pH

pH is one of the most often calculated and measured properties of solutions, products and substances.
When in 1936 Arnold Beckman was readyin his first commercial pH meter, total lobal demand for
such a de!ice was estimated for 6"" pH meters o!er 1" years before the market saturation. #ear later
lobal demand had to be ree!aluated, as first year sales reached $$$ pH meters %see pH meter history&'
pH is so important as it can drastically chane e(uilibrium state and speed of many reactions. )any
plants tolerate only narrow pH rane of the soil. *mall chane in the pH of blood can be fatal for any
animal. +recise control of pH is !ital for ood yield in many industrial processes , and so on.
-heck out pH definition and pH scale articles for more information on pH, and .ernst e(uation article
for the basic e/planation of how , and why , the pH meter works.
pH definition
pH describes amount of H
0
cations in solution. -oncentration of these ions can chane in !ery wide
rane , most often it has !alues lyin somewhere between 1) and 1"
,1$
), althouh sometimes e!en
hiher and lower concentrations can be obser!ed.
1sin numbers differin by many orders of manitude is impractical, thus in 19"9 2anish biochemist
*3ren *3rensen de!eloped the pH scale and introduced pH definition , minus loarithm base 1" of
4H
0
56
While pH defined this way can be usefull when doin simple pH calculation for diluted solutions of
acids and bases, it is not correct in eneral. Beha!ior of the ions in the solution depends not on their
concentrations, but on acti!ities. 7n case of !ery diluted solutions %say below ".""1)& difference
between concentration and acti!ity can be nelected. 7n case of more concentrated solutions , it ha!e
to be taken into account. 8hus in reality more precise definition is used6
and is sometimes called 9thermodynamic pH9 as opposed to 9concentration pH9. What is important is the
fact, that all pH meters measure thermodynamic pH !alues, as present in the .ernst e(uation.
:or more information see pH definition lecture %and other lectures on pH& at -hemBuddy , chemical
calculators site.
pH scale
pH definition automatically introduced pH scale. As in most water solutions pH is in the ",1$ rane it
is commonly belie!ed that pH scale is limited to this rane, but in some cases pH !alues can be
neati!e or hiher than 1$.
Water solutions always contain H
0
and ;H
,
ions , either from water autodissociation or from
introduced bases or acids. Water containin same amounts of both ions is called neutral. 7n neutral
solution 4H
0
5<4;H
,
5<1"
,=
%read about water autodissociation to find more&, so pH of neutral solution is
= %it can be slihtly lower, especially in hiher temperatures&. 7f solution contains more H
0
than ;H
,
it
1
is acidic, and the pH !alue is lower than =, if there is more ;H
,
than H
0
, solution is basic , and pH
!alue is hiher than =.
pH scale is widely used as it makes comparison of different solutions or samples !ery easy, besides it
often i!es !ery fast information about the sample. 7t is much easier to say that sea water pH is about
>, than to state H
0
concentration is 1"
,>
). Besides, knowin that sea water pH is > one already knows
that it is slihtly basic.
8o et a better feelin about pH scale it is worth to remember few pH !alues6
substance pH scale value
battery acid ?1
astric @uice A
lemon @uice A.$
milk 6.B
blood =.3$,=.$B
hand soap 9,1"
bleach 1A.B
.ote that for a purpose some !alues are i!en with hiher accuracy then others. pH of blood is kept
!ery precisely in the i!en rane by the carbonic buffer, when the pH of blood oes down it forces us
to pant, while when it oes up it can effect in in!oluntary muscle contractions. pH of astric @uice
!aries dependin on the diet and how much time elapsed from the last meal. pH of hand soap is in the
rane 9,1", but as natural pH of skin is slihtly acidic %around pH B& such soap lefts skin dry and
rouh, thus more and more soap producers modify their recipes to lower soap pH. :inally pH of lemon
@uice depend on the fruit ripeness %in fact first pH meters were produced for lemon planters&.
:or more information see pH scale lecture %and other lectures on pH& at -hemBuddy , chemical
calculators site.
pH calculation
pH calculation can be , dependin on the system , !ery easy, or e/tremally complicated. 8here are
three reasons. :irst of all, most acids and bases are weak and to calculate concentration of H
0
one ha!e
to find out e/act e(uilibrium of the system , the more compounds present, the more interactions ha!e
to be taken into account and the more difficult calculations are. *econd, water by itself is a source of
H
0
cations due to autodissociation, which plays important role in diluted solutions of acids and bases
%that9s why pure water has pH<=&. 8hird, in case of solutions more concentrated than "."1) %or e!en
".""1)& acti!ities start to play important role, which makes calculations e!en harder.
7n case of diluted , but not !ery diluted , stron acid, like H-l, we can assume that acti!ity of H
0

e(uals its concentration and that acid is completely dissociated. 8hus pH of 1"
,$
) H-l solution is @ust
Howe!er, if the solution is !ery diluted , say 1"
,=
) , this easy approach is not sufficient, as the pH of
such solution is not = , but 6.=9, due to H
0
from water autodissociation.
7n case of weak acid %acetic acid for e/ample& apart from water autodissociation you ha!e to take
e(uilibrium constant for the dissociation into account. 7n eneral it leads to cubic e(uation, which in
A
most cases can be simplified to (uadratic, as usually concentration of acid is hih enouh to allow
nelection of water autodissociation. C/planation of the process is out of scope of this site, please refer
to the pH calculation lectures where this problem is addressed in details.
7f you ha!e to calculate pH of solution, but you are not interested in detailed e/planation and theory of
such calculations, we stronly ad!ice you to use BA8C , pH calculator proram. 7f you are lookin for
a way of calculatin composition of buffer, use Buffer )aker , buffer calculator.
Nernst equation - electrode potential as function
of pH
.ernst e(uation describes potential of electrochemical cell as a function of concentrations of ions
takin part in the reaction6
Where D is a reaction (uotient and n is number of electrons e/chaned. :or constant temperature
e/pression E8F: has constant !alue. 8o simplify calculations it is often combined with con!ersion
factor between natural loarithm %denoted here by ln& and decimal loarithm %denoted here by lo& to
form !alue of "."B91 %for ABG-&. 8hus for e/ample for half reaction of )n;
$
,
in acidic media6
)n;
$
,
0 >H
0
0 Be
,
,H )n
A0
0 $H
A
;
potential is i!en by
8o be precise we should use not concentrations, but thermodynamic acti!ities of the ions present in the
solution.
When applied to the full cell formed from half cells present on inside and outside of lass pH
electrode, .ernst e(uation takes form6
or %usin pH definition&
pH inside of the electrode has constant !alue, thus it can be included in the potential part of the
e(uation6
8his form of the e(uation describes beha!ior of the lass electrode used for pH measurements.
3
7t is necessary to add two remarks here. :irst, abo!e e(uation assumes ideal response from the lass
electrode. *econd, "."B91 !alue was calculated for ABG- temperature. 7n most cases electrode doesn9t
beha!e as ideal and the temperature is not e/actly ABG-, thus slope of the electrode response in not
"."B91. 8o o!ercome these problems electrode should be calibrated before each use or series of uses.
$
pH meter - history
:irst pH meter was constructed in 193$ by Arnold Beckman. Ilass pH electrode that ha!e potential
dependent on acti!ity of H
0
ions was constructed much earlier, in 19"6 by :ritJ Haber and Kymunt
LlemensiewicJ, but the technical difficulties were pre!entin lare scale use of potentiometric
measurements of the pH %note that before 19"9 pH was not called this way&. )ain problem was caused
by lare internal resistance of lass electrodes, which make measurements !ery difficult. 8o obtain
reliable results one was forced to use !ery sensiti!e al!anoscope , e/pensi!e and difficult to maintain.
8o o!ercome the problem Arnold Beckman proposed to use simple hih,ain amplifier made usin
two !acuum tubes. Amplified current was much easier to measure with cheap miliamperometers.
Beckman9s first pH meter , predecessor of )odel I. 8his is a picture of oriinal model made in 193$
and patented. +icture courtesy of Beckman -oulter, 7nc.
7dea soon proo!ed to be workin and in 1936 Beckman decided to try to sell the pH meter
commercially as )odel I acidimeter, later renamed to )odel I pH meter. He decided to put whole
apparatus , amplifier, electrochemical cell, electrode, calibration dials, batteries and measurin aue ,
into one wooden bo/, idea not so ob!ious in 1936 as it is now. 7nitially market was e!aluated as 6""
pH meters that will saturate lobal demand in 1" years. :irst year sales reached $$$ items, showin
that new market for measurin de!ices was disco!ered. )odel I was made and sold till fifties, with
de!ice serial numbers reachin 1A6 thousand rane in 19BB.
B
)odel I pH meter. 2e!ice was closed in wooden bo/ 1AM wide by >M deep by 9M hih. 7t had a leather
carryin handle, but , as for todays standards , was hardly portable, weihtin almost > kilorams.
Eeference electrode and lass electrode were fastened to the door and could be used for measurements
in this position, but they could be also remo!ed if necessary&. +icture courtesy of Beckman -oulter,
7nc.
While the )odel I pH meter was commercial succes, it was soon disco!ered that the reliability of the
lass electrode was !ery low. As the construction of apparatus forced the electrode to be used always
in almost the same position in the solution %see the picture abo!e&, it was not so e!ident, but the
independent study done at *tanford 1ni!ersity showed that pH measurements results were !ery hihly
dependent on the depth of electrode immersion. 8his lead to the complete redesin of the electrode in
193=.
At the same time other manufacturers started to produce pH meters too , in Curope 2annish
Eadiometer introduced its first commercially a!ailable pH meter, model +H)1, in ;ctober 193=.
Althouh =3 years passed since then, almost all pH meters follow the same eneral idea , e/ternal pH
and reference electrodes %often in the same housin&, hih ain amplifier, and amperometer, all in one
portable bo/.
And the market is still not fully saturated 6&
pH meter - construction
As it was sinalled before, pH meter is nothin else, but precise !oltmeter, that measures C): of the
pH electrode. Howe!er, most commercially a!ailable !oltmeters will be of no use. pH electrode has
internal resistance in the rane of 1",1"" )N. 8o reliably measure potential !oltmeter must ha!e
internal resistance at least 1"" times larer, while most diital meters a!ailable ha!e resistance in the
rane of 1,1" )N, thus they are unsuitable.
)akin hih,resistance !oltmeter is not easy, as such de!ices are much more sensiti!e to temperature
chanes and electromanetic noise, as well as to electrostatic chares. Howe!er, with electronic
elements a!ailable today it is not !ery difficult to create an amplifier of !ery hih ain and !ery hih
input resistance. *uch amplifier can be used as interface between pH electrode and !oltmeter %see
e/ample circuit diaram below& , and that9s how many of the shelf pH meters work.
While the basic ideas behind the pH meter workin didn9t chane much since 193$ %see pH meter
history&, reliability and precision of todays pH meter are much better, althouh they are still limited by
the electrode construction and properties of the solution itself. As e!ery other lab de!ice todays pH
meter is diitiJed and able to communicate with computer, some models can automatically record data
for e/tended period of time and print the results and so on.
8here are two roups of pH meters , bench and portable. Bench pH meter is usually more precise and
has more options built in , most often it can be used in any potentiometric application. +ortable de!ices
are much simpler, and often able to measure pH only. Howe!er, in field they can be in!aluable.
Below is e/ample circuit diaram of the pH meter. .ote that de!ice is built usin se!eral resistors and
switches, the only acti!e element bein carefuly selected operational amplifier. *witches and resistors
are necessary to select the mode of operation %pH meter or mili!oltmeter for potentiometric
applications& and to allow calibration.
6
8he meter is a dual mode non,in!ertin amplifier. A 2+28 switch is used to select between mili!olt
mode %ain<1"OFO, reference<"O& and pH mode %ad@ustable ain and reference&. A 1"L ohm trimmer
potentiometer is used for Jero ad@ustment %offset null&.
1. 7nput section , the cell is connected to the non in!ertin input of a 8P">1 Q:C8 input operational
amplifier throuh a shortin type A.B mm plu %not shown in the schematic diaram&. When the cell is
not connected, the A.Bmm plu shorts the input to round, this permits ad@ustin Jero in mili!olt mode,
and reference in pH mode.
A. Amplifier section , a 8P">1 operational amplifier is connected as a non,in!ertin amplifier, with the
feedback resistor network selected by one pole of a 2+28 switch.
7n mili!olt mode, the network consists of a 9."9L ohm resistor in the feedback loop %E1&, and a 1."" L
ohm resistor to round %EA&. 8he ain is i!en by6
Iain< 1 0 E1FEA < 1 0 9."9LF1.""L < 1"."9 < R1"
7n pH mode, the network consists of a B6"L ohm resistor %E3&, a 1" L ohm linear taper potentiometer
%E$&, and a 3" L ohm resistor to round %EB&. 8he !ariable terminal of the potentiometer is connected
to the in!ertin input of the op,amp and the ain is i!en by the e(uation that follows, where + is the
position of the potentiometer9s wiper with respect to the B6" L resistor, it !aries between " %all the way
counter clockwise& and 1 %all the way clockwise&6
Iain < 1 0 %E30+ / E$&F%EB0%1,+& / E$&
At the lowest point %+<"&6
Iain<1 0 B6"LF%3"L 0 1"L&< 10B6"LF$"L < 1B
At the hihest point %+<1&6
Iain<1 0 %B6"L01"L&F3"L< 10B="LF3"L < A"
=
8he ain re(uired at ABG-, for 1 Oolt per pH unit is about 16.=, the circuit allows for ad@ustin between
9"S and 1A"S appro/imately.
3. ;utput section , the output is taken from the output of the 8P">1 directly and can be read with any
2- !oltmeter. 7n mili!olt mode the reference is ". 8he !oltae readin is 1" times the cell !oltae,
permittin ".1 mili!olt resolution with low cost !oltmeters. 7n pH mode the reference can be ad@usted
from pH " to pH 1A throuh a 1"L ohm linear taper potentiometer, for use with -arbonFDuinhydrone
electrodes. With the reference properly ad@usted, the output in !olts will be the actual pH of the
indicator solution. With low cost !oltmeters the accuracy is about "."B pH units when properly
calibrated.
-urcuit diaram and description used with permission and slihtly modified %power supply replaced
with battery, for the sake of clarity&. :or oriinal !ersion refer to 8he Pow -ost C(uipment +ro@ect
1.C*-;F71+A- site.
Here are some links to pH meter producers www paes6
American )arine 7nc. pH meter
BT- Clectronics
Beckman -oulter pH meters
Bluelab pH )eter
-2 Hihtech pH meters
-ole,+armer pH meters
-onsort
2en!er 7nstrument pH meters
Crlich 7ndustrial 2e!elopment, -orp. pH meters
2iital 7nstruments -orporation pH meter
Cutech 7nstruments pH meters
Hanna 7nstruments pH meters
7ndustrial T -hemical )easurement pH meters
Qenco pH meters
Lelilon pH meters
2r. A.LuntJe ImbH pH meters
)etrohm pH meters
)ettler 8oledo
)ilwaukee )eters pH meters
)onokrystaly s.r.o. pH meters
.ieuwkoop BO pH meters
Eadiometer analytical pH meters
8hermo,:isher *cientific, 7nc.
8rans 7nstruments
Weiss Eesearch pH meters
8his list is not intended to be complete, but if you are a manufacturer of the pH meters and you want
us to add link to your products to the list, please use Let us Know! link at the bottom of the pae to
contact us and we will add link to your pae for free.
Also feel free to tell us if links are outdated. We try to occasionally check them, but they tend to rot
nonetheless.
Before use pH meter must be calibrated. Cach pH electrode used for measurements is slihtly different
and its characteristic chanes with ain. Without proper pH meter calibration results will be usually
off by at least se!eral tenths of the unit. pH meter calibration procedure calls for use of two or three pH
calibration buffers of e/actly known pH %these can be bouht as either solutions or in solid form& in
>
which pH electrode is dipped and pH meter indications are corrected. 2ependin on the pH meter type
it may either reconiJe buffer automatically and perform calibration procedure almost on its own %@ust
askin for buffer chane when needed& or you will ha!e to calibrate it usin knobs and chanin
buffers once each calibration step is completed. 7n both cases underlyin principle is the same , ain
and offset parameters are set assumin linear dependence between pH and electrode !oltae.
pH meter calibration is more often referred to as pH electrode calibration, as parameters set are not
de!ice dependent, but electrode dependent. -orrect procedure of the pH meter calibration is usually
described in the pH meter manual. Ieneral outline of the procedure is presented in the pH electrode
calibration section.
pH electrode
:irst lass pH electrode was constructed in 19"> by :ritJ Haber and Kymunt LlemensiewicJ. As the
paper describin electrode was published year later %K. +hys. -hem. 19"9,. 6=, 3>B.& it is usually
assumed that the electrode was created in 19"9. 8he oriinal electrode had a lass bubble, was filled
with stron electrolyte and there was an AFA-l half cell inside, with A wire as a contact.
8oday the eneral idea did not chaned much. +otential difference builds up on the sides of thin lass
in the bubble thanks to the difference between H
0
acti!ities on both sides, this potential difference is
measured with the help of reference electrodes , and is known to be proportional to the pH on the
outside of the bubble.
Howe!er, our practical knowlede about the pH electrodes is much wider now , and it allowed new
desins, like combined electrode, double @unction electrode or electrode with elled electrolyte. At the
same time thanks to the careful selection of lass todays pH electrode has much hiher selecti!ity.
8here are also completely new, solid state electrodes, not as popular yet.
pH electrode - flowing and gel
combination pH electrode
9
pH el electrode
7n flowin electrodes internal solution of L-l slowly flows to the outside throuh the @unction , small
hole with porous membrane, or ceramic or , in older models , asbestous wick. While such electrode
contaminates solution with L-l it does it !ery slowly and traces of L
0
and -l
,
ions released durin
measurements are in most cases @ust spectators.
As the internal solution is lost from the flowin electrodes it must must be refilled so that its le!el is
always abo!e the le!el of the e/ternal %measured& solution. 8his way internal solution should ne!er et
contaminated. Howe!er, refillin of the combination electrodes adds to their maintenance cost and
makes them difficult to use in portable pH meters.
8o o!ercome problems with fillin internal solution is sometimes elled. While this helps slow down
leak, it doesn9t pre!ent diffusional ion e/chane throuh @unction , thus internal solution ets
contaminated by the ions diffusin from the e/ternal sources, at the same time loosin its own ions. As
the composition of internal solution chanes and can9t be restored by refillin, el electrodes ha!e in
eneral shorter life time, althouh they are easier to use and maintain.
;ther method of prolonin the lifetime of the electrode is use of double @unction.
*peed of the flow is one of important electrode parameters. 7t can9t be too fast nor to slow. :low can be
too fast in case of broken membrane or lost %loose& wick, it can be too slow if the membraneFwick was
cloed by some chemical precipitate , for e/ample A-l if the electrode was used to measure pH of
solution containin A
0
ions. *ee electrode cleanin to learn how to unclo electrode.
1"
pH electrode - single and double junction
sinle @unction pH electrode
double @unction pH electrode
7n classical combined pH electrode reference electrode is separated from the e/ternal solution by the
@unction throuh which the electrolyte leaks. Post electrolyte must be periodically refilled throuh the
fillin hole, which makes these electrodes incon!enient to use, especially in field. )ethods of slowin
down the leak , like ellin of the electrolyte , ha!e a side effect of shortenin the lifetime of the
electrode, as it is more prone to the chanes in electrolyte composition due to contamination and
diffusional leak of the ions. -ontaminated el can not be replaced, thus lifetime of el electrode is
rarely loner than se!eral months.
8o prolon lifetime of such electrodes double @unction is sometimes used. 7n double @unction
electrodes additional chamber is introduced between reference electrode and e/ternal solution. Before
contamination from the e/ternal solution can et to the reference electrode it must diffuse throuh not
one @unction, but two %hence the name&. Additional chamber works as a buffer, slowin down the
11
chanes in the composition of the reference electrode electrolyte. 2ouble @unction electrodes can work
loner, but they are more difficult to make, thus more e/pensi!e.
.ote, that sinle or double @unction refers only to the way reference electrode is made. While you will
often see combination electrodes described as pH double junction, e/ternal reference electrode can be
made double @unction as well.
solid state pH electrode
-ommercially a!ailable solid state pH electrodes are mainly built around 7on *electi!e :ield Cffect
8ransistors %7*:C8&.
8he basic principle of the 7*:C8 workin is the control of the current flowin between two
semiconductor elements %drain and souce& by electrostatic field, enerated by the protonated o/ide
ate. +rotonation of the ate is in a way identical to the process takin place in lass pH electrode, @ust
the methodoloy used to measure protonation deree is different. 7nstead of measurin potential
difference on two sides of the lass, we measure the current flowin throuh the transistor. 8he lower
the pH, the more protonated and chared ate is which chanes its electric field , chanin in turn
current flowin throuh the transistor. 8his current is a sinal that can be measured to check the pH
!alue.
7*:C8 electrodes can be !ery small when compared to the bulky lass bubble of the standard lass
electrode. 8hey are also much more sturdy, so they can be easily used in places where fraile lass
electrodes will not sur!i!e. Howe!er, 7*:C8 electrode can9t be used with standard pH meters %unless it
is connected throuh special interface& and the pH measurements are enerally less precise when
compared to lass electrode.
pH electrode - potential
+otential measured by pH meter is a sum of all potentials present in the system. +uttin aside @unction
potentials that can be present in the e/perimental setup, we are left with three sources of electromoti!e
force. :irst builds up on the lass electrode, thanks to different acti!ities of the H
0
ions on both sides of
the lass. *econd source is the lass electrode sil!er wire co!ered with A-l and immersed in the
solution of chlorides, and third is the reference electrode , sil!er chloride or calomel, dependin on the
application.
8hus the real potential measured is sum of three potentials6
where %see .ernst e(uation section&
which finally leads us to the %almost , read on& final e(uation describin measured potential6
Where C
"
99 contains all constants mentioned abo!e and in the .ernst e(uation section. As you see after
takin %almost , read on& all factors into account we can e/pect perfect linear dependence between
measured potential and pH.
1A
;ne may ask at this point, why do we complicate thins addin two additional sources of potential
%C
AFA-l
and C
ref
&, instead of measurin @ust the potential of lass electrode which beha!es as the
concentration cellU 8he answer is simple , there is no easy and practical way of measurin the lass
electrode potential. We may think of two added reference cells @ust as of reliable contacts, interfacin
metal wires and solution. While they add their own potentials shiftin lass electrode potential
readouts, it doesn9t matter. :irst of all, we ne!er need absolute !alues of lass electrode potential, as
only difference bein proportional to the difference in pH of both sides of the lass counts. *econd,
e!en if we will be able to measure absolute potential it will not help us much, as it depends on many
additional thins , like internal tensions in the lass, or the smoothness of the lass surface. As we
already ha!e to compensate for these impredictable factors, additional, constant shift in !oltae doesn9t
chane our situation.
Qunction potential, that we ha!e inored in the abo!e e(uation, in practice can be an important source
of error. 7t was an important issue back in the early eihties of the A"th century. )ost modern
electrodes are less prone to this effect.
C!ery electrode has a characteristic pH where its potential is " %so called isopotential point&. -arefully
choosin potentials of both reference electrodes %which can be done with selection of chlorides
concentration& it is possible to compensate for all other sources of potential in the electrode so that
isopotential point is at pH<=.". )ost modern pH electrodes are made this way.
As it was mentioned abo!e so far we ha!e looked at almost all factors, but some are still left
uncommented. Ilass electrode potential depends on the presence of other then H
0
ions in the solution.
While carefull selection of the lass used makes this difference small, it can9t be nelected. )ore on
that in electrode selecti!ity section.
pH electrode - selectivity
7deal pH electrode should ha!e potential dependent solely on the acti!ity of the H
0
. 1nfortunately,
there is no such thin as ideal pH electrode.
+otential that builds up on the electrode surfaces has its source in the ions attachin themsel!es to the
lass surface. Ilass structure is such that only sinle chared ions are attracted. 2ependin on the ion
this effect can be stroner or weaker, but the result will be always the same , other ions will interfere
with the determination of pH.
8o describe effect of other ions on the electrode potential we can use slihtly simplified !ersion of
.icolsky,Cisenman e(uation6
where k
i
are so called selecti!ity coefficients, determined e/perimentally.
C!ery lass electrode potential depends not only on pH but on concentrations of all other sinle
chared ions present. -arefull selection of the lass composition is crucial, as lass is solely
responsible for the selecti!ity coefficients !alues. 8hese can take !alues from the 1"
,1
, 1"
,1B
rane. 8he
smaller the !alue the better. 7mportance of the small selecti!ity coefficient can be shown with simple
e/ample. Pet9s assume selecti!ity coefficient H
0
F.a
0
of 1"
,>
and ".1) .a
0
solution6
13
real pH measured pH
1."" 1.""
=."" =.""
>."" =.96
9."" >.="
1"."" >.96
)easurement will ne!er show pH abo!e 9."" in this case. 8his effect is called alkaline error or sodium
error, but not only sodium can interfere with pH measurements. ;ther sinle chared cations interfere
as well. 7t is especially important in the case of buffers %for e/ample 8E7* based& where the
concentration of interferin ion can be relati!ely hih. )ost commercial pH electrodes ha!e selecti!ity
ceofficients hih enouh to not allow such situations. 2etailed information about selecti!ity should be
a!ailable from electrode manufacturer.
7t is worth of notin here, that usin proper lass one can make lass electrode that can be used for
determination of other sinle chared ions , like A
0
, .a
0
, L
0
and so on.
choosing pH electrode
8here are many types of pH lass electrodes. 7n some specific applications you should be !ery carefull
when selectin one, but in most cases the selection is easy. Pook for other users workin in similar
en!ironment and ask them about their e/perience with different types and makes of electrodes, that
way you should be able to find the best offer pretty fast.
7f you are workin with a(ueous solutions containin at least BS water and your solutions doesn9t
contain any substances reactin with sil!er, look for eneral purpose electrodes.
7f you work with solutions containin oranic material, proteins, 8E7* buffers, hea!y metals, or with
!ery low ionic strenth solutions, look for calomel electrode. Pisted substances can react with sil!er
and clo the @unction.
7nstead of usin calomel electrode you may look for double @unction electrode, as it will ha!e similar
properties.
7f you are workin with solutions that can clo normal electrode @unction %like oils, foods or paints&
look for teflon @unction electrode. Qunction in these electrodes is made of porous teflon, makin it
resistant to impurities.
2on9t foret to check electrode pH rane , some electrodes can9t work in hih pH, and electrode
temperature rane , especially if you are oin to measure pH in solutions abo!e 6"G-.
7n most cases manufacturers sites contain a wealth of information about a!ailable pH electrode models
and their applications.
1$
pH electrodes producers
*elected links to the different pH electrode manufacturers and resellers paes6
Ad!anced *ensors 8echnoloies, 7nc. pH electrodes
BT- Clectronics
Bluelab pH probe
-ole,+armer pH electrodes
-onsort pH electrodes
Crlich 7ndustrial 2e!elopment, -orp. pH electrodes
Cutech 7nstruments pH electrodes %scroll down the pae& pH electrodes
Hanna 7nstruments pH electrodes
)ettler 8oledo
ionode pH electrodes
2r. A.LuntJe ImbH pH electrodes
Lelilon pH electrodes
)ilwaukee )eters pH electrodes
)onokrystaly, s.r.o. pH electrodes
.ieuwkoop BO pH electrodes
Eadiometer pH electrodes
*ense/ pH electrodes
*ensore/ pH electrodes
8hermo,:isher *cientific, 7nc.
1nisense pH microelectrode
Weiss Eesearch pH electrodes
8his list is not intended to be complete, but if you are a manufacturer of the pH electrodes and you
want us to add link to your products to the list, please use Let us Know! link at the bottom of the pae
to contact us and we will add link to your pae for free.
Also feel free to tel us if links are outdated. We try to occasionally check them, but they tend to rot
nonetheless.
pH electrode - maintenance
Handle electrode with care , it is fraile'
Leep electrode always immersed. 1se the solution recommended by manufacturer or neutral
solution of L-l %3),$)&.
Eemember to always keep internal le!el of fillin solution abo!e the le!el of measured
solution.
:ill electrode %the flowin type& with correct fillin solution %as recommended by manufacturer
, usually L-l solution, 3) to saturated& to not let it dry internally.
7f the electrode will be not used for a lon period of time, you may store it dry to pre!ent ain
%ain takes place only when the electrode is wet&. 2on9t try it with el electrodes , these ha!e
to be stored in concentrated solution of L-l only.
7f dried incidentally, or after storin , soak for at least A$ hours before usin.
7f you are usin the electrode in solution containin substances able to clo the @unction or stick
to the lass bubble, clean the electrode as soon as possible after use.
2on9t put electrode in solutions that can dissol!e lass , hydrofluroic acid %or acidified fluroide
solution&, concentrated alkalies.
2on9t put electrode into dehydratin solution such as ethanol, sulfuric acid, etc.
1B
2on9t rub or wipe electrode bulb, to reduce chance of error due to polariJation.
2on9t use oranic sol!ents for cleanin of the electrode with epo/y body.
storing pH electrode
Clectrodes with li(uid electrolytes %not el types& may be stored either wet or dry.
A wet stored electrode allows an immediate use and a short response time, which is not true for dry
stored ones. 1nfortunately, the wet stored electrode is ain faster, because the process of ain
%chanin of the structure in the membrane& proceeds also in the case of non,use. Leepin electrodes
wet should preferably be made in L-l solution %3),$)&. )ost electrodes ha!e a protecti!e cap that
can be filled with storae solution before placin.
8o store pH electrode dry you must first remo!e internal solution, rinse the electrode in 27FE; water,
and let it dry.
.ote that you can9t store dry combination electrodes and el electrodes. 7n fact electrodes that can be
stored dry are ettin more and more rare.
7f electrode is stored wet, don9t foret to co!er fill hole to prohibit e!aporation of reference fill
solution.
Iel type electrodes can be stored only wet, soaked in the L-l solution %3),$)&. .e!er store them in
27FE; water.
-heck your electrode owners manual for details, as these may depend on the electrode make.
pH electrode - calibration
Before measuring pH you have to calibrate %standardiJe& electrode. 8o calibrate the electrode you
need at least two solutions of known pH. )ost commonly used commercially a!ailable calibration
buffers ha!e pH of $."1, =."" and 1"."".
2etails of the calibration procedure depend on the pH meter model. :irst step is usually related to
temperature correction. *ome models will measure temperature by itself, others need e/ternal
temperature probe, or you will ha!e to enter temperature measured by others means usin dials or
buttons. .ote that this settin chanes only slope of the calibration cur!e and doesn9t take into account
fact, that buffer pH chanes with temperature.
.e/t step is to put the electrode into pH =."" buffer. Einse the electrode with distilled water from a
wash bottle into an empty beaker before immersin it into new solution. #ou should do it e!ery time
electrode is mo!ed from one solution to other to minimise contamination. -heck if the workin part of
the electrode is completely immersed in the buffer. 8ake care to not hit bottom of the baker with the
electrode. Wait for the readin to stabiliJe %it takes seconds usually, up to a minute sometimes&.
)odern pH meter models workin in calibration mode often reconiJe the buffer automatically and
take necessary action by themsel!es. 7n case of older pH meters you will probably ha!e to turn one of
calibration knobs so that the pH meter shows =."".
*ometimes pH readins will oscillate. 7f the oscillations are small try to find out the best position of
the knob so that =."" is a mean displayed !alue. 7f the oscillations are lare and erratic, they may be
caused by faulty @unction %check all&, faulty cable %check them&, faulty electrode %try other electrode&
or faulty pH meter. *ometimes also static electricity can be a reason of erratic readins , consider
16
chanin clothes, roundin yourself or shieldin pH meter, cables and electrode. 7f you are usin
manetic stirrer check if switchin it off doesn9t stop oscillations.
.e/t steps will depend on the solution you want to measure pH of. 7f you plan to measure pH in acidic
solutions, use pH<$."1 buffer. 7f you plan to measure hih pH use pH<1"."" buffer. 7f you want to be
able to measure pH in the wider rane, you may want to proceed with three point calibration and you
will need both buffers. Eemember that hih pH buffers tend to absorb atmospheric -;
A
thus they
should be used as fresh as possible , don9t left the bottle open and do the calibration immediately after
fillin the beaker with the buffer.
Einse the electrode and mo!e it to the second buffer. ;nce aain pH meter will either act on itself, or
you will ha!e to use a knob %probably different from the one used in the pre!ious step&. Eepeat the
action for the third buffer if needed %usin third knob , if present&.
After that you are ready to take measurements.
+lease remember, that abo!e outline is !ery eneral. 2ifferent pH meters may re(uire slihtly different
operatin procedures. #ou should consult your manual to be sure how to proceed and how to maintain
the electrode.
pH electrode - calibration buffers
7n eneral you will probably use commercially a!ailable calibration buffers, sold either as ready
solutions or as tablets to dissol!e in deioniJed water. Howe!er, it may be interestin to look at the table
of standard solutions that can be used for the electrode calibration. pH i!en is for 256
*tandard calibration buffers
substance!s" concentration pH
hydrochloric acid
H-l
".1""") 1."9$
potassium trihydroen o/alate
LH
3
-
$
;
>
"."B"""m 1.6=9
potassium hydroen phthalate
LH-
>
H
$
;
$
"."B"""m $.""B
potassium hydroen tartrate
LH-
$
H
$
;
6
saturated in ABG- 3.BB=
disodium hydroen phosphate
.a
A
H+;
$
potassium dihydroen phosphate
LH
A
+;
$
"."AB""m
"."AB""m
6.>6B
disodium hydroen phosphate
.a
A
H+;
$
potassium dihydroen phosphate
LH
A
+;
$
"."3"$3m
"."">69Bm
=.$13
disodium tetraborate
.a
A
B
$
;
=
"."1"""m 9.1>"
sodium hydroen carbonate
.aH-;
3
sodium carbonate
.a
A
-;
3
"."AB""m
"."AB""m
1"."1A
calcium hydro/ide
-a%;H&
A
saturated in ABG- 1A.$B
1=
m stands for molality, ) for molarity.
+lease note that hih pH buffers are less stable, as they tend to absorb atmospheric -;
A
which lowers
their pH. 2urin calibration you should open the bottle only to pour the buffer to the beaker. .e!er left
the bottle open.
7t is also important to remember that pH of buffer solutions chane with temperature. pH of potassium
hydroen phthalate solution rises to $.16 at >"G-. )any pH meters doesn9t take these chanes into
account automatically, e!en if they allow automatic temperature compensation durin measurements.
pH electrode - testing parameters
8o ensure your electrode works correctly you may want to measure its parameters.
e/ample correct pH electrode parameters
property value
isopotential point V 1B mO oriinal !alue
slope BB , 61 mOFpH unit
lass membrane resistance A",1"" )N
electrolyte leak rate ".A to 1.B mPFA$ hours
.ote that !alues presented can be wron in case of specific electrode %for e/ample electrolyte leak rate
in electrodes with slee!e @unction can be much faster&. -onsult owners manual if in doubt.
8o test isopotential point and slope, switch your pH meter to display results in mO, not as pH units. 7f
not possible, you ha!e to use other pH meter or laboratory !oltmeter able to work with pH electrodes.
7sopotential point of most eneral use electrodes is set at pH<=."". 8o measure it put the electrode into
pH = buffer and measure the electrode potential. Eemember to take the measurements in the
temperature electrode was oriinally calibrated in.
8o check the slope mo!e electrode to the pH $ buffer. When potential stabiliJes, read the !alue. 8he
difference between pre!ious readin and current readin should be in the 166,1>$ mO rane.
)easurements of the electrode resistance and electrolyte leak rate are more difficult. Ilass membrane
resistance measurements re(uire electrode test stand. 8o check electrolyte leak rate fill the electrode
wil fillin solution. 1se a waterproof pen to mark the initiall fill le!el. *uspend the electrode in a
beaker of pH = or pH $ buffer so that the lower electrode plu is le!el with the water. Wait for A$
hours. Eefill the electrode usin a seroloical pipet, notin the !olume of fillin solution re(uired.
Amount of solution added di!ided by A$ is a flow rate.
cleaning pH electrode
-leanin of the electrode %note that in case of el electrodes replacin of the reference solution is
usually impossible&6
Ieneral
o *oak in ".1) H-l for half an hour.
o 2rain and refill the reference solution.
o *oak the electrode in fillin solution for one hour.
1>
7noranic6
o *oak in ".1) tetrasodium C28A solution for 1B minutes.
o 2rain and refill the reference solution.
o *oak the electrode in fillin solution for one hour.
+rotein6
o *oak in 1S pepsin F ".1) H-l for 1B minutes.
o 2rain and refill the reference solution.
o *oak the electrode in fillin solution for one hour.
Irease and ;il6
o Einse with deterent or ethanol solution.
o 2rain and refill the reference solution.
o *oak the electrode in fillin solution for one hour. Clectrode response may be enhanced
by substitutin a mi/ture of 161 pH $ buffer and fillin solution for the soakin solution.
-leanin of the cloed @unction6
+ollution by sulfides6
o 1se a solution of >S thiocarbamide in 1 molFP H-l.
o Leep the electrode in the abo!e solution till @unction9s color turns pale.
+ollution by sil!er chloride6
o 1se concentrated ammonia solution.
o Leep the electrode in the abo!e solution for about 1A hours.
o Einse and put into pH $ buffer for at least 1 hour.
;ther contamination ha!e to be remo!ed by cleanin with distilled water, alcohol or mi/tures of acids.
7f nothin else helps you may consider use of ultrasonic cleaner as last resort.
rejuvenating pH electrode
.ote6 followin procedures are a last resort. 8hey may work, they may won9t. #ou may try them before
throwin electrode away.
:irst of all , clean the electrode as described in electrode cleanin section, then6
*oak the electrode for $,> hours in 1) H-l solution.
Einse it and mo!e to pH = buffer for an hour.
Ii!e it a try.
7f the electrode is still not workin6
:ill the electrode with fillin solution.
)o!e to the fume hood'
+lace the electrode in the 1"S nitric acid solution on a hotplate. Heat to boilin, and keep it in
the solution for 1" minutes.
+lace B" mP of fillin solution in a second clean beaker. Heat, althouh boilin is not
necessary.
While the electrode is still hot, transfer it to the beaker of heated fillin solution. *et aside to
cool.
When the electrode has cooled, test the electrode as described in the testin electrode parameters
section. 8his re@u!enatin procedure is particularly effecti!e with el filled combination electrodes. 2o
19
not be concerned if a small amount of the el protrudes throuh the reference frit durin the boilin in
nitric acid step. 8his is both acceptable and useful.
7f this procedure does not result in a pH electrode that responds (uickly and has a slope of BB , 61
mOFpH unit, the electrode is unreco!erable and should be thrown away. Eemember, the procedure was
proposed for the electrode that was to be thrown away anyway.
*ome manufacturers suest the electrode may be reacti!ated by treatin with a diluted solution of
hydrofluoric acid followed by subse(uent conditionin in electrolyte. Before considerin the
procedure, take into account that hydrofluoric acid is e/tremally danerous' *afer %but still danerous&
approach can be to use some slihtly acidic solution containin fluorides, like A" wtS ammonium
bifluoride, .H
$
H:
A
, put lass bulb part of the electrode in the solution for a minute followed by 1B
seconds bath in 6 ) hydrochloric acid. Einse the electrode well and soak for A$ hours in a pH buffer
with pH ? =.
pH measurements
pH measurements ha!e been performed in the chemistry from the !ery beinnin, althouh before
19"9 , for ob!ious reasons %see pH definition to find out why& , they were not called this way.
Howe!er, fact that solution must be acidic or basic, and that its acidity can be checked with natural
indicators %like litmus or red cabbae @uice& was known much earlier.
At present pH measurements are part of routine tests done to check potable water (uality, soil usability
for different plants, water (uality in a(uaristics, they are done to control industrial processes, in wine,
makin and beer,makin, to check milk (uality, to check cosmetics , not to mention all labs
throuhout the world where pH measurements are performed many times a day to control reactions
and analysis conditions.
pH can be measured in se!eral ways, of which two are widely used. ;ne , simple and often enouh
precise , is a use of pH strips %pH papers&. *econd, more costly and more demandin in terms of
procedure that ha!e to be used, but i!in much more precise results , is a potentiometric method with
usae of pH electrodes and pH meters. -olorimetric %spectroscopic& methods ha!e ne!er ained much
popularity, althouh they are occasionally used in places where pH electrodes can9t be immersed in the
solution and the pH stripes can9t be used.
pH measurements - indicators
pH indicators are usually weak acids or weak bases that chane their color dependin on their
dissociation %protonation& state. *ometimes both forms are colored, sometimes only one. 7n most cases
you may assume that to completely chane color of bicolored indicator pH must chane by A units.
Howe!er, human eye is more sensiti!e to some colors than to others, thus some color chanes can be
percei!ed o!er wider pH rane.
pH indicators can be used to check pH of the solution, althouh they are rarely added directly. ;nly in
acid,base titrations indicator should be added to the solution. 8o check pH it is much more con!enient
to use pH strips. 7t is worth of notin here that pH strips are nothin else but pieces of paper
imprenated with indicator or a mi/ture of indicators.
pH indicators , colors and color chane pH rane
indicator name pH pH
A"
color color
)alachite reen o/alate
"."
reen
A."
reen,blue
Brilliant reen
"."
yellow
A.6
reen
Cosin yellowish
"."
yellow
3."
reen fluoresc.
Crythrosine B
"."
yellow
3.6
red
)ethyl reen
".1
yellow
A.3
blue
)ethyl !iolet
".1
yellow
A.=
!iolet
+icric acid
".A
colourless
1."
yellow
-resol red
".A
red
1.>
yellow
-rystal !iolet
".>
yellow
A.6
blueF!iolet
m,-resol purple
1.A
red
A.>
yellow
8hymol blue
1.A
red
A.>
yellow
p,Wylenol blue
1.A
red
A.>
yellow
Cosin, bluish
1.$
colourless
A.$
pink fluoresc.
Duinaldine red
1.$
colourless
3.A
pink
A,$,2initro phenol
A.>
colourless
$.=
yellow
$,%2imethylamino& aJobenJol
A.9
red
$."
yellowForane
Bromochlorophenol blue
3."
yellow
$.6
blueF!iolet
Bromophenol blue
3."
yellow
$.6
blueF!iolet
-ono red
3."
blue
B.A
yellowForane
)ethyl orane
3.1
red
$.$
yellowForane
Bromocresol reen
3.>
yellow
B.$
blue
A,B,2initrophenol
$."
colourless
B.>
yellow
AliJarin sulphonic acid
$.3
yellow
6.3
!iolet
)ethyl red
$.$
red
6.A
yellowForane
-hlorophenol red $.> 6.$
A1
yellow purple
Pitmus
B."
red
>."
blue
Bromocresol purple
B.A
yellow
6.>
purple
Bromophenol red
B.A
oraneFyellow
6.>
purple
$,.itrophenol
B.$
colourless
=.B
yellow
Bromo/ylenol blue
B.=
yellow
=.B
blue
Bromothymol blue
6."
yellow
=.6
blue
+henol red
6.$
yellow
>.A
redF!iolet
3,.itrophenol
6.6
colourless
>.6
yellowForane
.eutral red
6.>
blueFred
>."
oraneFyellow
-reosol red
=."
orane
>.>
purple
1,.aphtholphthalein
=.1
brownish
>.3
blueFreen
m,-resol purple
=.$
yellow
9."
purple
8hymol blue
>."
yellow
9.6
blue
p,Wylenol blue
>."
yellow
9.6
blue
+henolphthalein
>.A
colourless
9.>
redF!iolet
8hymolphthalein
9.3
colourless
1".B
blue
Alkali blue
9.$
!iolet
1$."
pink
AliJarin yellow II
1"."
briht yellow
1A.1
brownFyellow
7ndio carmine
11.B
blue
13."
yellow
Cpsilon blue
11.6
orane
13."
!iolet
8itan yellow
1A."
yellow
13."
red
pH measurements - pH strips
pH strips , or pH papers , can be used for rouh estimation of solution pH. 8hey are made of paper
imprenated with pH indicators or mi/tures of indicators. 8o use a paper you ha!e to immerse it in the
solution, wait se!eral seconds and compare color of the paper with scale usually printed on the side of
the bo/. )odern pH stripes contain se!eral small pieces of indicator imprenated fabric, which makes
AA
measurements more precise when compared to older ones , where whole paper was imprenated with
identical indicators mi/ture.
8here are different types of pH papers. )ost often used are uni!ersal strips, that can be used to check
pH from the 1,1$ rane. Pess often, but still (uite popular are strips prepared for checkin pH in much
more narrow rane, like 3,6, =,1" or e!en only two pH units.
:inally there are litmus stripes sold in two !ersions , blue ones, and red ones. *uch litmus stripes can
be used to check presence of acid or base , blue will chane color to red if immersed in acid and won9t
chane color if immersed in base. Eed work @ust the opposite.
potentiometric pH measurements
7n potentiometric pH measurements ion selecti!e electrode is used. +otential of such electrode is
usually i!en by simplified .ernst e(uation6
C < C
"
9 0 "."B91Fn pa
where n is a chare of an ion and pa is minus loarithm of its acti!ity. 7n case of H
0
ions this e(uation
takes simplest possible form6
C < C
"
9 0 "."B91 pH
7n practice both constants present in the e(uation %C
"
9 and "."B91& are not as constant as we would like
them to be and can chane with the electrode ae and temperature. Howe!er, usually dependence
between electrode potential and solution pH is linear in the wide rane of pH and stable in few hours
time. 8hus it is enouh to calibrate electrode usin two buffer solutions of known pH before
measurements, to obtain !ery precise and reliable results.
7t is important to remember that potential of pH electrode is measured not as an absolute !alue, but
aainst reference electrode of known potential. )ost often used reference electrodes are sil!er chloride
electrode and saturated calomel electrode. 2ependin on the details of pH electrode construction
reference electrode can be closed in the same housin or can be separated. 8his is co!ered in much
more details in pH electrode section.
standard procedure for pH measurements
2ependin on the pH meter used and the electrode used procedure can look slihtly different, but in
most cases pH measurements procedure will be at least !ery similar.
:irst of all , remember, that the electrode should be always immersed. 8hus between pH
measurements it should be put into a baker with distilled water or , much better , L-l solution %".1)
to 1)&. 2on9t worry that you will destroy the electrode mo!in it between solutions. 7t can easily
sur!i!e minute in the air, but don9t let it dry.
*econd, e(ually important thin is , the electrode is very fragile. Bubble at the end is made of !ery
thin lass , the thinner the lass, the lower the internal electrode resistance, which is ood for
measurements. At the same time thin lass is !ery delicate, thus you should treat your electrode with
care.
Cnsure that pH meter is on. 7f you want hih precision of measurements it is better to let the pH meter
to warm up for some time %like 3" minutes& to ensure it will not drift later.
A3
Before e!ery sinle pH measurement, or before any serie of uses, you must calibrate pH electrode.
After calibration you are ready to measure pH. Einse electrode and submere it in the tested solution.
Eead the result and write it down in your lab notebook. Einse the electrode and mo!e it to the storae
baker. 2one.
+lease remember, that abo!e outline is !ery eneral. 2ifferent pH meters may re(uire slihtly different
operatin procedures. #ou should consult your meter manual to be sure how to proceed and how to
maintain the electrode.
pH measurements - temperature compensation
Accordin to the .ernst e(uation cell potential depends on the temperature. 8hus when measurin pH
temperature chanes must be taken into account.
7n most cases it is enouh to take care about the temperature at the time of calibration. 8emperature
chanes slope which is checked durin the calibration process. 8here are two thins to take into
account6
for best results measurements should be done in the same temperature calibration took place,
pH of calibration buffers chanes with temperature, so you can9t assume , especially usin
warm and hot buffer solutions , that their pH is nominal. pH !alues of calibration buffers
should be tabelariJed by manufacturer.
)any commercially a!ailable pH meters, especially better ones, ha!e built in temperature
compensation. 8he temperature compensation may be either manual or automatic. With manual
compensation, a separate temperature measurement is re(uired, and the pH meter manual
compensation control can be set with the appro/imate temperature !alue. With automatic temperature
compensation %A8-&, the sinal from a separate temperature probe %sometimes built into the electrode&
is fed into the pH meter, so that it can accurately determine pH !alue of the sample at that temperature.
perfecting pH measurements
8here are se!eral rules that you should follow to obtain perfect results of pH measurements.
Between measurements, rinse electrodes with distilled water.
-alibrate electrode before each use or series of uses.
Always use fresh buffers for calibration. 1se buffers that are no more than 3 pH units apart and
bracket the e/pected sample pH. .ote that standard calibration buffers %$."1, =."" and 1".""&
don9t bracket pH below $."1 and abo!e 1"."".
Leep buffer bottles tiht closed, especially in case of hih pH buffers.
Pet the temperature of the pH meter and measurin setup to stabiliJe before use.
-heck all @unctions.
2on9t allow static electricity to build up durin measurements.
*tir all buffers and samples durin measurement.
+lace a piece of insulatin material %styrofoam, cardboard& between manetic stirrer and beaker
to pre!ent heatin of the sample.
.e!er rub or wipe electrode bulb, to reduce chance of error due to polariJation. Blottin is
ideal.
2on9t use pH electrode to measure pH outside of its workin rane.
*tore pH electrode in electrode storae solution %or pH $."1 buffer or ".1) L-l solution& when
not in use. .e!er store in deioniJed water.
A$
8ry to always soak lass electrodes in electrode storae solution o!erniht prior to first use.
1se appropriate cleanin procedure if electrode becomes sluish or drifts e/cessi!ely.
Additionally, in the case of the open electrodes6
Always remo!e co!erin from electrode fill hole prior to measurement.
Be careful not to use incorrect fill solution for electrode or application.
2o not allow salt crystals to form inside pH electrodes.
:re(uently inspect electrodes for damae and cloin of e/ternal @unction.
pH of soil and other procedures for pH
measurements
When it comes to pH measurement of solutions, especially diluted, standard procedure is usually
enouh. Howe!er, there are situations when pH measurement can9t be taken out directly , like pH
measurement of meat, cheese or soil. *uch cases re(uire specific sample preparation and preparation
procedure can influence final result.
Pet9s see how the pH measurement of soil looks alike.
pH of soil can chane sinificantly , from acidic in the coniferous forest or on peat bo, to basic on
karst terrain. pH of the soil chanes ability of plants to take nutrients from the round, and some plants
will not row in acidic or basic soils perfect for other plants. 8hus measurement of soil pH is !ery
important , but in no way it is easy. *oil can be dry, and the pH electrode needs to be immersed to
work. pH electrodes are !ery fraile so they can9t be hammered into the round. 8hus measurement
must be done in some other way.
Widely accepted method is to take a sample of the soil, crush any clumps, and close it in a @ar filled
with distilled water. After some !iorous shakin sample should be left for B to 1" minutes to let all
soluble substances to dissol!e and to let all hard parts to sediment. 8hen pH of the solution abo!e
sediment is measured in a standard way and called Msoil pHM.
+rocedure sounds pretty simple, and in fact it is not !ery difficult, howe!er, it must be done !ery
carefully, if the results are to be reliable and comparable. *ample must be taken with a tool that will
not influence final readins. Amount of soil sampled must be always the same. Amount of added water
must be always the same. 8ime of shakin and time the sample is left to dissol!e and to sediment must
be always the same.
Will it sufficeU .ot. A pH measured in the supernatant li(uid may be considerably different than the
readin obtained by placin electrode in the slurry at the bottom. :or a lon time it was belie!ed that
this Msupension effectM is created by the lare @unction potential caused by the presence of chares on
the soil particles. A contrary !iew was published more recently which arued that the chares on the
soil particles either held or repelled hydroen ions, and that the difference in readins was a true
estimate of real differences in pH which e/isted between the suspension reion and the supernatant
li(uid.
But e!en if you will insert electrode always e/actly the same way into the solution, consecuti!e
measurements accuracy will be rarely better then ".A pH unit, as there are still too much unknowns and
chanin elements in the whole process.
pH measurements - further reading
AB
27. 19A66
27. 19A6=
)easurement of pH. 2efinition, standards, and procedures %71+A- Eecommendations A""A& ,
pdf file
E.I. Bates, 2etermination of pH, Wiley, .ew #ork, 196B.
Hans B@arne -hristensen, Arne *alomon and Iert Lokholm, 7nternational pH *cales and
-ertification of pH, Anal. -hem. !ol. 63, no. 1>, >>BA , >91A ,1991.
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