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Senzori

potentiometrici.
Electrozi ionselectivi.
Curs 03

Senzori potentiometrici. Electrozi ionselectivi.


Aparitia potentialului in celula de masura la
curent zero

Senzori potentiometrici. Electrozi ionselectivi.


Aparitia potentialului in celula de masura la
curent zero

Potentiometric Methods
1.) Potentiometric Methods: based on measurements of the
potential of electrochemical cells in the absence of
appreciable currents (i = 0)
2.) Basic Components:
a) reference electrode: gives reference for potential
measurement
b) indicator electrode: where species of interest is
measured
c) potential measuring device

Electrozi ionselectivi cu
membrana solida
Membrana

monocristal
substanta cristalina
sticla
Din punct de vedere construnctiv
Varianta totul solid
varianta membrana

Varianta membrana
totul solid

Varianta

EIS cu membran solid

Din aceast clas de EIS, exemplul cel mai bine cunoscut l constituie electrodul de
sticl pentru msurarea pH-ului. Gruprile schimbtoare anionice din structura
membranei de sticl apar ca urmare a defectelor din matricea de SiO 2 i datorit
vacanelor cationice provocate de constituienii sticlei, diferii de SiO 2. n stratul de
sticl hidratat, de cca 5-100 nm grosime, ce se formeaz la suprafaa membranei de
sticl activ, concentraia de grupri schimbtoare este relativ mare (cca. 3 - 10 M).
Astfel se explic domeniul de lucru excepional de ntins pentru electrodul de sticl
de pH.
Dac se admite c diferena de potenial care apare ntre cele dou soluii
adiacente membranei de sticl este rezultatul unui proces de schimb ionic, localizat
la cele dou interfee membran-soluie, cuplat cu un proces de difuzie prin
membran, atunci nsumarea acestor contribuii conduce la urmtoarea expresie
pentru potenialul electrodului de sticl [41]:
= 0 + (RT/F)ln[ i.KpotA,i.ai(1/zi)]
(16)
unde: A semnific ionul primar (i = 1), z i - sarcina fiecrui ion determinant de
potenial, KpotA,i - coeficientul de selectivitate poteniometric, iar R,T,F i 0 au
semnificaiile cunoscute.
Pentru electrozii de sticl, coeficientul de selectivitate poteniometric este dat
de relatia :
KpotA,B = (uB/uA).A,B (17)

unde: A,B este constanta de echilibru pentru reacia de schimb ionic care descrie
procesul de interferen:
(1/(zB) Baq + (1/zA) Amembran (1/zB) Bmembran + (1/zA) Aaq
(18)

iar uA i uB sunt mobilitile ionilor respectivi n faza membran.

EIS cu membran solid

Relaiile (16) - (18) sunt valabile i n cazul EIS cu membrana


relizat dintr-un schimbtor de ioni solid. Pentru EIS cu membran
solid din monocristal (de ex. LaF3) sau policristalin (ex. Ag2S, Ag2SAgX, etc.) procesul de difuzie prin membran fiind extrem de lent nu
joac un rol notabil n apariia potenialului de electrod. De aceea,
pentru aceti electrozi coeficientul de selectivitate poteniometric
are o expresie simplificat [42]:
KpotA,B = (AgX)/(AgY)
(19)
unde: reprezint produsul de solubilitate al srurilor greu solubile
implicate n funcionarea electrozilor pe baz de sruri de Ag. Se
observ c n acest caz coeficientul de selectivitate poteniometric
se va identifica cu constanta de echilibru a reaciei de schimb ionic
care st la baza apariiei fenomenului de interferen :

AgXmembran + Yaq AgYmembran + Xaq (20)


Relaia (19) permite deci o estimare rapid a valorii coefientului de
selectivitate pentru EIS din sruri greu solubile. Aceast ipotez a
fost verificat experimental [43] gsindu-se o excelent concordan
ntre coeficienii de activitate calculai i cei msurai (fig. 9).

Electrodul de sticla. Masurarea


pH-ului

10

Electrodul de sticla
i. most common example of an ISE

based on use of glass membrane that preferentially


binds H+

ii. Typical pH electrode system is shown

Two reference electrodes here

one SCE outside of membrane


one Ag/AgCl inside membrane
pH sensing element is glass tip of Ag/AgCl
electrode

11

Electrodul
de sticla

12

Electrodul de sticla.
Masuratori

13

Electrodul de sticla

14

Electrodul de sticla
iii. pH is determined by formation of
boundary potential across glass
membrane

Si OGlass Surface

At

each membrane-solvent interface, a small local


potential develops due to the preferential adsorption
of H+ onto the glass surface.
15

Electrodul
de sticla

16

iii.

Electrodul de
sticla
pH
is determined by

formation of boundary potential


across glass membrane

Boundary potential difference (Eb) = E1 =E2 where


from Nernst
Equation:
-log aH+ (on exterior of
E = k 0.592pHprobe or
constant b
in analyte

solution)
Selective binding of cation
(H+) to glass memb
17

Electrodul de sticla: eroare


alcalina

H+ not only cation that can bind to glass surface


- H+ generally has the strongest binding
Get weak binding of Na+, K+, etc
Most significant when [H+] or aH+ is low (high pH)

- usually pH =11-12
Eroare alcaline: O eroare sistematic care apare atunci cnd electrozii de sticl sunt utilizate pentru a citi pH-ului
unei soluii extrem alcalin; electrodul rspunde la ionii de sodiu ca i cum ar fi ionii de hidrogen, dnd unui pH care
este n mod constant prea sczut

At low aH+ (high pH),


amount of Na+ or K+
binding is significant
increases the apparent
amount of bound H+
pH masurat mai mic decat cel real!
18

Electrodul de sticla: eroare


acida

Errors at low pH (Acid error) can give


readings that are too high
Exact cause not known
- usually occurs at pH =0.5

19

Alkali error range - at low concentration of hydrogen ions (high values of pH)
contributions of interfering alkali metals (like Li, Na, K) are comparable with the one
of hydrogen ions. In this situation dependence of the potential on pH become nonlinear.
The effect is usually noticeable at pH > 12, and concentrations of lithium or sodium
ions of 0.1 moles per litre or more. Potassium ions usually cause less error than
sodium ions.
Acidic error range at very high concentration of hydrogen ions (low values of pH)
the dependence of the electrode on pH becomes non-linear and the influence of
the anions in the solution also becomes noticeable. These effects usually become
noticeable at pH

Electrodul de sticla : Eroare acida,


eroare alcalina

21

Electrodul de sticla

Potential de asimetrie ???


Avantaje
Dezavantaje
22

Calibrarea electrodului
de sticla
pH 4
pH 7
pH 9

??????

Calibrarea electrodului
de sticla

Potential de asimetrie
The
Theisopotential
isopotentialpoint
point(usually
(usuallyat
atpH
pH7)
7)of
ofaaglass
glasselectrode
electrodeisistemperature
temperatureinsensitive.
insensitive.
The
Thepotential
potentialisisset
setat
atzero
zerohere
here(if
(ifdifferent
differentthan
thanzero,
zero,this
thisisisthe
theoffset).
offset).

Fig. 13.11. Isopotential


point.

Electrod de sticla pentru alti


cationi

i. Maximize kH/Na for other ions by


modifying glass surface
change composition of glass
membrane

putting Al2O3 or B2O3 in glass

enhances binding for ions other


than H+
ii. Possible to make glass
membrane electrodes for Na+, K+,
NH4+, Cs+, Rb+, Li+, Ag+

27

Electrod monocristal
de LaF3

LaF3 crystal doped with EuF2


mechanism similar to pH
electrode with potential
developing at two interfaces of
the membrane from the reaction:

Presence of F- analyte pushes


equilibrium right, reduces +ve
c
charge on
surface
RT electrode
F ,ref
const

ln

c
F ,test

the side of the membrane with the


lower aF- becomes positive relative
to the other surface:

28

Electrod monocristal de
LaF3

29

Electrod monocristal de
LaF3
Electrodul pentru F are membrana din LaF3, o
solutie interna continand 0,1 mol dm3 NaF si
0,1 mol dm3 NaCl si un electrod intern de
referinta Ag, AgCl.

Ag, AgCl Cl (0,1 mol dm3), F (0,1mol dm3) LaF3 solutie de


testat Cl (saturata) Hg2Cl2, Hg

Limitari
- domeniul de concentratii: 106 (pH solutiei < 8) 10-1 M (pH
solutie < 12);
- pH < 3 interfera formarea HF.

Electrozi cu
membrana
solida omogena
Electrozi Ag2S
selectivi
Electrozi Ag2S-AgX
Electrozi Ag2S-MeS

Ag+ sau S2 X - selectivi


Me+ - selectivi

Ag2S-AgX