pH Measurement Elements

Hanna Instruments R&D Baciu

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Definition of pH
- pH is a measure of relative amount of hydrogen
and hydroxide ions in a aqueous solution:

H2O --->H + OH
concentration

- is another way of expressing the hydrogen ion

pH = -log H !
- is really a measure of ion activity
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Principle of measurement
"erst #quation:

E = Eind - Eref = E - 2.3 !R " # $ n$ lo% aH&

where:
# #' ) 3 4 - measured voltage %m&$ - reference potential including other sta(le and fixed potentials - gas constant %*+,-.. /012mol$ - a(solute temperature %1$ - 4araday5s 6onstant %78.*9 6$

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Measurement setup

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Measurin% electrode
3he essential element of the glass electrode is a pH sensitive glass mem(rane: ;n electrical potential develops at glass liquid interfaces:

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Reference electrode

3he reference electrode supplies a constant potential value against which we measure the potential of the pH electrode:

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"'pes of electrodes
<epending on the constructing criteria pH electrodes are: (in%le %half cell$ )om*ined

sin%le +unction electrodes dou*le +unction electrodes

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"'pes of electrodes

(in%le +unction electrode

Dou*le +unction electrode

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"'pes of electrodes

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= =

Reference electrode
)alomel electrode: consists of a pool mercury with its surface completely covered with mercurous chloride> (il,er - (il,er ).loride %;g = ;g6l$: formed (y electolytic deposition of silver chloride on a silver wire> ".alamid electrode/ is essentially a metal in contact with a saturated solution of its chloride salt %thallous chloride$> Mercur' - Mercurous sulp.ate: is exactly li?e a calomel electrode (ut is covered with solid mercurous sulphate:

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Ho0 does t.e measurement ta1e place2

- in acidic solution the H+ diffuse in+ and a positive charge is esta(lished on the outer side of gel layer - in al1aline solution the H+ diffuse out+ and a negative charge is esta(lished on the outer side of gel layer

".e total mem*rane potential is a result of t.e difference *et0een t.e inner and outer c.ar%e.
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3imitation of pH electrodes

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4l1aline error

High concentrations of sodium ions interfere with readings in al?aline solutions: 3he pH at which the interference starts to (e significant depends upon the composition of the glass: 3his interference is called al?aline error and causes the pH to (e underestimated: Hanna@s glass formulations have the indicated characteristics:

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"'pical Electrode 3ife

;m(ient 3emperature - = , years 7' A6 %-7. A4$ Bess than . months -2' A6 %2.* A4$ Bess than - month

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Elements t.at compete in pH measurement

"emperature effect pH value changes with temperature 3he slope of the electrode changes with the temperature Interference Effect

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Isopotential pH
4requently+ the cali(ration temperature and the process temperature are different: 3herefore+ the cali(ration slope which depends on temperature+ is not appropriate to the sample: Definition: the isopotential pH is the pH at which the cell voltage does not change when the temperature changes:

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(olutions used for pH measurement

$illin% solution: is a solution containing the anion to which the reference electrode of the operational pH cell is reversi(le+ eg: 6hloride for ;g- ;g6l electrode: (tora%e solution/ is the solution which is in the protective cap in which is always ?eep the glass (ul( and the Cunction of the pH electrode: )leanin% solution/ is the solution used for cleaning the glass (ul( of the electrode once a day at least once a wee? to prevent Cunction clogging and to maintain the accuracy: )onditionin% solution/ is the solution in which the electrode must (e immerse to activate the glass selective mem(rane:
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Buffer solutions

;re formed most usually from a 0ea1 acid and his salt formed 0it. a stron% *ase. #D: 6H,6OOH06H,6OO"a 3he main characteristic of (uffers is the *ufferin% capacit'.

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pH *uffer temperature dependence

3emperature has an effect on pH: 3he cali(ration (uffer solutions are affected (y temperature changes to a lower degree than normal solutions: <uring cali(ration the instrument will automatically cali(rate to the pH value corresponding to the measured or set temperature:
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)ali*ration
WHY...?

pH cells are not perfect: 3herefore t.e' must *e cali*rated: )ali*ration tries to compensate any deviation from ideal (ehavior )ali*ration is made with solutions having exactly the ?nown pH: ".e cali*ration process is generally performed (y measuring in two different (uffer solutions:
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(teps for t.e )ali*ration Process

Measurin% solutions

Rinsin% solutions

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)ali*ration Pro*lems
6ontamination of (uffer solutions #lectrode internal elements degradation #lectrode aging

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)ontamination of *uffer solutions

#xpiration date )oom temperature Esed (uffer <O "O3 return to stoc? (ottle #xposure to air 6lean the electrode (efore inserting in (uffer

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Electrode internal elements de%radation

Biquid Cunctions with fi(ers or ceramic pins = (loc?ed due to

crystalliFation precipitation

3rapped air (u((les

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Electrode 4%in%
G 3he sum of internal elements degradation and effects of all external physico-chemical actions %temperature+ pressure+ interference+ etc$: G Hroper clean of electrode = oil solutions G #lectrode slope+ offset+ response time+ quality of glass change over time

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)al ).ec1
Most users *elie,e t.at if t.e' cali*rate often9 t.e' 0ill %et accurate readin%s.

3his is only true in certain cases+ for example:

6ontaminated (uffers o(viously lead to (ad readings

Enconditioned or dirty electrodes also lead to (ad readings as the performance of the electrode will change after cali(ration

)ali*ration ).ec1"M is the Hanna name for a class of techniques for automatically detecting these pro(lems and improving the accuracy of pH measurements

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)al ).ec1
pH Electrode 4%in% E:periment

Ie have done experiments ?eeping electrodes for over . months in: milk, juice, pH 1, pH 13, oil

6onclusions of experiments:

3he actual electrode slope and offset c.an%e slo0l' over time If not properl' cleaned+ the slope and offset can change dramatically over time even over a short period of time It is ,er' difficult to clean the electrodes properly %particularly for the oil solution$+ and to tell whether the electrodes have (een cleaned sufficiently

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)al ).ec1
pH )leanin% electrode e:periment

Jtart with , new+ conditioned electrodes <irty 2 electrodes with solution containing oil 6lean electrodes in different way with standard cleaning solution %to simulate user cleaning electrodes$ 6ondition electrodes 6ali(rate in pH K and pH -' Beave electrodes in pH -' and log the readings

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)al ).ec1
pH )leanin% electrode e:periment
-':,' -':29 pH Readin% -':2' -':-9 -':-' -':'9 -':'' ' ':9 -:9 "ime !.ours; 2 2:9 ,

Lmmediately after cali(ration

3est 2 3est 6lean

all electrodes measure accurately 3he dirty electrodes get cleaned with time and approach the real offset and slope However the cali(ration continues to compensate for the dirty parameters+ quic?ly leading to errors

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)al ).ec1
Most important point/ point #ven if the user thin?s he is doing a good Co( during cali(ration+ normal meters give no warnings when the cali(ration can (e (ad as the cali(ration parameters have changed more than expected

)ali*ration ).ec1 features can significantly improve the accuracy of pH readings (y alerting the user that something can (e wrong

;pplication-specific cleaning solutions need to (e used to clean electrodes properly

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4pplications
3ess common applications/
G G G G G G G Melatin and glue manufacturing /am and Celly manufacturing #lectrical equipments Beather Hrinting 3ropical fish (reeding Herfume industry

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pH meter features

Neasured parameters: pH+ m&+ )elative m&+ LJ# and temperature> Nanual selection+ automatic and semiautomatic pH cali(ration in up to five points and custom (uffers %up to 9 custom (uffers$> Nanual Jelection and 6ustom Jtandard LJ# cali(ration in up to five points+ with standard %up to five standard solutions for each measurement unit$ and custom solutions %up to 9 custom solutions$+ with or without temperature compensation> ;utoHold feature to freeFe first sta(le reading on the B6<>
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pH meter features

3wo selecta(le alarm limits %for pH+ m&+ LJ#$> 3hree selecta(le logging modes: ;utomatic+ Nanual+ ;utoHold logging> Ep to -'' logging lots for automatic or manual modes and up to -'' LJ# methods reports> Jelecta(le area and sampling period feature for automatic logging> MBH feature

Operator L< = this option allows you to edit the name of the operator: Lnstrument L< = this option allows you to edit an identification name0num(er for the instrument: 6ompany "ame = this option allows you to edit the company name: ;dditional Lnfo - O ;dditional Lnfo 2 = for general purpose notations:
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pH meter features

Hrofile 3emperature compensation: ;36+ N36 Jta(ility 6riteria: 4ast Nedium ;ccurate Online and offline graph> Opto-isolated H6 interface via )J2,2+ respectively EJP:

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Thank you for your attention!!!

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