Senzori u industriji i zaštiti okoliša

POTENTIOMETRIC DETERMINATION OF LOW LEVELS OF ANIONIC AND NONIONIC SURFACTANTS IN EFFLUENTS

SENZORI U INDUSTRIJI I ZATITI OKOLIAProf. dr.sc. Milan Sak-BosnarSveuilite Josipa Jurja Strossmayera u OsijekuOdjel za kemijuEdukacija: Inovativne metode pouavanja u nastavi kemije

SADRAJUvod2.Elektrokemijski senzori i biosenzori3.Potenciometrijski senzoriPotenciometrija5.Tenzidni senzori6.Odreivanje tenzida u industrijskim proizvodima7. Odreivanje tenzida u industrijskim otpadnim vodama8. Tenzidni senzori u analizi injektiranjem u protok9. Prednosti i ogranienja tenzidnih senzora10. Trendovi razvoja tenzidno-selektivnih senzora11. Plinski senzori12. Elektronski nos13.Elektronski jezik

1. Uvod

Analitika kemijaDefinicija: Znanstvena disciplina koja razvija i primjenjuje metode, instrumente i strategije za dobivanje informacija o sastavu i prirodi tvari u prostoru i vremenu.

Kvalitativna analitika kemija

Kvantitativna analitika kemija

to su senzori?

Definicija American National Standards Institute (ANSI):Ureaj koji daje uporabljiv izlazni signal kao odgovor na tvar koja se mjeri

Senzor mjeri fizikalni parametar i prevodi ga u signal pogodan za obradu (npr. optiki, elektrini, mehaniki)

AnalitPretvaraElektrokemijski signalReceptor

Svjetsko trite senzora:$79.5 bilijuna u 2013$86.3 bilijuna u 2014, $95.3 bilijuna u 2015, $154.4 bilijuna do 2020, Godinji rast proizvodnje: 10.1% od 2015 do 2020.Svjetsko trite kemijskih senzora:$20.45 bilijuna do 2018$31.2 bilijuna do 2020Godinji rast proizvodnje: 7.60% od 2014-2020.Posebno je brza ekspanzija u medicini, automobilskoj industriji i zatiti okolia.Trite senzora

Kemijski senzori klasificiraju se prema principu rada pretvaraa (transducer):

1. Optiki senzori pretvaraju promjene optikih fenomena kao rezultat interakcije analita s receptorom.

2. Elektrokemijski senzori pretvaraju efekt elektrokemijske interakcije analit elektroda u uporabljiv signal. Ti efekti mogu biti stimulirani elektrino ili spontanom interakcijom pri uvjetima nulte struje. Razlikuju se sljedee podgrupe:

a) Voltametrijski senzori ukljuivi amperometrijske senzore

b) Potenciometrijski senzori

3. Elektrini ureaji zasnovani na mjerenjima gdje ne dolazi do elektrokemijskih procesa, ali signal nastaje zbog promjene elektrinih osobina izazvanih interakcijom s analitom

4. Ureaji osjetljivi na masu pretvaraju promjenu mase na posebno modificiranoj povrini u promjenu osobina nosaa (mase)

5 . Magnetski ureaji zasnovani na promjeni paramagnetskih svojstava plina koji se analizira

6. Termometrijski ureaji zasnovani na mjerenju toplotnih efekata specifine kemijske reakcije ili adsorpcije koja ukljuuje analit

Klasifikacija kemijskih senzora

2. Elektrokemijski senzori i biosenzori

(Bio)kemijski senzori su ureaji za pretvorbu kemijske ili bioloke veliine u elektrini signal. Podruje primjene kemijskih senzora je raznoliko. Ciljani analiti mogu biti razni kationi ili anioni, zatim plinovi, otrovne organske pare, razliiti metaboliti, proteini, mikroorganizmi itd. Veliku podgrupu kemijskih senzora ine biosenzori, senzori koji odreuju neku bioloku veliinu (eere, proteine, enzime, antitijela). Najrazvijenija grupa senzora su elektrokemijski senzori. S obzirom na elektrokemijsku veliinu koju mjere, dijele se na potenciometrijske (napon), amperometrijske (struja) i konduktometrijske senzore (otpor). Zajednika karakteristika im je da koriste elektrode na kojima se odvijaju kemijske reakcije ili na njima dolazi do izmjene prijenosa naboja. Ime senzora koje se koristi u praksi esto oblikuje veliina koja biva pretvorena u elektrini signal, i/ili princip konverzije.

Tako se npr. kemijski senzori za detekciju plinova u zraku nazivaju plinski senzori, kemijski senzor za detekciju vlage skraeno se naziva senzor vlage, amperometrijski senzor za odreivanje eera u krvi glukozni senzor itd.Kemijski senzori omoguavaju odreivanje ciljanog analita u prisutnosti interferirajuih sastojaka. Imaju sposobnost vie ili manje selektivnog prepoznavanja analita.

Shema kemijskog senzora

Za selektivno vezanje analita na senzor odgovoran je element za prepoznavanje (recognition element) tzv. receptor. Kao posljedica interakcije analita i receptora dolazi do promjene jednog ili vie fizikalno-kemijskih parametara. Pretvornik (transducer) ih prevodi u mjerljiv izlazni signal, koji se moe pojaati, obraivati i prikazivati u pogodnom obliku.

Dobre osobine kemijskog senzora postiu se dobrim odabirom receptora i pretvornika. Karakteristike senzora odreuje njegova selektivnost, osjetljivost, stabilnost i trajnost. Selektivnost pokazuje u kojoj mjeri senzor razlikuje analit od supstanci sline ili razliite kemijske strukture, i praktino je odreena elementom za prepoznavanje (receptorom). Osjetljivost senzora je odreena receptorom i pretvornikom. Osjetljivot senzora mogue je poveati uvoenjem dodatnih stupnjeva pojaavanja signala, i tako poveati njegovu preciznost i sniziti granicu detekcije. Kod potenciometrijskih senzora pri interakciji analita i receptora dolazi do promjene elektrodnog potencijala receptora u funkciji koncentracije analita. Pretvornik pojaava izlazni naponski signal (pri nultoj struji), obrauje ga i prikazuje u pogodnom obliku.

Ionsko-selektivne elektrode (Ion-selective electrodes, ISE)elektrokemijski senzori iji potencijal (u sprezi s odgovarajuom referentnom elektrodom) ovisi o logaritmu aktiviteta ispitivanog iona u otopini

za reakciju Ox + ne- Red vrijedi Nernstova jednadba:

za sluaj:Cu2+ + 2e- Cu

Nernstova jednadba glasi:

R = univerzalna plinska konstantaT = Termodinamika temperaturaF = Faradayeva konstanta3. Potenciometrijski senzori

Kako je aktivitet vrstih specija po konvenciji = 1 (a = 1), to u naemsluaju pa imamo:

openito za kation Mn+:

ako zamijenimo gdje = nagib (slope)

dobiva se

analogno za anion An- :

odnosno, nakon sreivanja: tj.

Koritenjem Nernstove jednadbe, mjerenjem elektrodnog potencijala moe se izraunati aktivitet/koncentracija nekog iona-analita u otopini.

Mjerni sustav za rad s ion-selektivnom elektrodom

Staklena pH elektroda (Glass electrode) prva i najee koritena ISE !!!!

Od ranije iz Nernstove jednadbe:

Isto vrijedi i za i kako je n = 1:

Kako je ili ispravnije

pa je

Odreivanje osjetljivosti (1), granice osjetljivosti (2), linearnosti (3) i ukupnog mjernog podruja (4) potenciometrijskog senzora. Granice osjetljivosti

E/mVlog a 1234

Kemijske interferencije / selektivnost Selektivnost ionsko-selektivne elektrode odreuje njezinu osjetljivost kada otopina uz primarni ion (analit) A, sadri i interferirajui ion B.

Odziv membrane u prisustvu nekoliko vrsta iona uvjetovan je konstantama ravnotee reakcija izmjene primarnog i interferirajueg iona izmeu organske i vodene faze.

Rezultirajui potencijal se moe tono opisati pomou koeficijenata potenciometrijske selektivnosti, ne znajui pri tome niti jednu konstantu ravnotee.

Utjecaj interferenta na odziv ionsko-selektivne elektrode (potenciometrijskog senzora) definira NikolskyEisenmanova (N-E) jednadba:

= elektromotorna sila galvanskog lanka, = faktor konstantnog potencijala (constant potential term),

= Nernstov nagib,

= koeficijent potenciometrijske selektivnosti,

= aktiviteti iona analita A i interferenta B,

= naboji iona analita A i interferenta B.

4. PotenciometrijaMetoda kojom se mjeri razlika potencijala izmeu elektroda elektrokemijske elije uz ravnotene uvjete. Napon elije mjeri se tako da kroz eliju ne tee struja, odnosno tee tako mala struja da ona ne utjee na mjerljivo stanje ravnotee na elektrodama.koncentracijsko podruje za potenciometrijska mjerenja iznosi od 10-5 10-1 M,mjerni ureaji za mjerenje razlike potencijala:potenciometrivoltmetri s velikom ulaznom impedancijom: pH - metripIon - metri

Potenciometrijska mjerenja provode se uz upotrebu dviju elektroda:

referentna elektrodapotencijal je konstantanuniverzalna referentna elektroda: standardna vodikova elektroda

sekundarne referentne elektrode:kalomelova elektroda Hg/Hg2Cl2 elektroda srebro/srebrov klorid Ag/AgCl

indikatorska elektrodapotencijal ovisi o aktivitetu (koncentraciji) jedne ili vie ionskih vrsta u eliji

uglavnom ima visoko selektivan odziv na ispitivane ione

u ai s homogenom otopinom uzorka su dvije elektrode koje su spojene na milivoltmetar elektrokemijski lanak

potencijal ovog elektrokemijskog lanka (Ec) iznosi:

EC = EIE - EREEC = EMJERENI

Odjel za kemiju

elija za potenciometrijska mjerenjaKompletna elija sastoji se od indikatorske elektrode koja odgovara na analit i referentne elektrode iji je potencijal konstantan. Mjeri se razlika potencijala izmeu te dvije elektrode. Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Potencijal indikatorske elektrode odreen je Nernstovim izrazom:

U Nernstovom izrazu koristi se aktivitet, a ne koncentracija iona:

ax = fx [X] ax = aktivitet iona [X] = molarna koncentracija iona fx = koeficijent aktiviteta

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Standardne (referentne) elektrode

Potencijal im je stalan tijekom elektroanalitikog postupka, pa slue kao standard prema kojem mjerimo potencijal druge elektrode (radne ili indikatorske).

Primjena referentnih elektroda: mjerenje pH, mjerenje s ion-selektivnim elektrodama, potenciometrijske titracije, voltametrija.Odjel za kemiju

Analitika primjena potenciometrije

a) direktna potenciometrijab) potenciometrijska titracija

a) Direktna potenciometrija (Direct potentiometry)

Priredi se serija otopina razliitih koncentracija (aktiviteta) ispitivanog iona: a1, a2, a3, .. an,izmjere se pripadajue vrijednosti za E: E1, E2, E3, .. En,konstruira se badarni dijagram E = f(log a),za odreivanje aktiviteta koristi se linearni dio dijagrama.

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Instrumentacija

pH-metar / milivoltmetar (ionometar), komercijalne ISE esto u svojoj konstrukciji imaju ugraenu i referentnu elektrodu tada je to kombinirana ISE.

Badarni dijagram

5. Tenzidni senzori (Tenzidne ionsko-selektivne elektrode)

Trite tenzidaSvjetsko trite tenzida: preko US$ 41 bilijun u 2018.

Svjetska potronja tenzida (%) prema tipu tenzidaAnionski tenzidi ine oko 50 % svih tenzida u Europi i oko 60 % u USA.

27IV INTERNATIONAL CONGRESS "Engineering, Environment and Materials in Processing Industry

Supstance koje smanjuju povrinski napon.

U svojoj molekularnoj strukturi sadre hidrofobne i hidrofilne funkcionalne grupe. Tenzidi (povrinski aktivne tvari): definicija

Klasifikacija povrinski aktivnih tvari (tenzida)

Prema hidrofilnim skupinama u strukturi molekula i njihovom elektrokemijskom ponaanju tenzidi se svrstavaju u etiri glavne kategorije (Tablica 1). Anionski tenzidi su povrinski aktivne tvari s jednom ili vie funkcionalnih grupa, koje u vodenim otopinama ioniziraju dajui negativno nabijene povrinski aktivne organske ione. Kationski tenzidi su povrinski aktivne tvari s jednom ili vie funkcionalnih grupa, koje u vodenim otopinama ioniziraju dajui pozitivno nabijene povrinski aktivne organske ione.Neionski tenzidi su povrinski aktivne tvari koje ne disociraju u vodenoj otopini. Topljivost neionskih tenzida u vodi potjee od funkcionalnih grupa u njihovoj strukturi s jakim afinitetom prema vodi. Amfolitski tenzidi su povrinski aktivne tvari s jednom ili vie funkcionalnih grupa koje u zavisnosti od uvjeta sredine u kojoj se nalaze mogu disocirati u vodenoj otopini tako da spoj dobije karakteristike anionskih ili kationskih tenzida.

Anionski tenzidi Kationski tenzidiNeionski tenzidiAmfolitski tenzidiPrimjer: Sodium dodecylbenzenesulfonate (Alkylbenzenesulfonate) Primjer: N-Hexadecyltrimethylammonium chloride (Alkyl Quaternary Ammonium Salts)Primjer: Dodecanol 9-mole ethoxylate (Ethoxylated Alcohols)Primjer: Dodecyldimethylammoniomethane carboxylate (Alkylbetaine)Tenzidi: klasifikacija

Tenzidni senzori (Tenzidne Ionsko-Selektivne Elektrode) Tenzidne ionsko-selektivne elektrode (tenzidni senzori, surfactant sensors) su elektrokemijski senzori koji omoguavaju potenciometrijsko odreivanje povrinski aktivnih tvari (tenzida). Potencijal takve elektrode logaritamski ovisi o aktivitetu tenzidnog iona/molekule na kojeg je elektroda selektivna. Mjerenje tenzidnom ionsko-selektivnom elektrodom se izvodi u elektrokemijskoj mjernoj eliji koja se sastoji od dva galvanska polulanka: tenzidne ionsko-selektivne elektrode i referentne elektrode:

Slika 2. Elektroda s tekuom membranom i unutranjim referentnim elektrolitom

Slika 3. Elektroda s PVC membranom i vrstim kontaktom i elektroda s presvuenom icom (CWE)

Elektrode s prevuenom icom (Coated-wire electrode)

1 tanak sloj tenzidno-selektivnog materijala u PVC matrixu,

2 platinska ica,

3 sloj izolatora.

Dizajn senzora

Slika 4. Uobiajeni sastav PVC membrane

Elektrode s tekuom membranom

Priprema membrane

Ag/AgCl referentna elektroda,Unutarnja referentna otopina,PVC cijev, Polimerna membrana s ugraenim tenzidnim senzorskim materijalom (ionofor).

Screen-printed senzor

Screen-printed senzor http://www.dropsens.com/img/productos/screen_printed_elect2.gif)

Odziv tenzidnih senzora (elektroda)

Ionski tenzidi (ionic surfactants)

Tenzidni ioni stvaraju ionske asocijate (ionske parove, ion-pairs) sionima suprotnog naboja:(1),gdje je

Cat+ = veliki "onium" kationi (ukljuivi kvaterni amonijev, arsonijev, piridinijev, fosfonijev itd.), bazne boje, veliki kompleksni kationi nastali iz metalnih iona i neutralnih liganada, veliki organski kationi, itd. (lipofilnog karaktera),

An- = anioni anionskih tenzida, veliki organski i anorganski anioni, itd. (lipofilnog karaktera).

Elektromotorna sila koja se uspostavlja na membrani senzora uronjenog u otopinu anionskog tenzida (analita) definirana je Nernstovim izrazom:

(2),

gdje je Eo = konstanta, S = nagib senzora (elektrode), a(An-) = aktivitet tenzidnog aniona.Za ionski par CatAn (jedn. 1) konstanta produkta topljivosti je

gdje su a(Cat+) i a(An) aktiviteti odgovarajuih tenzidnih iona.(3)

Iz jedn. (3) slijedi

,te nakon uvrtenja u jedn. (2), dobiva se sljedei izraz za odziv elektrode:

koji nakon preureenja daje:(4)

(5),gdje je

Neionski tenzidi (nonionic surfactants) Etoksilirani neionski tenzidi (ethoxylated nonionic surfactants)Barijev ion tvori pseudokationske komplekse s etoksiliranim neionskimtenzidima (EONS) prema sljedeoj shemi:(6)Vrijednost x varira u ovisnosti o broju etoksi (EO) jedinica u molekuli tenzida.Radi jednostavnosti gornja se jednadba moe napisati kao:(7),gdje je L=EONS

Membrana senzora sadri teko topljivi pseudokationski tetrafenilboratni ionsko-izmjenjivaki kompleks kao senzorski materijal, koji se dobiva reakcijom tetrafenilboratnog iona (TPB) s pseudokationskim kompleksom: (8)Stehiometrija reakcija (6) - (8) ovisi o duini lanca etoksiliranog (hidrofilnog) lanca ispitivanog neionskog tenzida kao i o prirodi ostatka molekule tenzida (hidrofobni dio).

Senzor pokazuje odziv na TPB- i na BaLx2+ ione prema Nernstovoj jednadbi:

(9)

(10)i

Karakterizacija tenzidnih senzora

Slika 5. Odziv tenzidno-selektivne elektrode s tekuom membranom zasnovane na ionskom paru DMI-TPB, u odnosu na dodecilsulfat () i dodecilbenzensulfonat NaDBS ().Anionski odziv tenzidnog senzora

PARAMETRIANIONSKI TENZIDIDodecilsulfatDSDodecilbenzensulfonatDBSNagib / (mV/dekada)59,3 0,657,8 0,6Koeficijent korelacije (r)0,99930,9994Donja granica odreivanja / (mol/L)0,320,60Korisno podruje / (mol/L)0,4 - 50000,8 630

Tablica 2

Karakteristike odziva elektrode s tekuom membranom selektivne na anionske tenzide, zasnovane na ionskom paru DMI-TPB, navedene zajedno s granicama pouzdanosti.

Fig. 6. Karakteristike odziva DMI-TPB tenzidnog senzora prema Hyamine (), CPC () i CTAB ().Kationski odziv tenzidnog senzora

Slika 7. Karakteristike dinamikog odziva DMI-TPB senzora u otopinama dodecilsulfata (DS) i dodecilbenzensulfonata DBS).Dinamiki odziv DMI-TPB senzora

Primjena tenzidnih senzora

Detekcija zavrne toke pri potenciometrijskim titracijama

Potenciometrijske titracije ionskih tenzida Potenciometrijske titracije su titracijske metode u kojima se za odreivanje zavrne toke koriste potenciometrijski senzori. Ispitivanjima mogunosti primjene potenciometrijskih titracija za odreivanje anionskih tenzida kao zamjene za vizualne titracije u velikoj mjeri su pridonijela opaanja interferencije anionskih tenzida u titracijama u kojima je kao senzor bila upotrijebljena kalcijeva ili nitratna ionsko-selektivna elektroda. Nakon toga su uslijedila istraivanja na razvoju tenzidnih ionsko-selektivnih elektroda, potenciometrijskih senzora namijenjenih za primjenu u analitici tenzida. Najvaniji dio elektrode/senzora je membrana, koja se najee sastoji od ionskog asocijata, tzv. ionofora, te odgovarajueg plastifikatora i PVC matrice. Ionofor je odgovoran za elektroaktivnost membrane.

Potenciometrijske titracije ionskih tenzidaPrimjena potenciometrijskih tenzidnih senzora je vezana za promjene potencijala u otopini analita (anionskog tenzida): U sluaju odreivanja anionskih tenzida, veliina promjene potencijala ovisi o koncentraciji analita i produktu topljivosti soli koja je nastala u reakciji izmeu anionskog tenzida (analita) i kationskog tenzida (titranta). Soli niskog produkta topljivosti daju stabilne ionske asocijate, zbog ega je promjena potencijala u toki ekvivalencije kod njih vea nego kod soli s viim produktom topljivosti.

a koje su posljedica kemijske reakcije titranta (kationskog tenzida) i analita (anionskog tenzida)

Potenciometrijske titracije ionskih tenzidaBudui da za veliku promjenu potencijala u podruju zavrne toke titracije ionski asocijat treba biti to je mogue manje disociran, dobar titrant je reagens s velikom afinitetom za analit. Istraivanja su pokazala da je 1,3-didecil-2-metil-imidazolijev klorid (DMIC), koji je po svojoj prirodi takoer kationski tenzid, dobar izbor kationskog titranta za potenciometrijske titracije anionskih tenzida:

Potenciometrijske titracije s tenzidnim ionsko-selektivnim elektrodama pogodne su za iste otopine tenzida. U detergentima se primjenjuju manje ili vie uspjeno. U analizi detergenata, koji su po svojoj prirodi viekomponentni sustavi, potencijalni interferenti prisutni u titracijskoj otopini mogu nepovoljno utjecati na odziv elektrode i znaajno naruiti preciznost odreivanja.

Potenciometrijske titracije ionskih tenzidaTako npr. poveana koncentracija nekih soli moe tetno utjecati na odziv elektrode to uzrokuje deformaciju titracijske krivulje, tj. njezino proirenje u podruju infleksije uzrokovano nastajanjem micela tenzida. Na neke interferencije mogue je utjecati ispravnim odabirom pH-podruja u kojem je utjecaj interferenta zanemarljiv. Primjenom potenciometrijskih senzora za odreivanje zavrne toke u titracijama tenzida, odreivanja je mogue automatizirati, ime se poveava brzina odreivanja i izbjegavaju subjektivne pogreke analitiara. Sljedei ne manje vaan razlog razvoja potenciometrijskih titracija u analitici tenzida je upotreba kloroforma u titraciji u dvije faze, to predstavlja ozbiljan ekoloki problem koji za sobom povlai trokove oko zbrinjavanja otpada. Primjena potenciometrijskih senzora u analitici tenzida, proizala iz njihovog razvoja u posljednja etiri desetljea, je danas sve znaajnija.

Indikatori zavrne toke u potenciometrijskim titracijamaAnionski tenzidi

Figure 8. Titracijske krivulje anionskih tenzida analitike istoe i tehnikih tenzida primjenom TG-TPB senzora i CPC kao titranta. (OS = n-octylsulfate; DES = decansulfonate; SAS = sec-alkansulfonate; DBS = dodecylbenzensulfonate; DS = dodecylsulfate; SS = diisooctylsulfosuccinate; LES = laurylethersulfate; TPB = tetraphenylborate).R. Matei-Pua, M. Sak-Bosnar, M. Bilic, B.S. Grabari, Sens. Actuators B, 106 (2005) 221-228.

Kationski tenzidi

Figure 9.Titracijske krivulje odabranih istih kationskih tenzida primjenom DMI-TPB tenzidnog senzora i NaDS kao titranta ( DMIC, CPC, CTAB, Hyamine 1622).

R. Matei-Pua, M. Sak-Bosnar, M. Bili, B.S. Grabari, Electroanalysis 16 (2004) 843-851.Indikatori zavrne toke u potenciometrijskim titracijama

Potenciometrijske titracije etoksiliranih neionskih tenzidaPotenciometrijske titracije se danas esto primjenjuju kao alternativa ostalim metodama za odreivanje neionskih tenzida. Zasnivaju se na sposobnosti polietera da stvaraju komplekse s velikim metalnim kationima, najee barijevim i olovnim, koji se zatim titriraju s natrijevim terafenilboratom. Za odreivanje zavrne toke titracije koristi se tenzidno-selektivna elektoda za neionske tenzide. Osim za odreivanje neionskih tenzida, primjena potenciometrijskih titracija je omoguila izuavanje mehanizama nastajanja kompleksa velikih metalnih kationa i etoksiliranih neionskih tenzida. Znaajno podruje primjene potenciometrijskih titracija u analizi neionskih tenzida predstavlja analiza otpadnih voda. Rezultati pokazuju zadovoljavajui nivo slaganja u odnosu na standardnu metodu (BiAS, Bismuth Active Substances) . Prednosti potencimetrijskih titracija u odnosu na standardnu metodu su mnogobrojne. Odreivanje je jednostavno za izvoenje, nije potrebna posebna priprema uzorka, a cijena je prihvatljiva.

Neionski tenzidiFigure 10. Titracijske krivulje odabranih neionskih tenzida primjenom NSE koristei 5 x 10-3 mol/L NaTPB kao titrant.

M. Sak-Bosnar, D. Madunic-Cacic, R. Matesic-Puac, Z. Grabaric, Anal. Chim. Acta, 581 (2007) 355-363.Indikatori zavrne toke u potenciometrijskim titracijama

6. Odreivanje tenzida u industrijskim proizvodima

6.1. Odreivanje anionskih tenzida u detergentskim proizvodima

Table 1. Rezultati potenciometrijske titracije tehnikih anionskih tenzida i komercijalnih proizvoda u usporedbi s titracijom u dvije faze.Fig. 2. Potenciometrijske titracijske krivulje i njihove prve derivacije tehnikih anionskih tenzida primjenom DDA-TPB senzora kao indikatora zavrne toke i CPC (c = 410-3 M) kao titranta.NaDBSNaDDSO. Galovi, M. Samardi, S. Petrui, M. Sak-Bosnar, Int. J. Electrochem. Sci. 9 (2014) 3802-3818.

Fig. 3. Titracijske krivulje tri komercijalna detergenta uz dodatak poznate koncentracije NaDDS

prakasti detergentgel detergenttekui detergent za runo pranje suaO. Galovi, M. Samardi, M. Sak-Bosnar, Int. J. Electrochem. Sci. 10 (2015) 5176-5193.

97 BF00.010.020.030.268000000000000020.477999999999999980.792000000000000041.10200000000000011.2941.41199999999999991.5441.66599999999999991.7861.86400000000000011.912.0122.02999999999999982.042.05399999999999982.082.15200000000000012.21200000000000022.3062.42799999999999992.58599999999999992.7743.0283.33400000000000013.72400000000000024.21400000000000044.80799999999999985.5166.2427.00600000000000027.8068.61200000000000019.428000000000000810452.9452.9453453.2461.7468.9480494505.8514.5525.9537.79999999999995551.9563.6570.1592.5600.79999999999995604.20000000000005608.29999999999995614.9637.20000000000005647.9660.1671.5683.1692.2701.4708.7714.4718.5720.7722.9724.3725725.6726726.5726.7116 BF + 2 mL DDS00.010.020.30.684000000000000050.766000000000000010.914000000000000031.0121.381.82200000000000012.24800000000000022.70400000000000023.14199999999999993.443.64599999999999993.783.88600000000000014.0244.06400000000000014.08800000000000014.11800000000000034.13199999999999974.14400000000000014.17400000000000044.18799999999999974.264.36200000000000014.47400000000000024.58600000000000034.71400000000000044.92600000000000025.18400000000000025.48200000000000025.82599999999999966.23200000000000026.767.34400000000000037.9928.67399999999999959.4210441.3441.2441.2450461.8465.5468.8471.2478486.9494.3502.9514.1524.79999999999995535.29999999999995544.5552.9569.29999999999995576.29999999999995581.6585589.29999999999995592.5596.70000000000005600.1611.9626.70000000000005642.79999999999995656.4664.4674.5684.3693.2700.8705.7710.4713.9716.9718.6720720.7122 BF + 5 mL DDS00.010.020.030.353999999999999980.841999999999999971.2781.7442.24000000000000022.76799999999999983.313.84200000000000014.37800000000000014.925.40800000000000045.73800000000000046.066.31599999999999986.646.927.07800000000000037.16399999999999977.18599999999999997.19800000000000047.21199999999999977.22400000000000027.24399999999999987.39599999999999997.53800000000000037.64599999999999997.75199999999999987.7827.91600000000000048.17399999999999958.47199999999999958.81600000000000079.24799999999999939.7310.22810.83799999999999911.49612.21599999999999912.96599999999999913.7514.55599999999999915442441.9442442446.8455.3461.9467.9473.9479.8486.2492.4498.4505.7515.5523.9534.5543555.1569.1580.4592.4600.20000000000005605.79999999999995610.20000000000005613.20000000000005615.1631.29999999999995653669679.4682.8689.1698.9707.8714.5721.1727.9731.7735.1737.3739740740.6741.2741.7146 Frosch 00.010.020.037.3999999999999996E-20.145999999999999990.701999999999999961.18599999999999991.5081.7521.87799999999999992.09600000000000012.332.47000000000000022.5362.56400000000000012.60800000000000012.662.81599999999999983.01799999999999983.19600000000000023.40600000000000013.68599999999999993.95400000000000024.31200000000000034.69800000000000045.09600000000000015.54600000000000036.016.53800000000000037.11800000000000037.7348.34399999999999948.98199999999999939.653999999999999910249.1248.9248.2247.9248.1248.8257.2267.7277.5289295.60000000000002307.39999999999998323336345.6348.6351.9356.8367.2383.2394.6403.4416423.5432.2441.1448.2455.7461.3466.1470.4475.1479482.2487.6490148 Frosch + 2 mL DDS00.010.020.030.3039999999999999911.632.20800000000000022.7023.15200000000000013.493.75199999999999983.9684.14799999999999974.36200000000000014.534.61000000000000034.714.79399999999999964.93799999999999975.15200000000000015.38199999999999975.635.92199999999999976.2586.63600000000000017.077.53800000000000038.04400000000000058.60599999999999999.19800000000000049.823999999999999810246.2245.9245.7245.6246.7251.4257.2264.2271.7281.2291301311.5321.2334.7349357364.9372.2381.1393.1404.6414.3423.4431.9439.2446.3452.6457.7462.5466.6470.1471.7155 Frosch + 5 mL DDS00.010.020.030.353999999999999981.0321.68599999999999992.33199999999999992.9723.614.21600000000000024.825.35400000000000015.83399999999999966.36.58600000000000036.88799999999999997.11599999999999977.32200000000000017.51799999999999987.547.55400000000000037.587.59600000000000017.72799999999999987.93400000000000028.12199999999999998.33200000000000078.57600000000000058.83799999999999929.11999999999999929.44800000000000049.837999999999999210.2410.71411.21211.72600000000000112.3112.93399999999999913.58799999999999914.26399999999999914.98199999999999915238238238.1238.1239.4243.3247.3251.4255.5260.3265.10000000000002271.3278.3285.60000000000002296.39999999999998304.60000000000002315.8326.2337.2361.1366.5369.1371.5373.3381.9397.1409419.8431.1442451.2459467.8474.2480.9487.4492496.1499.7502.9505.2507.7508.7161 Denk Mit00.010.020.030.506000000000000010.861999999999999991.19199999999999991.5381.882.09399999999999992.27199999999999982.522.65799999999999992.72800000000000022.7542.84200000000000012.91400000000000012.92600000000000022.9933.013.02199999999999983.0323.0443.08400000000000013.13600000000000013.213.32799999999999983.553.86200000000000014.214.63600000000000015.15399999999999995.75399999999999966.39400000000000017.07599999999999967.77799999999999968.5169.275999999999999810-108.1-108.4-108.5-108.4-95-84.1-74.5-64.099999999999994-50.7-40.1-31.2-15.5-3.29999999999999726.700000000000002810.70000000000000322.5999999999999944346.40000000000000685.69999999999998996.1108.69999999999999120.4128.4134.6149.69999999999999162.1172.2179.1186.9196.10000000000002203.10000000000002208.5212.7216.5219.5222.2224.10000000000002225.60000000000002227229.7166 Denk Mit + 2 mL DDS00.010.020.030.506000000000000010.936000000000000051.37799999999999991.7662.25599999999999982.70400000000000023.16400000000000013.48200000000000023.7824.10200000000000034.324.494.59400000000000034.68200000000000044.7264.794.85799999999999974.92400000000000044.94000000000000044.974.98200000000000024.99399999999999985.01199999999999965.0245.05799999999999985.11200000000000015.185.285.43200000000000045.64599999999999995.96199999999999976.31799999999999966.687.17.60799999999999978.16399999999999978.79199999999999989.445999999999999710-108.3-108.9-109-108.9-99.5-91.5-86.2-80.5-71.7-64.5-54.1-45.1-35.700000000000003-22.9-11.799999999999997-0.100000000000001429.09999999999999432026.4000000000000063749.567.872.90000000000000689.19999999999998997.699999999999989107118126.30000000000001138.80000000000001153.19999999999999164.6174.4183.8191.2200.10000000000002209.8217.3222.89999999999998228.2232235.60000000000002238.39999999999998240.3171 Denk Mit + 5 mL DDS00.010.020.030.268000000000000020.520.953999999999999961.44199999999999991.9742.5323.08800000000000013.64800000000000014.21199999999999974.74399999999999985.2665.7426.22400000000000026.66.927.18599999999999997.39400000000000017.49800000000000027.647.767.78599999999999967.817.87800000000000017.92799999999999997.967.98200000000000027.99800000000000028.018.03999999999999918.05000000000000078.08399999999999968.13199999999999978.20599999999999958.2988.44800000000000048.67600000000000028.97400000000000029.31799999999999969.589.884000000000000310.32410.81811.36211.96599999999999912.57600000000000113.24200000000000113.92800000000000114.62599999999999915-120.7-120.7-120.6-120.4-117-112.7-106.3-100.5-95-89.2-83.5-77.900000000000006-71.5-65-57.5-50.3-40.799999999999997-31.3-21-102.59.899999999999998621.939.09999999999999444.348.76375.785.995104.69999999999999112.30000000000001123.5130.1144.4156.19999999999999169.9179.1187.6196.2205.1221.1230.7236.39999999999998242.7248.2252.5257.10000000000002260.3263.3266.10000000000002268.5269.5Vt/mL

E/mV

SPMS microsensorPMS sensor*AS naeno (mol/L)NaDDSAs naeno (mol/L)NaDDSDodano (mol)Naeno (mol)Recovery (%)Dodano (mol)Naeno (mol)Recovery (%)Detergent typeGel detergent6.7110-4810-68.3110-6103.96.7110-4810-68.3410-6104.3210-52.0010-5100.0210-52.0010-5100.0Powdered detergent8.1510-4810-68.2310-6102.99.2010-4810-68.3410-6104.3210-52.0910-5104.5210-52.0410-5102.0Liquid hand-dishwashing detergent2.3910-3810-68.0010-6100.02.3210-3810-68.0810-6101.0210-52.0110-5100.5210-52.0110-5100.5

Table 2. Rezultati potenciometrijskih titracija komercijalnih detergenata uz poznati dodatak NaDDS primjenom SPMS tenzidnog mikrosenzora kao indikatora i CPC (c = 4 x 10-3 M) kao titranta usporeeni s rezultatima dobivenim s PMS senzorom.

Table 3. Rezultati potenciometrijskih titracija komercijalnih proizvoda primjenom SPMS tenzidnog mikrosenzora i PMS senzora kao indikatora usporeeni s rezultatima dobivenim titracijom u dvije faze.

IV INTERNATIONAL CONGRESS "Engineering, Environment and Materials in Processing Industry

6.2. Odreivanje kationskih tenzida u dezinficijensima i farmaceutskim proizvodima

Fig. 4. Potenciometrijske titracijske krivulje i njihove prve derivacije nekoliko otopina kationskih tenzida (c = 4 x 10-3 mol/L) s natrijevim tetrafenilboratom (NaTPB ()) i NaDDS () koristei DMI-TPB tenzidni senzor kao indikator. SURFACTANT USEDSURFACTANT CONTENT*DMI-TPB sensorCommercial sensorTwo-phase titration**found (%)RSD %) found (%)RSD (%) found (%)DDAC52.830.5151.500.7152.42ADBAC 150.030.9951.110.3150.87ADBAC 253.250.7953.670.4853.94 Hyamine 162298.360.5898.270.5498.59CTAB95.410.5495.680.5795.90CPC97.520.2497.360.2298.23

Table 4. Rezultati potenciometrijskih titracija nekoliko tehnikih kationskih tenzida koristei NaTPB (c = 5 x 10-3 M) kao titrant i DMI-TPB tenzidni senzor kao indikator, usporeeni s rezultatima dobivenim komercijalnim tenzidnim senzorom i standardnom titracijom u dvije faze. PRODUCTCATIONIC SURFACTANT CONTENT*DMI-TPB sensorCommercial sensorfound (%)RSD (%)found (%)RSD (%)Mouthwash A Mouthwash B Disinfectant for food industryDisinfectant for hospital use A0.05540.05844.33605.02300.990.940.960.340.05360.05644.36905.00401.020.970.890.12found (M)RSD (%)found (M)RSD (%)Disinfectant for hospital use BDisinfectant for hospital use C0.15100.003730.230.790.15050.003510.190.73

Table 5. Rezultati potenciometrijskih titracija est dezinficijenasa koristei NaTPB (c = 5 x 10-3 M) kao titrant i DMI-TPB tenzidni senzor kao indikator,u usporedbi s rezultatima dobivenim komercijalnim senzorom. D. Maduni-ai, M. Sak-Bosnar, O. Galovi, N. Saka, R. Matei-Pua, Talanta 76 (2008) 259-264.


Fig. 5. Titracijske krivulje i njihove prve derivacije smjese Tritona X-100 s razliitim kationskim tenzidima koristei NaTPB kao titrant i DMI-TPB senzor kao detektor zavrne toke ( DMIC + Triton X-100; CTAB + Triton X-100; Hyamine + Triton X-100; CPC + Triton X-100).SampleSurfactant contentCationic surfactant (%)Nonionic surfactant (%)DMI-TPB electrode*Two-phase titration**DMI-TPB electrode*Gravimetric method**Product A1.02 0.031.001.42 0.041.60Product B5.04 0.074.957.58 0.096.85Product C4.44 0.054.504.89 0.074.46

Table 6. Rezultati tri komercijalna tekua detergenta za ienje i dezinfekciju dobiveni potenciometrijskom titracijom koristei DMI-TPB senzor i NaTPB(5 103 M) kao titrant, u usporedbi s rezultatima dobivenim titracijom u dvije faze za kationske tenzide i gravimetrijskom metodom za neionske tenzide.M. Samardi, M. Sak-Bosnar, D. Maduni-ai, Talanta, 83 (2011) 789-794.

6.3. Odreivanje neionskih tenzida u detergentskim proizvodima

Fig. 6. Titracijske krivulje nekoliko komercijalnihdetergenata koristei tenzidni senzor za neionsketenzide (NSE) i NaTPB (c = 5 x 10-3 mol dm-3 ) kao titrant: heavy duty prakasti detergent (); tekui detergent zapranje rublja (); tekui color detergent ().UzorakSadraj tenzida*NSECommercial electrodeM naeno% naenoM naeno% naenoHeavy duty powder detergent3.57 0.052.61 0.044.02 0.12 2.68 0.08Liquid laundry detergent9.12 0.0412.88 0.059.75 0.3213.23 0.43Liquid color detergent9.15 0.1426.31 0.409.32 0.1626.39 0.44

Table 7. Rezultati potenciometrijskih titracija komercijalnih detergenata koristei NaTPB (c = 5 x 10-3 mol dm-3 ) kao titrant, NSE i komercijalnu tenzidnu elektrodu kao indikator.M. Sak-Bosnar, D. Madunic-Cacic, R. Matesic-Puac, Z. Grabaric, Anal. Chim. Acta 581 (2007) 355-363.

7. Odreivanje tenzida u industrijskim otpadnim vodama

7.1. Anionski tenzidi

Titracija industrijskih otpadnih vodapH uzoraka: 6 9 (bez podeavanja),Detekcija zavrne toke titracije: Savitzky-Golay-Barak metoda.

Fig. 11. Titracijske krivulje uzoraka industrijskih otpadnih voda i s poznatim dodatkom NaDDS (c = 110-3 M)M. Samardi, O. Galovi, S. Petrui, M. Sak-Bosnar, Int. J. Electrochem. Sci. 9 (2014) 6166-6181.

S100.010.020.030.2470.643000000000000020.846999999999999981.05499999999999991.23900000000000011.40450000000000011.51251.66151.75449999999999991.8651.93151.97752.0154999999999992.12250000000000012.26149999999999982.40850000000000012.5754999999999992.77700000000000012.99650000000000023.23349999999999983.52150000000000013.8374999999999994.14799999999999884.48700000000000014.85499999999999865.235.62549999999999886.02650000000000046.41650000000000016.81149999999999977.22649999999999977.64549999999999938.068.47050000000000138.88650000000000349.30450000000000279.71450000000000110753752.8752.6752.7753.3771.9780.8791.4802.2815.3824.1839.3849.9865.6877.9883.8888.9898.7910.3920.2928.2936.3943.7948.5952.6957.5960.8962.9964.9966967968.4969.6969.9970.1970.4970.9971.2971.4971.9972.1972.4S1 + 2 mL DDS00.010.020.030.200500000000000010.261500000000000010.56550.856999999999999981.1091.3831.6571.93799999999999912.21700000000000012.49900000000000012.78500000000000013.0354999999999993.30399999999999983.50950000000000013.70449999999999993.90850000000000014.09249999999999944.26149999999999984.44500000000000034.6334.86049999999999925.05199999999999965.09149999999999995.10799999999999885.15099999999999895.16649999999999925.32599999999999875.58655.79049999999999986.04199999999999986.30149999999999996.56849999999999936.87749999999999867.18049999999999947.51549999999999947.8654999999999998.22899999999999928.58350000000000088.95250000000000069.33200000000000079.722999999999997210.11700000000000110.47899999999999910.84800000000000111.24949999999999911.65349999999999912.06712.47450000000000112.880513.292513.70214.12449999999999914.533514.9495717.6717.6717.3716.8717.6718.6724.5731.7737.5743.8749.8756762767.8775.2781.3790.4799807.8818.4829.2838.4846.8853.8865.8886.7896.3899.5901.6902.7907919.2925.2932938.5942.7948951.4954.4956.8959.8962963.8965.1966.3969.1969.4970.3971.1971.4972.1972.8973.2973.8973.8974.4974.7975975.5S1 + 5 mL DDS00.010.020.030.303499999999999990.464500000000000020.8791.29451.7161.79750000000000012.03650000000000022.17750000000000022.46899999999999992.79300000000000013.10199999999999993.43550000000000023.76299999999999994.06649999999999964.37899999999999964.69449999999999885.01799999999999895.32299999999999865.59749999999999935.86749999999999886.12949999999999936.31949999999999976.52799999999999876.72699999999999946.86449999999999876.9156.98749999999999987.06199999999999947.14649999999999967.33800000000000017.537.73449999999999977.90800000000000048.03300000000000138.26050000000000048.568.81850000000000029.13699999999999879.47250000000000019.79300000000000110.12850000000000110.45250000000000110.853511.18911.59650000000000112.005512.415512.82900000000000113.239513.63414.03850000000000114.43950000000000114.85249999999999915736.3736.1736735.8735.9735.8736.1736.2750.9753.5755.4758.1761.9767770.6774.7780.2784.6789.1793.2798.6804.9811.4818.3828835.9845.5857.7872.4879.1886.6892.1896.6906.6915.6928.5935.6940.2944.2952.4956959.6964.2967.7972.1972.8977.3977.8978.4979979.4979.9981981.8982.7983.1983.3983.4S2 00.010.020.030.354499999999999980.691999999999999950.978999999999999981.26699999999999991.55099999999999991.81652.07350000000000012.30399999999999982.55100000000000022.72650000000000012.90600000000000013.08349999999999993.26949999999999993.4923.71099999999999993.96050000000000014.22900000000000014.52699999999999924.82699999999999915.14749999999999915.47700000000000035.80900000000000026.16249999999999886.53150000000000036.89399999999999927.25849999999999977.64149999999999978.01200000000000058.39750000000000268.78150000000000129.16200000000000089.54849999999999899.947999999999998610547547547.1547550.5556561.4567.4574.20000000000005581.29999999999995589.6596.5606.9615.79999999999995625.9634.6641.79999999999995650.79999999999995657.4663.5668.3673.6677.7681.5685.4688.2690.4693695.5697.1699.4700.9702.6704.4705.9706.9707.8708.3S2 + 2 mL DDS00.010.020.030.172999999999999990.585500000000000020.951.27699999999999991.61451.96049999999999992.29450000000000022.6332.96553.22250000000000013.5154999999999993.8094999999999994.09199999999999964.35799999999999884.544.77299999999999974.91600000000000045.04150000000000015.17100000000000035.37800000000000015.63900000000000025.92156.15299999999999876.47449999999999996.80499999999999887.13157.4527.80749999999999928.178.56800000000000148.97499999999999969.39650000000000329.729999999999998610541.6541.5541.29999999999995541.20000000000005541.4544.20000000000005548.79999999999995551.9555.20000000000005559.1562.6566.5572.9577.79999999999995583.29999999999995589.4596.20000000000005605.9611.5622.70000000000005632.1637.70000000000005642.5648653.6663.7666.8670.7674.8679.3681.9684.4685.4686686.1690.9693.2694.3S2 + 5 mL DDS00.010.020.030.286499999999999980.422999999999999990.772000000000000021.13351.48100000000000011.8352.19200000000000022.5594999999999992.91800000000000013.27300000000000013.63899999999999983.99650000000000024.35399999999999924.71049999999999975.0775.42550000000000045.77299999999999976.0856.39199999999999866.67900000000000036.97250000000000017.16899999999999877.41950000000000027.64549999999999937.81549999999999928.00650000000000088.19450000000000148.42800000000000088.68050000000000038.96750000000000119.28600000000000149.56100000000000359.888000000000003510.22300000000000110.51549999999999910.86250000000000111.24311.603511.98600000000000112.366512.777513.164513.555513.95214.309514.68615543.4543.4543.1542.9543.4544.6547.1550.4553.20000000000005556558.29999999999995561.1564.1566.1569571.79999999999995574.6576.79999999999995580.20000000000005583.4587.9592.79999999999995598.5604613617.9625.79999999999995635.79999999999995641.20000000000005649.1655.7662.5667.6671.6679682.4686.1692.5695.2696.8699.7701.3703.1703.5705.2706.5707.6710.1711.9713713.8S300.010.020.030.31550.591500000000000030.850500000000000031.11651.3971.67050000000000011.91450000000000012.16752.28949999999999992.47900000000000012.63350000000000022.79599999999999982.9483.08800000000000013.22900000000000013.35449999999999893.5329999999999993.72500000000000013.92450000000000014.10849999999999944.29250000000000044.47949999999999984.70849999999999994.95049999999999995.22849999999999865.50549999999999965.80199999999999966.09049999999999966.416.75399999999999877.0937.47200000000000047.81849999999999938.1985000000000018.5795000000000038.97850000000000049.37250000000000059.767000000000001210261.39999999999992261.7261.60000000000002261.7268.2275.8281.8287.39999999999992294301.8308.8321.5328339.9350.4362.4374.8386.9396.7404.2413.6423434.3444.8454.4461.2468.6474480.3485.4491.3495.3498.4502503.7507.2508.9510.7511.7512.9514.1514.5514.9S3 + 2 mL DDS00.010.020.030.232000000000000010.484999999999999990.743999999999999991.01251.28851.58400000000000011.8932.22400000000000022.53452.84350000000000013.13899999999999983.43199999999999913.67953.91800000000000014.10799999999999884.30100000000000024.44899999999999984.62349999999999914.77149999999999964.925.06149999999999975.20549999999999985.35149999999999975.48700000000000015.6459999999999995.82049999999999915.99399999999999986.2266.47799999999999986.71100000000000036.99249999999999977.25849999999999977.587.89249999999999928.21399999999999868.54500000000000178.91700000000000169.28899999999999979.6710259.89999999999992260.10000000000002260.2260.39999999999992264.39999999999992270.5276.89999999999992282.5287.60000000000002292.3295.89999999999992301.10000000000002306311.5317.10000000000002324.5331.9341.5350.3361.8371383.4394.8407.1419.2431.4444.5454.4464.4475.4481.6488.3497.2502.3509.4513517.79999999999995522525.9527.79999999999995529.9531.70000000000005532.6533.9S3 + 5 mL DDS00.010.020.030.212499999999999990.289499999999999980.537000000000000030.818500000000000011.0931.36349999999999991.65351.95100000000000012.25249999999999912.55900000000000022.87650000000000013.20400000000000023.55053.89150000000000024.24449999999999864.59499999999999894.93299999999999985.26249999999999935.58199999999999995.8879999999999996.18999999999999866.46199999999999976.71956.9649999999999997.17649999999999997.28500000000000017.46449999999999927.6074999999999997.6817.84049999999999967.99249999999999978.05899999999999938.11850000000000098.14899999999999918.24499999999999928.27150000000000148.36600000000000328.53099999999999888.758.95550000000000079.15100000000000169.37650000000000019.6345000000000019.851500000000003310.12110.39410.69549999999999911.01350000000000111.32649999999999911.65711.98412.32600000000000112.680513.04850000000000113.43513.81150000000000114.20700000000000114.619515255.3255.6256.10000000000002256.60000000000002259.8262.10000000000002267.39999999999992273.89999999999992280.60000000000002285.89999999999992291.2296.3301.2305.5309.5312.60000000000002316.10000000000002319322.10000000000002325.8329.9334.3339.3344.5350.9357.8365.3374.3386.9393.3400.7411.3416.6428.8445.5449.9458.1462.5468.6472.8479.3486496.1506.5513.9520.1530.79999999999995536.1542.4547.1551.4556.20000000000005559.9564.1567.29999999999995570.1572.4573.9575.9577577.4578.9579.9S400.010.020.037.6999999999999999E-20.12050.530499999999999970.8721.17951.46249999999999991.70351.96449999999999992.14950000000000022.35099999999999912.5442.70800000000000022.8014999999999992.9384999999999993.09350000000000013.28100000000000013.48749999999999983.70353.97400000000000024.26049999999999864.56099999999999914.88849999999999965.21100000000000035.55149999999999995.91249999999999966.26549999999999946.63156.97799999999999987.36299999999999877.75749999999999948.12399999999999888.51650000000000068.90400000000000359.29600000000000129.69050000000000011069.368.90000000000000668.868.368.40000000000000668.40000000000000672.59999999999999478.09999999999999484.191.598108116125.9137.1150.6157164.8173.3181.9190.5195.7201.2206.2209.9214.3217.6220.1223.1225.5228.9230.3231.5234.1235.3236.8238.1239.3240.7241.3S4 + 2 DDS00.010.020.030.204499999999999990.598999999999999980.94051.2581.56800000000000011.87949999999999992.1942.50199999999999982.80900000000000023.07799999999999983.3633.6364999999999993.894.12349999999999914.31999999999999944.42900000000000034.59049999999999964.67649999999999994.8064.93949999999999985.04849999999999985.2185.42349999999999985.64549999999999935.90200000000000016.1779999999999996.47850000000000046.77500000000000047.09149999999999997.42749999999999937.76399999999999938.118.48250000000000538.83900000000000049.2130000000000019.58450000000000029.96600000000000291051.651.451.251.251.755.860.665.570.274.879.884.791.296.8103.3110.6118.7128.1140.5147.80000000000001163171.4183.8193.9201.1208.8216.9223.1229233.8239.3243.5247250.7253.9255.9258.8260.8263264.7266.2266.7S4 + 5 DDS00.010.020.030.11350.145999999999999990.352499999999999980.68851.02299999999999991.37400000000000011.72352.08449999999999982.43000000000000022.77899999999999993.15399999999999993.51853.87749999999999914.22649999999999974.56299999999999884.91399999999999975.24449999999999865.57150000000000035.88156.17699999999999966.45699999999999996.72949999999999986.98749999999999987.16649999999999927.37349999999999997.56249999999999917.64999999999999867.74150000000000037.87249999999999967.99500000000000018.15199999999999928.32150000000000038.49400000000000158.67500000000000078.89050000000000129.169.45300000000000129.779000000000001710.117510.40710.68311.049511.40450000000000111.7712.13212.51549999999999912.8913.28550000000000113.677514.0514.43699999999999914.7985000000000011545.445.846.34747.749.251.455.258.161.363.867.370.372.274.877.59999999999999480.784.486.990.794.799.5104.9111117.4124.6134.5142.19999999999999152.4166.9175.5184.6195.9205.1215.4226.2236.3243.9249.1254.3258261.5268.2271.10000000000002272.89999999999992275.89999999999992278.2280.8282.39999999999992284.5285.60000000000002287289.2290.2292.39999999999992293.60000000000002293.89999999999992S500.010.020.030.271000000000000020.642000000000000020.975500000000000031.28150000000000011.55550000000000011.79699999999999992.02950000000000012.23450000000000022.44099999999999982.65499999999999982.75150000000000012.90953.02199999999999983.24549999999999983.47650000000000013.71953.99900000000000014.31249999999999914.64149999999999974.96349999999999985.35.65099999999999896.01699999999999866.38649999999999986.76349999999999967.15849999999999927.53399999999999987.91600000000000048.29658.69200000000000029.09700000000000139.48450000000000069.877500000000003110-141.6-141.9-141.9-142.1-140.69999999999999-136.4-131-124.6-117.2-109.5-100.3-91.5-82.800000000000011-68.300000000000011-61.400000000000013-53.8-49.5-41.400000000000013-34-28.699999999999989-24.5-20.699999999999989-16.300000000000011-12.7-9.8000000000000131-7.5-5.1999999999999886-3.3000000000000109-2.1999999999999882-9.9999999999994302E-21.59999999999999413.40000000000000614.55.30000000000000966.90000000000000578.09999999999999618.30000000000001318.8000000000000131S5 + 2 DDS00.010.020.030.363999999999999990.773000000000000021.11800000000000011.41850000000000011.74152.08550000000000012.42200000000000022.74849999999999993.04349999999999993.34200000000000013.63899999999999983.87950000000000024.134.3914.51749999999999924.72399999999999934.90650000000000035.10199999999999945.27500000000000045.52699999999999925.85349999999999866.1524999999999996.49600000000000046.81099999999999917.15299999999999877.4847.84249999999999948.14849999999999858.43758.79199999999999989.17750000000000029.57499999999999939.94700000000000110-151.5-151.6-151.5-151.5-151.1-147.1-142.1-139.6-136.5-132.69999999999999-128.6-123.2-118.1-112.6-105.1-98.2-91.9-79.900000000000006-74.099999999999994-63.400000000000013-54.100000000000009-47-42-38.799999999999997-33-30.099999999999991-25-21.800000000000011-17.800000000000011-15.30000000000001-9.4000000000000057-7.4000000000000057-5.0999999999999943-3.5999999999999939-2.5999999999999939-0.199999999999988990.51.0999999999999941S5 + 5 DDS00.010.020.030.346499999999999970.654499999999999971.02499999999999991.421.8192.20900000000000012.58449999999999982.96200000000000023.33449999999999893.70299999999999984.06249999999999914.42349999999999984.78855.13449999999999925.48350000000000035.81499999999999866.14049999999999946.44850000000000016.74950000000000037.02349999999999947.26100000000000017.47100000000000017.68399999999999937.90800000000000048.09650000000000078.30600000000000278.54950000000000018.80800000000000169.07450000000000059.39300000000000079.700000000000001110.056510.36849999999999910.74050000000000111.078511.44100000000000111.80150000000000112.19400000000000112.5512.91649999999999913.302513.675514.072514.488514.89415-148.80000000000001-148.80000000000001-148.80000000000001-148.9-148.1-146.30000000000001-145.19999999999999-144.19999999999999-142.69999999999999-140.80000000000001-138.80000000000001-136.69999999999999-134.4-131.6-129-126.6-123.4-120.3-116.3-112.2-107.3-102.1-95.7-88.1-79.7-71.2-63.2-52.900000000000013-45.2-38.600000000000009-31.900000000000009-25.400000000000009-21.699999999999989-16.599999999999991-14.1-8.6999999999999904-6.9000000000000057-2.9000000000000061-0.52.19999999999998823.30000000000001096.58.59999999999999619.511.712.71313.71414Vt/mL

E/mV

Table 10. Rezultati potenciometrijskih titracija industrijskih efluenata s dodatkom poznate koncentracije NaDDS koristei DDA-TPB tenzidni senzor kao indikator i CPC kao titrant.

Effluent uzorakIzraunato AS (M)*NaDDSDodano (mol)Naeno* (mol)Recovery (%)15.3010-4810-68.1610-6102.0210-51.9810-599.029.49 10-6210-72.2610-7113.0510-75.2710-7105.435.7010-4810-67.9410-699.3210-52.0010-5100.049.6710-5210-72.2910-7114.5510-75.1110-7102.255.5210-5210-72.0810-7104.0510-75.1410-7102.8

* Srednja vrijednost 5 odreivanja N-1

7.2. Neionski tenzidi

Titrant: DMICNS: octylphenol decaethylene glycol ether (Triton X-100), C14H22O(C2H4O)n (n=10), Mr=647

Senzor: DMI-TPB

octylphenol decaethylene glycol ether (Triton X-100)

Figure 12. Titracijske krivulje nekoliko industrijskih otpadnih voda (uzorci 1, 2 i 3) i sa dodanom poznatom koliinom neionskog tenzida (NS) koristei NIO tenzidnu elektrodu i NaTPB kao titrant (11=1+50 g, 12=1+100 g, 13=1+150 g, 21=2+100 g, 31=3+100 g).

M. Sak-Bosnar, D. Maduni-ai, R. Matei-Pua, Z. Grabari, Tenside Surf. Det. 44 (2007) 11-18.

Table 16. Rezultati potenciometrijskih titracija industrijskih otpadnih voda.Uzorakc(tenzida)*/MStandardna devijacija (N-1)10.0470.00620.1140.01230.0720.00740.0750.00550.0960.00560.1120.00670.1790.00680.1510.009

* Srednja vrijednost 5 odreivanja (izraunato kao koncentracija Tritona X-100)

8. Tenzidni senzori u analizi injektiranjem u protok (Flow-Injection Analysis (FIA))

Tenzidni senzori kao detektori u analizi injektiranjem u protok (FIA)Fig. 14. Shema SIA/FIA analizatora

80IV INTERNATIONAL CONGRESS "Engineering, Environment and Materials in Processing Industry

SIA/FIA analizator vlastite proizvodnje

Kontrola sustava pomou vlastitog softvera

Fig. 15. SIA/FIA analizator (vlastita proizvodnja)

Fig. 16. SIA signali za standardne otopine DDS : (A) 1x10-5 M, (B) 2,5x10-5 M, (C) 5x10-5 M, (D) 7,5x10-5 M, (E) 1x10-4 M, SIA signali za razliite efluente (F-H)

Table 17. Rezultati odreivanja koncentracije DDS u modelnim efluentima dobiveni SIA sustavom vlastite proizvodnje koristei DMI-TPB potenciometrijski detektor.AS dodano AS naeno Recovery AS dodano AS naeno Recovery AS dodano AS naeno Recovery (mg/L)(mg/L)(%)(mg/L)(mg/L)(%)(mg/L)(mg/L)(%)66,27104,51514,3295,53030,2910165,8196,91515,57103,83028,7695,965,8797,81514,2895,23032,43108,165,7395,61514,7398,23031,210465,9298,71515,91063028,5595,2Srednja vrijednost5,9298,6814,9699,7330,25100,82SD0,193,090,744,921,645,47CV (%)3,133,134,944,945,425,42CL (p = 0.95)0,162,710,654,311,444,79

9. Prednosti i ogranienja upotrebe tenzidno-selektivnih elektroda u odnosu na klasine metodePrimjena tenzidno-selektivnih elektroda prua uvjete neophodne za rad u modernim visoko-automatiziranim laboratorijima.

Prednosti upotrebe tenzidno-selektivnih elektroda su sljedea:

Rutinske analize mogu se automatizirati, ime se znaajno skrauje vrijeme analize.Analiza se moe prilagoditi zahtjevima koji se mogu usuglasiti sa standardima dobre laboratorijske prakse (good laboratory praxis, GLP).Pri analizi se koriste manje koliine reagenasa bez potrebe za primjenom toksinih otapala.Odreivanje zavrne toke titracije lieno je subjektivnih procjena pa je time i znatno pouzdanije.Iskljueni su problemi vezani za titraciju zamuenih ili obojenih uzoraka.Priprema uzorka obino je nepotrebna, osim ako je potrebno raditi s razrjeenjima, kada je zbog slabijeg odziva elektrode potrebno stvoriti to bolje uvjete. Podeavanje pH-vrijednosti otopine za titraciju obino je nepotrebno, osim u posebnim sluajevima.

Prednosti i ogranienja upotrebe tenzidno-selektivnih elektroda u odnosu na klasine metode

Ogranienja upotrebe tenzidno-selektivnih elektroda su sljedea:

ograniene mogunosti primjene direktne potenciometrije,postepeni gubitak odzivnih karakteristika elektrode (skraen vijek trajanja),ograniena selektivnost.

10. Trendovi razvojatenzidno-selektivnih senzora

a) Sinteza novih tipova senzorskih materijalab) Uvoenje novih nosaa (carrier)c) Uvoenje novih vodljivih supstrata: vodljivi polimeri i nanomaterijali (NM)Budui trendovi

a) Sinteza novih tipova senzorskih materijala

Vea selektivnost diferencijalna titracija smjese tenzida

Dizajniranjem anionskog i/ili kationskog dijela ionskog para (geometrija molekule, veliina hidrofobnog dijela, polarnostitd.) mogla bi se postii poveana selektivnost elektrode, ime bi se otvorila mogunost diferencijalne titracije smjese tenzida. Vea osjetljivost proirenje podruja linearnog odziva senzora sniavanje granice detekcije


b) Uvoenje novih nosaa senzoraUvoenjem novih nosaa senzora, npr. sol-gel materijalamogli bi se izbjei ili umanjiti nedostatci klasine polimernematrice.

Poboljanja obuhvaaju sljedee osobine:

poveanje kemijske inertnostipoveanje otpornosti prema bubrenjuobrada pri niskim temperaturamaprilagoena poroznostkemijsko vezivanje elektroaktivnih mjesta na nosa senzora, ime bi se produljio vijek trajanja senzora, sprijeilo ispiranje elektroaktivnih komponenata te smanjio drift signala.uvoenje elektriki-vodljivih polimera moglo bi se, pored poboljanja gore spomenutih osobina, poboljati i elektrine osobine senzora (smanjenje impedancije, uma itd.).

c) Uvoenje novih vodljivih supstrata: vodljivi polimeri i nanomaterijali (NM)

1) Ispitivanje nanomaterijala (NM) kao vodljivih supstrata (solid contacts) u razvoju potenciometrijskih tenzidnih senzora,

2) Ispitivanje NM kao supstrata za imobilizaciju elektroaktivnog materijala (ionofora),

3) Ispitivanje funkcionalnih NM kao potencijalnih senzorskih materijala.

- Za monitoring plinova kao CO2, O2, NH3, H2S

- Vrlo osjetljiv i selektivan za mjerene otopljene plinove

- Za monitoring okolia

- Za klinike i industrijske primjene11. PLINSKI SENZORI

Membrana propusna za plinove (teflon, polietilen) imobilizirana je na pH elektrodi ili ionsko-selektivnoj elektrodi (ISE)

Izmeu elektrode i membrane unesen je tanak film otopine elektrolita (fiksna koliina, ~0.1 M)

- Ugraena je referentna elektroda

Ciljani analit difundira kroz membranu i dolazi u ravnoteu s otopinom internog elektrolitaPLINSKI SENZORI

PLINSKI SENZORI- Mjereni plin podlijee kemijskoj reakciji, a rezultirajui ion detektira se ionsko-selektivnom elektrodom

- Odziv elektrode u direktnoj je relaciji s koncentracijom plina u uzorku

- Debljina membrane je ~ 0.01 0.10 mm

- Membrana je nepropusna za vodu i ione

PLINSKI SENZORICO2 Senzori

Sastoji se od pH elektrode prevuene membranom selektivnom na CO2 (silikon)

Elektrolit izmeu elektrode i membrane je otopina NaHCO3-NaCl

pH unutranje otopine opada kad CO2 difundira kroz membranu

- Unutarnja staklena elektroda mjeri promjene pH

Ukupni elektrodni potencijal odreen je koncentracijom CO2 u uzorku

PLINSKI SENZORICO2 Senzori

HCO3- otopinaCO2 + H2O H+ + HCO3-H+ sniava pH

pH staklena elektrodaMembrana (silikon)

PLINSKI SENZORINH3 Senzor

Sastoji se od pH elektrode prevuene membranom selektivnom na NH3 (teflon ili polietilen)

- Elektrolit izmeu elektrode i membrane je otopina NH4+-KCl

- NH3 prolazi kroz membranu i poveava pH

- Unutarnja staklena elektroda prati promjene pH

- Porast pH srazmjeran je koliini NH3 u uzorku

PLINSKI SENZORIOstali plinski senzori

NO2 i SO2- Koristi modificiranu pH elektrodu

H2S- Koristi S2- ISE ili modificiranu pH elektrodu

HF- Koristi F- ISE ili modificiranu pH elektrodumodificiranu pH elektrodu

PLINSKI SENZORISenzori za kisik

Temelje se na amperometrijskim mjerenjima (prethodni plinski senzori su potenciometrijski senzori)

Sastoji se od para elektroda (Ag anoda i Pt katoda) u otopini elektrolita

Elektrode su razdvojene plinsko-propusnom hidrofobnom membranom

- Membrana moe biti od teflona, silikonske gume, polietilena

PLINSKI SENZORISenzori za kisik

- Elektrolit je otopina KCl i pufera

- O2 difundira kroz membranu i biva elektrolitiki reduciran

- Mjeri se elektrolitika struja

12. Elektronski nos (The Electronic Nose)Olfaktorni sustav (njuh) funkcionira na principu da relativno mali broj neselektivnih receptora omoguava razlikovanje tisua razliitih mirisa.Elektronski nos sastoji se od niza kemijskih senzora (obino plinskih senzora) i algoritma za prepoznavanje ablona/mustri (kemometrija). Niz senzora njui pare uzorka i daje set mjerenja Prepoznava ablona (pattern- recogniser) usporeuje ablone mjerenja sa pohranjenim ablonama poznatih materijala.Plinski senzori imaju vrlo iroku selektivnost, koja je definitivna prednost u elektronskom nosu. Premda svaki senzor u nizu moe odgovarati na danu supstancu, ti su odgovori obino razliiti.

Digitalni mirisi!

Primjer

Niz od 8 senzora daje razliite ablone/mustre za svaki plin.Ako je niz dobro treniran, moe prepoznati pojedine plinove u smjesi (kemometrija).

WSC 3, Pushkinskie Gory, Russia, February 16-20, 2004 13. Elektronski jezik (Electronic tongue)Elektronski jezik je analitiki instrument koji obuhvata niz nespecifinih, slabo selektivnih kemijskih senzora s parcijalnom specifinosti (cross-sensitivity) za razliite komponente u otopini, i prikladnim kemometrijskim alatom (metoda prepoznavanja ablona/mustri i/ili multivarijatna kalibracija) za obradu podataka. Izuzetno je vano:Stabilnost ponaanja senzora,Poveana parcijalna specifinost (cross-sensitivity) ponovljiv odziv senzora na to vie supstanci,Ako je dobro konfiguriran i treniran (kalibriran), elektronski jezik sposoban je prepoznati kvalitativni i kvantitativni sastav viekomponentnih otopina.

to je elektronski jezik?

Stanica okusaNervne stanice

Supstance koje daju okus

Elektrini odzivi

Mozak

Osjeaj okusa

Bioloki sustav okusa Umjetni tekui sustav elektronski jezik

Odzivi senzora

Raunalo

Niz senzora

Prepoznavanje ablona/mustri

Y. Vlasov, A. Legin, A. Rudnitskaya, Anal. Bioanal. Chem. 2002, 373, 136.

SensorInput SignalOutput SignalSensor

Input Signal

Output Signal

dOxaanFRTEERe0ln+=CuCuaaFRTEE++=2ln201,Cua=++=2ln20CuaFRTEE002.303lnlognnMMRTRTEEaEanFnF++=+=+2.303RT0.059S,nFn==--=nAanFRTEEln0--=nAanEElog059.00S0lognMEESa+=+0lognAEESa-=-++=nManEElog059.00+Ha++=HaEElog059.00logpHH+=-+-=HapHlogpHEE-=059.00RTzFpotA,BKAB,aa+ABzzpotAA,BBAlogNB=1=+2.303RTEEaKazFABz,zEE00,0592logEEaz=Chart1593371

Consumption (%)

Sheet1Surfactant typeConsumption (%)Anionic surfactant (59)59Nonionic surfactant (33)33Cationic surfactant (7)7Amphoteric surfactant (1)1

Sheet1

Consumption (%)

Sheet2

Sheet3

SO3-Na+NCH3CH3CH3Cl-+O(CH2CH2O)8CH2CH2OH+NCH3CH3CH2COO-PlastifikatorPolimer (PVC)IonoforGrafikon166331

Uobiajeni sastav PVC membrane

List1Plastifikator66Polimer (PVC)33Ionofor1

List1000

Uobiajeni sastav PVC membrane

List2

List3

()0log-=-EESaAn()()+-=spKaCataAn()()-+=spKaAnaCat()0log+=-spKEESaCat()log+=+EconstSaCat0log=-spconstESK0log----=-TPBTPBTPBEESTPB22202log++++=+xxxxBaLBaLBaLEESBaL-6040140240-7,5-6,5-5,5-4,5-3,5-2,5-1,5log a (An-)E/mVChart2232.2222.7230.1219.7228.3216.5226.5212.1224.5208.1222.3204.3214.7197.7208.9192.3198.6182.3188.9173.8182.8163177.4154.8173.2148.3167.1142.6161.4133.9154.2128.5145.3121.8138.4113.7130.7105.3120.996.8111.688.1105.279.795.770.886.560.980.753.97443.565.836.461.129.35623.852.417.250.211.448.67.545.33.542.3-0.240.6-7.340-13.839.3-21.338.7-26.238.2-30.737.9-32.437.7-33.5-1.9237651065-34.2-1.8497129304-33.9-1.7426003962

DBSDDSlog a (An-)E/mV

DBS, DDS, TPB Response (2)DBSDDSTPBE/mVlog(ai)E/mVlog(ai)E/mVlog(ai)192.2-7.0670194989207.730.6190.1-6.7663407159232.7-7.097141615114.5-6.4953130813188.3-6.5905859975229.7-6.79625836126.1-6.1945763663186.5-6.4659761065226.5-6.6202998621-1.4-6.018750374184.5-6.3693899475222.1-6.4954866372-7.2-5.8940623608182.3-6.2905289512218.1-6.3986974962-13.1-5.7973937466175.7-6.0673431757214.3-6.3196338205-19.1-5.700393898168.9-5.9569222109207.7-6.1949232223-27.4-5.55234157.5-5.7667980349201-6.0974542731-36.5-5.4000528706148.9-5.5911456507192.3-5.924-48.4-5.2245295133142.8-5.4666218712183.8-5.7967002238-54.8-5.1000959399138.5-5.3701114465173-5.6208407342-59.7-5.0036509491134.5-5.2913188061166.7-5.4961108841-64.6-4.9249061763127.1-5.1671338513158.3-5.3993951235-70.3-4.80077989121.4-5.0709553134152.6-5.3203977267-76.4-4.7046252615114.2-4.9580802122143.9-5.1958046582-84.5-4.591741954105.3-4.8184788507138.5-5.0992195494-92.6-4.45204970698.4-4.6781574557131.8-4.9857370129-98.3-4.311500610991.6-4.5352846913123.7-4.8451287882-107.2-4.168182363582.8-4.3851239879115.3-4.7034079151-116.2-4.017202732571.6-4.2451336816106.8-4.5585542467-122.8-3.875967195965.2-4.099151498698.1-4.4054592785-131.4-3.727953652855.7-3.964504061489.7-4.2616211205-139-3.590468678746.5-3.826115446980.8-4.1099966973-147.3-3.447766115440.7-3.70091241970.9-3.9680529262-155.6-3.316918347934-3.575445469663.9-3.819170377-165.5-3.183431689125.8-3.471184500653.5-3.6807440951-173.2-3.070002230121.1-3.377955003346.4-3.5369074886-181.2-2.965947241816-3.299734528840.1-3.4118244878-185.6-2.876117988612.4-3.235858490134.2-3.293926903-190.3-2.800570168710.2-3.190526000827.2-3.1889100336-193.2-2.74548310198.6-3.146968898521.4-3.097551501-196.4-2.691178798417.5-3.028726831713.5-2.9586337753E/mVE/mV164.5156.1217.7148.6242.7142.8239.7136.9236.5130.9232.1122.6228.1113.5224.3101.6217.795.221190.3202.385.4193.879.718373.6176.765.5168.357.4162.651.7153.942.8148.533.8141.827.2133.718.6125.311116.82.7108.1-5.699.7-15.590.8-23.280.9-31.273.9-35.663.5-40.356.4-43.250.1-46.444.237.231.427.523.5

DBS, DDS, TPB Response (2)00

DBSDBS lowlog a(DBS)E/mVDMIC-TPB Electrode_DBS Response

DDS regr.SUMMARY OUTPUTRegression StatisticsMultiple R0.9996572337R Square0.999314585Adjusted R Square0.9992924748Standard Error1.9125737155Observations33ANOVAdfSSMSFSignificance FRegression1165328.099066781165328.09906678145197.07257169321.28877860033747E-50Residual31113.3960847343.6579382172Total32165441.495151515CoefficientsStandard Errort StatP-valueLower 95%Upper 95%Lower 95,0%Upper 95,0%Intercept-171.83511986671.2409430346-138.47140043637.51893205794107E-45-174.3660412836-169.3041984498-174.3660412836-169.3041984498X Variable 1-59.28847846010.2788785758-212.5960314111.28877860033758E-50-59.8572553826-58.7197015376-59.8572553826-58.7197015376RESIDUAL OUTPUTObservationPredicted YResidualsStandard Residuals1202.84635377781.45364622220.77220868752195.45245215882.24754784121.19394660283189.67366646542.62633353461.39516585324179.36611113962.93388886041.55854597335171.84241648981.95758351021.0399112046161.41597493061.58402506940.84146878467154.02093189880.77906810120.4138580268148.28680160890.01319839110.00701127429143.603166152-1.003166152-0.532903815110136.2162326945-2.3162326945-1.230433500111130.4898485495-1.9898485495-1.05705109912123.7616416308-1.9616416308-1.042066966513115.4251939306-1.7251939306-0.916460773314107.0227789986-1.7227789986-0.91517790861598.4346254001-1.6346254001-0.86834878771689.3578576725-1.2578576725-0.66820152491780.8299121438-1.1299121438-0.60023405991871.84033079-1.04033079-0.55264648421963.4247005745-2.5247005745-1.34117620042054.5976807667-0.6976807667-0.37062329262146.3905971302-2.8905971302-1.53554845882237.8627435877-1.4627435877-0.77704140722330.4467627857-1.1467627857-0.60918548972423.45679437140.34320562860.18231834132517.2305039699-0.0305039699-0.01620437642611.8139955778-0.4139955778-0.2199235116277.7334856581-0.2334856581-0.1240326916283.5777749917-0.0777749917-0.041315777829-0.1719949511-0.0280050489-0.014876894930-8.59448775371.29448775370.687660225731-16.31235623252.51235623251.334618615832-24.18054507642.88054507641.530208587833-30.86195183214.66195183212.4765308441

DBSDDSTPBlog a(An-)E/mV000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000

DDS regr.000000000000000000000000000000000

X Variable 1ResidualsX Variable 1 Residual Plot

DBS regr.SUMMARY OUTPUTRegression StatisticsMultiple R0.9996851315R Square0.9993703622Adjusted R Square0.9993417423Standard Error1.3291252529Observations24ANOVAdfSSMSFSignificance FRegression161686.501623368561686.501623368534918.72052651541.03733656431292E-36Residual2238.86462663151.7665739378Total2361725.36625CoefficientsStandard Errort StatP-valueLower 95%Upper 95%Lower 95,0%Upper 95,0%Intercept-133.275463471.4416854938-92.44420092995.38668142972193E-30-136.2653393969-130.285587543-136.2653393969-130.285587543X Variable 1-57.77057590660.3091558977-186.86551454591.03733656431277E-36-58.4117266848-57.1294251284-58.4117266848-57.1294251284RESIDUAL OUTPUTObservationPredicted YResidualsStandard Residuals1217.2384460128-2.5384460128-1.95278575972210.8593632825-1.9593632825-1.50730671323199.8757801413-1.2757801413-0.98143717854189.7282407458-0.8282407458-0.63715230745182.53443029080.26556970920.20429851326176.95896747670.44103252330.33927923887172.40707126360.79292873640.60998734558165.23283490841.86716509161.43638012539159.67654537921.72345462081.325825967610153.15568578191.04431421810.803374160211145.09083473040.20916526960.160907483512136.98438692971.41561307031.089008405613128.7305450471.9694549531.515070073314120.05567473470.84432526530.649525869915111.9683541147-0.3683541147-0.28336890616103.53487933361.66512066641.28095059311795.7562193398-0.0562193398-0.04324863541887.7614293822-1.2614293822-0.97039736991980.52837835270.17162164730.13202577772073.28008042910.71991957090.55382256672167.2568642098-1.4568642098-1.12074224482261.8709424556-0.7709424556-0.59307365272357.3521005997-1.3521005997-1.04014928172453.6619450581-1.2619450581-0.9707940712

YPredicted YX Variable 1YX Variable 1 Line Fit Plot-6.3196338205-6.3196338205-6.1949232223-6.1949232223-6.0974542731-6.0974542731-5.9236-5.9236-5.7967002238-5.7967002238-5.6208407342-5.6208407342-5.4961108841-5.4961108841-5.3993951235-5.3993951235-5.3203977267-5.3203977267-5.1958046582-5.1958046582-5.0992195494-5.0992195494-4.9857370129-4.9857370129-4.8451287882-4.8451287882-4.7034079151-4.7034079151-4.5585542467-4.5585542467-4.4054592785-4.4054592785-4.2616211205-4.2616211205-4.1099966973-4.1099966973-3.9680529262-3.9680529262-3.819170377-3.819170377-3.6807440951-3.6807440951-3.5369074886-3.5369074886-3.4118244878-3.4118244878-3.293926903-3.293926903-3.1889100336-3.1889100336-3.097551501-3.097551501-3.0287268317-3.0287268317-2.9586337753-2.9586337753-2.8953875926-2.8953875926-2.7533280724-2.7533280724-2.6231532276-2.6231532276-2.4904429769-2.4904429769-2.3777498039-2.3777498039204.30197.70192.30182.30173.801630154.80148.30142.60133.90128.50121.80113.70105.3096.8088.1079.7070.8060.9053.9043.5036.4029.3023.8017.2011.407.503.50-0.20-7.30-13.80-21.30-26.20

DBS regr.000000000000000000000000


DBS, DDS, TPB ResponseDBSDDSTPBE/mVlog(ai)E/mVlog(ai)E/mVlog(ai)192.2-7.0670194989207.730.6190.1-6.7663407159232.7-7.097141615114.5-6.4953130813188.3-6.5905859975229.7-6.79625836126.1-6.1945763663186.5-6.4659761065226.5-6.6202998621-1.4-6.018750374184.5-6.3693899475222.1-6.4954866372-7.2-5.8940623608182.3-6.2905289512218.1-6.3986974962-13.1-5.7973937466174.7-6.0673431757214.3-6.3196338205-19.1-5.700393898168.9-5.9569222109207.7-6.1949232223-27.4-5.55234158.6-5.7667980349202.3-6.0974542731-36.5-5.4000528706148.9-5.5911456507192.3-5.924-48.4-5.2245295133142.8-5.4666218712183.8-5.7967002238-54.8-5.1000959399137.4-5.3701114465173-5.6208407342-59.7-5.0036509491133.2-5.2913188061164.8-5.4961108841-64.6-4.9249061763127.1-5.1671338513158.3-5.3993951235-70.3-4.80077989121.4-5.0709553134152.6-5.3203977267-76.4-4.7046252615114.2-4.9580802122143.9-5.1958046582-84.5-4.591741954105.3-4.8184788507138.5-5.0992195494-92.6-4.45204970698.4-4.6781574557131.8-4.9857370129-98.3-4.311500610990.7-4.5352846913123.7-4.8451287882-107.2-4.168182363580.9-4.3851239879115.3-4.7034079151-116.2-4.017202732571.6-4.2451336816106.8-4.5585542467-122.8-3.875967195965.2-4.099151498698.1-4.4054592785-131.4-3.727953652855.7-3.964504061489.7-4.2616211205-139-3.590468678746.5-3.826115446980.8-4.1099966973-147.3-3.447766115440.7-3.70091241970.9-3.9680529262-155.6-3.316918347934-3.575445469663.9-3.819170377-165.5-3.183431689125.8-3.471184500653.5-3.6807440951-173.2-3.070002230121.1-3.377955003346.4-3.5369074886-181.2-2.965947241816-3.299734528839.3-3.4118244878-185.6-2.876117988612.4-3.235858490133.8-3.293926903-190.3-2.800570168710.2-3.190526000827.2-3.1889100336-193.2-2.74548310198.6-3.146968898521.4-3.097551501-196.4-2.69117879845.3-3.050462970917.5-3.02872683172.3-2.910292321313.5-2.95863377530.6-2.76357127629.8-2.89538759260-2.62746855042.7-2.7533280724-0.7-2.4864062932-3.8-2.6231532276-1.3-2.3572634628-11.3-2.4904429769-1.8-2.2257284498-16.2-2.3777498039-2.1-2.1141335554-20.7-2.2744351875-2.3-2.0119063263-22.4-2.1852963603-2.2-1.9237651065-23.5-2.1103661693-1.9-1.8497129304-24.2-2.0557505053-1.5-1.7426003962-23.9-2.0019278607E/mVlog(ai)E/mVlog(ai)E/mVlog(ai)232.2-7.0670194989197.7164.5230.1-6.7663407159222.7-7.0971416151156.1228.3-6.5905859975219.7-6.7962583612148.6226.5-6.4659761065216.5-6.6202998621142.8224.5-6.3693899475212.1-6.4954866372136.9222.3-6.2905289512208.1-6.3986974962130.9214.7-6.0673431757204.3-6.3196338205122.6208.9-5.9569222109197.7-6.1949232223113.5198.6-5.7667980349192.3-6.0974542731101.6188.9-5.5911456507182.3-5.92495.2182.8-5.4666218712173.8-5.796700223890.3177.4-5.3701114465163-5.620840734285.4173.2-5.2913188061154.8-5.496110884179.7167.1-5.1671338513148.3-5.399395123573.6161.4-5.0709553134142.6-5.320397726765.5154.2-4.9580802122133.9-5.195804658257.4145.3-4.8184788507128.5-5.099219549451.7138.4-4.6781574557121.8-4.985737012942.8130.7-4.5352846913113.7-4.845128788233.8120.9-4.3851239879105.3-4.703407915127.2111.6-4.245133681696.8-4.558554246718.6105.2-4.099151498688.1-4.40545927851195.7-3.964504061479.7-4.26162112052.786.5-3.826115446970.8-4.1099966973-5.680.7-3.70091241960.9-3.9680529262-15.574-3.575445469653.9-3.819170377-23.265.8-3.471184500643.5-3.6807440951-31.261.1-3.377955003336.4-3.5369074886-35.656-3.299734528829.3-3.4118244878-40.352.4-3.235858490123.8-3.293926903-43.250.2-3.190526000817.2-3.1889100336-46.448.6-3.146968898511.4-3.09755150115045.3-3.05046297097.5-3.028726831715042.3-2.91029232133.5-2.958633775315040.6-2.7635712762-0.2-2.895387592615040-2.6274685504-7.3-2.753328072415039.3-2.4864062932-13.8-2.623153227615038.7-2.3572634628-21.3-2.490442976915038.2-2.2257284498-26.2-2.377749803915037.9-2.1141335554-30.7-2.274435187515037.7-2.0119063263-32.4-2.1852963603150-33.5-2.1103661693150-34.2-2.0557505053150-33.9-2.0019278607

YPredicted YX Variable 1YX Variable 1 Line Fit Plot-6.0673431757-6.0673431757-5.9569222109-5.9569222109-5.7667980349-5.7667980349-5.5911456507-5.5911456507-5.4666218712-5.4666218712-5.3701114465-5.3701114465-5.2913188061-5.2913188061-5.1671338513-5.1671338513-5.0709553134-5.0709553134-4.9580802122-4.9580802122-4.8184788507-4.8184788507-4.6781574557-4.6781574557-4.5352846913-4.5352846913-4.3851239879-4.3851239879-4.2451336816-4.2451336816-4.0991514986-4.0991514986-3.9645040614-3.9645040614-3.8261154469-3.8261154469-3.700912419-3.700912419-3.5754454696-3.5754454696-3.4711845006-3.4711845006-3.3779550033-3.3779550033-3.2997345288-3.2997345288-3.2358584901-3.2358584901214.70208.90198.60188.90182.80177.40173.20167.10161.40154.20145.30138.40130.70120.90111.60105.2095.7086.5080.7074065.8061.1056052.40

DBS, DDS, TPB Response11

DBSDBS lowlog a(DBS)E/mVDMIC-TPB Electrode_DBS Response

DBSDDSTPBlog a(An-)E/mV00000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000DBSDDSlog a(An-)E/mV000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000-5050150250-6-5-4-3log a(Cat+)E/mVChart13268-164277.90.149.684.69.955.690.917.56196.423.465.6101.328.372.2108.434.778114.540.785.2121.647.494.4130.355.8103.5138.964.2113.7147.972.9123.3156.981.7130.3165.389.9136.9173.798.2142.4181.2101142.9188.7101.3142.6195.1101.1142.2201.2100.9142.3205.4100.5140.9205.4100.1140.3203.399.7140.8201.299.3140.719998.9141196.598.6

CPC in Na2SO4Hyamine in Na2SO4CTAB IN Na2SO4log a(Cat+)E/mV

SLOPE_CPC IN Na2SO4_9SUMMARY OUTPUTRegression StatisticsMultiple R0.9996233471R Square0.9992468362Adjusted R Square0.9991783667Standard Error0.8371481706Observations13ANOVAdfSSMSFSignificance FRegression110227.763320038210227.763320038214594.05586938641.56465045055594E-18Residual117.70898765410.7008170595Total1210235.4723076923CoefficientsStandard Errort StatP-valueLower 95%Upper 95%Lower 95,0%Upper 95,0%Intercept345.20078118152.3998395722143.84327401652.29662233891207E-19339.9187698998350.4827924633339.9187698998350.4827924633X Variable 159.78504668610.494885319120.80586024441.56465045055594E-1858.695811443660.874281928558.695811443660.8742819285RESIDUAL OUTPUTObservationPredicted YResidualsStandard Residuals114.94675152690.75324847310.9397886766222.4028737576-0.3028737576-0.3778797275328.1842754813-1.1842754813-1.4775585043432.90645728110.49354271890.6157674064540.3540522734-0.2540522734-0.3169677183646.1273361134-0.3273361134-0.408400128752.9104891014-0.2104891014-0.2626162297861.31474532110.08525467890.1063677986969.78515307130.11484692870.1432884991078.44237422951.15762577051.44430905561187.59158557061.00841442941.25814587871296.18698536580.31301463420.390531968313105.2469209066-1.6469209066-2.0547769753

SLOPE_CPC IN Na2SO4_90.7532484731-0.3028737576-1.18427548130.4935427189-0.2540522734-0.3273361134-0.21048910140.08525467890.11484692871.15762577051.00841442940.3130146342-1.6469209066


SLOPE_HYAMINE IN Na2SO4_19SUMMARY OUTPUTRegression StatisticsMultiple R0.998625804R Square0.9972534964Adjusted R Square0.9970818399Standard Error2.1859372562Observations18ANOVAdfSSMSFSignificance FRegression127760.082964104727760.08296410475809.58854955066.36606111551567E-22Residual1676.45314700644.7783216879Total1727836.5361111111CoefficientsStandard Errort StatP-valueLower 95%Upper 95%Lower 95,0%Upper 95,0%Intercept349.21151157943.3803139708103.30741895524.95494241925255E-24342.0455661273356.3774570316342.0455661273356.3774570316X Variable 156.80993709620.745335180176.2206569746.36606111551568E-2255.229897108658.389977083855.229897108658.3899770838RESIDUAL OUTPUTObservationPredicted YResidualsStandard Residuals135.3920585483-0.7920585483-0.3734943726242.477138487-1.577138487-0.7436979892347.9708377723-1.5708377723-0.7407268939452.4580275609-1.1580275609-0.5460666743559.535004606-1.135004606-0.5352102242665.0209899814-0.5209899814-0.245672276771.4665899420.1334100580.0629093721879.45262146060.84737853940.399580456987.50151258221.39848741780.65945526611095.72792063382.17207936621.02424173311104.42183574432.47816425571.168575739712112.58949887662.71050112341.278133944413121.19858085782.50141914221.179541556814129.25722839991.94277160010.916111897915137.70887139680.99112860320.467365646916145.5659360907-0.4659360907-0.219711671917153.7289024235-2.5289024235-1.192501269118160.8264446359-5.4264446359-2.5588342417

YPredicted YX Variable 1YX Variable 1 Line Fit Plot-5.5240239485-5.5240239485-5.3993084445-5.3993084445-5.3026053047-5.3026053047-5.223619303-5.223619303-5.0990464306-5.0990464306-5.0024790754-5.0024790754-4.8890200524-4.8890200524-4.7484454993-4.7484454993-4.6067644566-4.6067644566-4.4619586626-4.4619586626-4.3089235501-4.3089235501-4.1651518167-4.1651518167-4.013609984-4.01360998415.714.946751526922.122.40287375762728.184275481333.432.906457281140.140.354052273445.846.127336113452.752.910489101461.461.314745321169.969.785153071379.678.442374229588.687.591585570696.596.1869853658103.6105.2469209066

SLOPE_HYAMINE IN Na2SO4_19-0.7920585483-1.577138487-1.5708377723-1.1580275609-1.135004606-0.52098998140.1334100580.84737853941.39848741782.17207936622.47816425572.71050112342.50141914221.94277160010.9911286032-0.4659360907-2.5289024235-5.4264446359


SLOPE_CTAB IN Na2SO4_10SUMMARY OUTPUTRegression StatisticsMultiple R0.999951308R Square0.9999026185Adjusted R Square0.9998945033Standard Error0.3153053817Observations14ANOVAdfSSMSFSignificance FRegression112249.690561623912249.6905616239123214.6510191311.92393214856585E-25Residual121.19300980460.0994174837Total1312250.8835714286CoefficientsStandard Errort StatP-valueLower 95%Upper 95%Lower 95,0%Upper 95,0%Intercept333.86789848330.8202191658407.04718005943.25452234285541E-26332.0807944437335.6550025229332.0807944437335.6550025229X Variable 158.57931115360.1668833791351.01944535761.92393214856585E-2558.215703506758.942918800558.215703506758.9429188005RESIDUAL OUTPUTObservationPredicted YResidualsStandard Residuals1-0.02634849230.12634849230.417080354210.2743807855-0.3743807855-1.2358427692317.5801291016-0.0801291016-0.264508689423.24493241360.15506758640.5118829886527.87187798460.42812201541.4132442624635.1692710383-0.4692710383-1.5490784834740.8261201868-0.1261201868-0.4163267106847.4724715993-0.0724715993-0.2392310327955.70723208530.09276791470.30622980931064.00680996810.19319003190.63772638231172.48943363510.41056636491.35529250681281.45412510340.24587489660.81164078091389.87617421110.02382578890.078649681498.7533903796-0.5533903796-1.8267590795

YPredicted YX Variable 1YX Variable 1 Line Fit Plot-5.5240239485-5.5240239485-5.3993084445-5.3993084445-5.3026053047-5.3026053047-5.223619303-5.223619303-5.0990464306-5.0990464306-5.0024790754-5.0024790754-4.8890200524-4.8890200524-4.7484454993-4.7484454993-4.6067644566-4.6067644566-4.4619586626-4.4619586626-4.3089235501-4.3089235501-4.1651518167-4.1651518167-4.013609984-4.013609984-3.8717572034-3.8717572034-3.722986699-3.722986699-3.5846822915-3.5846822915-3.4409932337-3.4409932337-3.3160583618-3.316058361834.635.392058548340.942.47713848746.447.970837772351.352.458027560958.459.53500460664.565.020989981471.671.46658994280.379.452621460688.987.501512582297.995.7279206338106.9104.4218357443115.3112.5894988766123.7121.1985808578131.2129.2572283999138.7137.7088713968145.1145.5659360907151.2153.7289024235155.4160.8264446359

SLOPE_CTAB IN Na2SO4_100.1263484923-0.3743807855-0.08012910160.15506758640.4281220154-0.4692710383-0.1261201868-0.07247159930.09276791470.19319003190.41056636490.24587489660.0238257889-0.5533903796


FIGURES_WITH RAW DATACPCHYAMINECTABWATERlog(ai)7H23mV7G237G25009OO4019010in Na2SO$-15.914.113.733.718.968.9-22.7-6.0005981853-4.625.412321868-16-5.69986639315.635.6224227.977.90.1-5.524023948515.745.729.649.634.684.69.9-5.399308444522.152.135.655.640.990.917.5-5.30260530472757416146.496.423.4-5.22361930333.463.445.665.651.3101.328.3-5.099046430640.170.152.272.258.4108.434.7-5.002479075445.875.8587864.5114.540.7-4.889020052452.782.765.285.271.6121.647.4-4.748445499361.491.474.494.480.3130.355.8-4.606764456669.999.983.5103.588.9138.964.2-4.461958662679.6109.693.7113.797.9147.972.9-4.308923550188.6118.6103.3123.3106.9156.981.7-4.165151816796.5126.5110.3130.3115.3165.389.9-4.013609984103.6133.6116.9136.9123.7173.798.2-3.8717572034112142122.4142.4131.2181.2101-3.722986699118148122.9142.9138.7188.7101.3-3.5846822915125155122.6142.6145.1195.1101.1-3.4409932337132162122.2142.2151.2201.2100.9-3.3160583618137167122.3142.3155.4205.4100.5-3.1983194966142172120.9140.9155.4205.4100.1-3.0934613842145.4175.4120.3140.3153.3203.399.7-3.0022555794144.6174.6123.8140.8151.2201.299.3-2.933555653143.8173.8120.7140.714919998.9-2.8635987453141.8171.8126141146.5196.598.6CPC9RESPONSE IN WATER4IN Na2SO4Jedino kod CPC-a opravdano je prikazati response u vodiKod Hyamine i CTAB-a slope u vodi je nii od 50PRIKAZANI SU ODZIVI U OTOPINI Na2SO4

YPredicted YX Variable 1YX Variable 1 Line Fit Plot-5.6998663931-5.6998663931-5.5240239485-5.5240239485-5.3993084445-5.3993084445-5.3026053047-5.3026053047-5.223619303-5.223619303-5.0990464306-5.0990464306-5.0024790754-5.0024790754-4.8890200524-4.8890200524-4.7484454993-4.7484454993-4.6067644566-4.6067644566-4.4619586626-4.4619586626-4.3089235501-4.3089235501-4.1651518167-4.1651518167-4.013609984-4.0136099840.1-0.02634849239.910.274380785517.517.580129101623.423.244932413628.327.871877984634.735.169271038340.740.826120186847.447.472471599355.855.707232085364.264.006809968172.972.489433635181.781.454125103489.989.876174211198.298.7533903796

FIGURES_WITH RAW DATA0000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000

CPC in Na2SO4Hyamine in Na2SO4CTAB IN Na2SO4log a(Cat+)E/mVCationic Response

FIG. BLACK-WHITE_RSP IN WATER

CTAB IN Na2SO4CTAB IN WATERlog a(Cat+)E/mVCationic Response in Water and Salt0000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000

FIG. BLACK-WHITE_RSP IN WATER-1625.40.135.69.945.717.552.123.45728.363.434.770.140.775.847.482.755.891.464.299.972.9109.681.7118.689.9126.598.2133.6101142101.3148101.1155100.9162100.5167100.117299.7175.499.3174.698.9173.898.6171.8

CTAB IN Na2SO4CTAB IN WATERlog a(Cat+)E/mV

FIG. BLACK-WHITE_RSP IN Na2SO4

FIG. BLACK-WHITE_RSP IN Na2SO43268-164277.90.149.684.69.955.690.917.56196.423.465.6101.328.372.2108.434.778114.540.785.2121.647.494.4130.355.8103.5138.964.2113.7147.972.9123.3156.981.7130.3165.389.9136.9173.798.2142.4181.2101142.9188.7101.3142.6195.1101.1142.2201.2100.9142.3205.4100.5140.9205.4100.1140.3203.399.7140.8201.299.3140.719998.9141196.598.6

CPC in Na2SO4Hyamine in Na2SO4CTAB IN Na2SO4log a(Cat+)E/mV

-10001002000100200300400Vrijeme/sE/mV110-6mol/L 110-5 mol/L 110-4 mol/L 110-3 mol/L 110-6mol/L 110-5mol/L 110-4 mol/L 110-3 mol/L DSDBSChart212012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024012024090.82408824086.421085.120484.3200.483.5197.583195.682.4194.282.1193.281.8192.281.4191.481.2190.881190.380.7189.880.5189.380.5188.880.2188.580.2188.28018879.9187.779.9187.579.7187.279.718779.6186.979.4186.679.5186.579.3186.479.3186.279.3186.179.118679.2185.979.1185.779185.779.1185.678.9185.578.9185.478.9185.378.8185.378.9185.278.7185.278.7185.178.818578.7184.978.6184.978.6184.978.7184.878.5184.878.6184.744.1184.630.4136.226132.424.3130.223.5129.122.8128.322.4127.622.1127.222126.921.8126.721.6126.421.6126.221.412621.312621.3125.821.2125.721.1125.521125.521.1125.421125.420.8125.220.9125.221125.220.812520.7125.120.812520.8124.920.7124.920.7124.920.7124.720.6124.820.7124.720.6124.720.6124.620.6124.620.6124.520.5124.420.5124.420.6124.420.5124.420.5124.420.6124.320.5124.320.6124.320.4124.220.5124.220.5124.220.4124.120.6124.120.4124.220.5124.120.4124.120.5124.110124.1-35.882.7-37.170.5-37.469.2-37.768.8-37.868.5-3868.3-3868.2-38.268-38.168-38.267.9-38.267.8-38.267.3-38.367.1-38.267.1-38.367-38.266.9-38.366.9-38.466.7-38.366.7-38.266.7-38.466.5-38.366.5-38.366.4-38.366.3-38.266.3-38.466.3-38.366.2-38.266.1-38.366.1-38.366-38.466-38.365.9-38.265.9-38.365.9-38.265.8-38.365.8-38.365.8-38.265.8-38.365.7-38.365.7-38.265.7-38.265.7-38.365.7-38.265.7-38.165.7-38.265.7-38.165.7-38.113.8-38.29.6-38.28.5-91.87.9-93.27.5-93.57.3-93.77.2-93.97-93.96.9-946.8-94.16.7-94.16.7-946.6-94.16.5-94.16.5-946.4-94.26.4-946.5-94.26.5-94.16.5-94.16.4-94.16.4-946.5-94.16.5-946.4-94.16.4-946.5-94.16.5-946.4-946.4-93.96.4-946.44166.4418416420418422420424422426424428426430428432430434432436434438436440438442440444442446444448446450448452450454452456454458456458

110-6mol/L110-5 mol/L110-4 mol/L110-3 mol/L110-6mol/L110-5mol/L110-4 mol/L110-3 mol/LDSDBSVrijeme/sE/mV

Figure X02400239.312029024022402239.312029024042404239.312029024062406239.312029024082408239.31202902401024010239.31202902401224012239.31202902401424014239.31202902401624016239.31202902401824018239.31202902402024020239.31202902402224022239.31202902402424024239.31202902402624026239.31202902402824028239.31202902403024030239.31202902403224032239.31202902403424034239.31202902403624036239.31202902403824038239.31202902404024040239.31202902404224042239.31202902404424044239.31202902404624046239.31202902404824048239.31202902405024050239.31202902405224052239.31202902405424054235.890.82902405621056233882602105820458231.486.425420460200.460230.185.1250.4200.462197.562229.384.3247.5197.564195.664228.583.5245.6195.666194.26622883244.2194.2The dynamic response of the sensor was also evaluated.68193.268227.482.4243.2193.270192.270227.182.1242.2192.2As shown in Fig XY, the sensor reached about 95% of its equilibrium response within 30 s in the concentration range of 9_10_8 to 7.94_10_5 M.72191.472226.881.8241.4191.4At higher concentrations (>7.4_10_4 M), 95% of the sensors equilibrium response was reached after 10 s.74190.874226.481.4240.8190.8The lifetime of the sensor is at least 2 months with 97% reproducibility.76190.376226.281.2240.3190.378189.87822681239.8189.885.890.880189.380225.780.7239.3189.3838882188.882225.580.5238.8188.881.486.484188.584225.580.5238.5188.580.185.186188.286225.280.2238.2188.279.384.38818888225.280.223818878.583.590187.79022580237.7187.7788392187.592224.979.9237.5187.577.482.494187.294224.979.9237.2187.277.182.19618796224.779.723718776.881.898186.998224.779.7236.9186.976.481.4100186.6100224.679.6236.6186.676.281.2102186.5102224.479.4236.5186.57681104186.4104224.579.5236.4186.475.780.7106186.2106224.379.3236.2186.275.580.5108186.1108224.379.3236.1186.175.580.5110186110224.379.323618675.280.2112185.9112224.179.1235.9185.975.280.2114185.7114224.279.2235.7185.77580116185.7116224.179.1235.7185.774.979.9118185.611822479235.6185.674.979.9120185.5120224.179.1235.5185.574.779.7122185.4122223.978.9235.4185.474.779.7124185.3124223.978.9235.3185.374.679.6126185.3126223.978.9235.3185.374.479.4128185.2128223.878.8235.2185.274.579.5130185.2130223.978.9235.2185.274.379.3132185.1132223.778.7235.1185.174.379.3134185134223.778.723518574.379.3136184.9136223.878.8234.9184.974.179.1138184.9138223.778.7234.9184.974.279.2140184.9140223.678.6234.9184.974.179.1142184.8142223.678.6234.8184.87479144184.8144223.778.7234.8184.874.179.1146184.7146223.578.5234.7184.773.978.9148184.6148223.678.6234.6184.673.978.9150136.2150194.144.1186.2136.273.978.9152132.4152180.430.4182.4132.473.878.8154130.215417626180.2130.273.978.9156129.1156174.324.3179.1129.173.778.7158128.3158173.523.5178.3128.373.778.7160127.6160172.822.8177.6127.673.878.8162127.2162172.422.4177.2127.273.778.7164126.9164172.122.1176.9126.973.678.6166126.716617222176.7126.773.678.6168126.4168171.821.8176.4126.473.778.7170126.

Senzori u industriji i zaštiti okoliša

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