion

area

of the section

s"1]

ionophore (ligand)

ionophore-based membrane
total

ionophore

concentration in the membrane

index

membrane, if used

molar

mV

10~3 Volt

NTA

nitrilotriacetic acid

nM

nanomolar

ft,

stoichiometry

of the

primary ion-ionophore complex

_,

stoichiometry

of the

interfering ion-ionophore complex

PVC

poly(vinyl chloride)

ppm

part per milion

ppb

part per bilion

molar gas constant

RT

total

as

(mol/1)

(10"9 mol/1)

(8.314

concentration

of

J K"

lipophilic

membrane
if used

index

sample,

.?!

slope

of the/-selective ISE

s}

slope

of the J -selective ISE

absolute temperature

THF

tetrahydrofuran

as

[K]

mol"

anionic

sites

in

the

Chapter

TMA

tetramethylammonium

w,

absolute

WHO

World Health

counter anion

space coordinate measured

mobility

of the ion i

[cm

mol

-1

Organisation

perpendicularly

to the

section

[cm]
zl

charge

of the ion i

Zj

charge

of the cation /

Zj

charge

of the cation J

zx

charge

of the anion X

formal

complex

electrical

potential

<ps

electrical

potential

in the

(pu

electrical

potential

in the membrane

(f)(x)

electrical

potential

in x-coordinate

fii

electrochemical

fJLx

chemical

standard free energy of the ion /

fiis

electrochemical

potential

of the ion / in the

sample

fiiM

electrochemical

potential

of the ion / in the

sample

<5M

thickness of the

formation constant

potential

potential

sample

of the ion /

of the ion /

potential determining

diffusion

layer

in

potential determining

diffusion

layer

in

the membrane

thickness of the
the

v(x)

sample (Nernstian layer)

hydrodynamic velocity

in x-coordinate

[cm

s"1]

127

9. REFERENCES

(1) Morf,

Transport; Elsevier:

(2) Eisenman,
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Principles of Ion-Selective

W. E. The

York,

New

Electrodes and

York, 1981.

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1967.

Carrier-Based Ion-Selective Electrodes and Bulk

Potentiometrie and

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U.

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Analytica

1998, 98, 1593-1687,

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W. Anal.

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Determination

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E. Anal.

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1999, 71, 1210-1214, Lowering the Detection Limit of

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Solvent

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Electrolyte

Solution.

Composition

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130

Chapter

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1992, 6, 295-298, Principles

W. Sens. Actuators, B

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Optodes.

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137

Curriculum Vitae

the

1973

Born

1974-1984

Primary

1984-1988

Secondary

1988-1992

Post

on

(TI), Switzerland

school education at Bellinzona

education

at

Liceo

Cantonale, Bellinzona,

Matrick of scientific type

Studies at the
Institute of

1997

at Bellinzona

school education at Bellinzona

secondary

passing
1992-1997

8th of November

Chemistry Departement

Technology (ETH)

Chemistry degree

of the Swiss Federal

Zrich

of the Swiss Federal Institute of

(ETH) Zrich, diploma

Technology

thesis in the group of Prof. Dr. Ern

Pretsch
1997-2001

Ph. D.

studies in the group

chemical
1998-2000

of Prof.

Dr.

Ern

Pretsch

sensors

Laboratory

assistant for

gas-chromatography

and GC-MS in

analytical chemistry

Languages: Italian, German, French, English

Zurich, May 2001

on

Alan Ceresa