Hanna Instruments HI 4107 User manual

1
HI 4007HI 4007
HI 4007HI 4007
HI 4007
HI 4107HI 4107
HI 4107HI 4107
HI 4107
Chloride Ion
SelectiveElectrode
Instruction Manual
CHLORIDE
HI 4007
HI 410
COMBINATION
7
CHLORIDE
Half-cell
Combination

2
HI4007ChlorideHalf-cellHI4007ChlorideHalf-cell
HI4007ChlorideHalf-cellHI4007ChlorideHalf-cell
HI4007ChlorideHalf-cell
HI 4107 Chloride Combination ElectrodeHI 4107 Chloride Combination Electrode
HI 4107 Chloride Combination ElectrodeHI 4107 Chloride Combination Electrode
HI 4107 Chloride Combination Electrode
I.I.
I.I.
I. Introduction:Introduction:
Introduction:Introduction:
Introduction:
The Hanna HI 4007and HI 4107 are ion selective elec-
trodes designed for the measurement of chloride ions in
aqueous solutions. The HI 4007 is a solid state half-cell
sensorthatrequiresaseparatereference.TheHI4107isa
combinationionselectiveelectrode.
IIII
IIII
II. SpecificationsSpecifications
SpecificationsSpecifications
Specifications
Type: SolidStateelectrodewith
aSilverChloridepellet.
Ion(s)measured: Chloride(Cl-)
Measurementrange: 1.0Mto5X10-5M
35,500to1.8ppm
Interferingions: Cyanide,andMercuryions
mustbeabsent.RatioofinterferingiontoCl-mustbeless
thanthe ratio indicated below:
1.0 forl-iodide
3.5 forBr-bromide
forCO32- carbonate
1.0 forOH-hydroxide
0.01 forS2O3
2- thiosulfate
Operating Temperature: 0-80°C
Operating pH: 2-11pH
Dimensions: 12 mm (OD) X 120 mm
nominal insertion
(0.47”X4.72”)
Connection: BNC

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III.III.
III.III.
III. Theory of OperationTheory of Operation
Theory of OperationTheory of Operation
Theory of Operation:::::
TheHI4007orHI4107chlorideelectrodesarepotentio-
metricdevicesusedfortherapiddeterminationoffreechlo-
rideionsingroundwater,boilerwateranddrinkingwater.
Theelectrodefunctionsasasensororionicconductor. The
HI4007requiresaseparatereferenceelectrodetocomplete
itselectrolyticcircuit. TheHI4107hasareferenceelectrode
incorporatedinitsdesign.Thesilverchloridepelletisprac-
tically insoluble in the test solutions being measured and
producesapotentialchangeduetochangesinthesample’s
ionactivity.Whentheionicstrengthofthesampleisfixed
by the addition of ISA, the voltage is proportional to the
concentrationofchlorideionsinsolutionandtheelectrode
followstheNernstequation.
E=Ea +2.3RT/nFlogAion
E=observedpotential
Ea=Referenceandfixedinternalvoltages
R=gasconstant(8.314J/KMol)
n= Chargeonion (-1)
A i=ion activity in sample
T=absolutetemperatureinK
F=Faradayconstant(9.648x104 C/equivalent)

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IV.IV.
IV.IV.
IV. Design elements of the HI 4007 and HI 4107Design elements of the HI 4007 and HI 4107
Design elements of the HI 4007 and HI 4107Design elements of the HI 4007 and HI 4107
Design elements of the HI 4007 and HI 4107
electrodeselectrodes
electrodeselectrodes
electrodes
CHLORIDE
HI 4007
Cap
Sensing
Membrane
Sensor
Handle
UpperCap
Spring
O-Ring
CeramicJunction
onInnerStem
FillHole
O-Ringand
Plug
Sensing
Membrane
OuterSleeve
Upper
Threads
Liquidjunction

5
V. Equipment required:V. Equipment required:
V. Equipment required:V. Equipment required:
V. Equipment required:
•HannaHI5315DoubleJunctionReferenceElectrode
withHI7072FillSolutionforHI4007.
•Hanna HI 4222 pH/ISE/mV meter or other suitable
ionorpH/mVmeter.(Note:log/lineargraphpaperis
usefulif an ISE(ion) meter isnot available.
•Hanna HI 180 Magnetic Stirrer or equivalent with
Tefloncoatedstirringbars(HI731320). (Note:iso-
latebeakersfromstirrermotorheatbyplacinginsu-
latingmaterialsuchasfoamorcorkbetweenthem).
•HannaHI76404ElectrodeHolderorequivalent.
•Plasticbeakers(HI740036P)orothersuitablemea-
surementvessel.
VI.VI.
VI.VI.
VI. Solutions RequiredSolutions Required
Solutions RequiredSolutions Required
Solutions Required
for Chloride Measurementsfor Chloride Measurements
for Chloride Measurementsfor Chloride Measurements
for Chloride Measurements
Select appropriate Hanna Instruments standard and ISA
fromthelistbelow:
0.1MSodiumChlorideStandard,500mL HI4007-01
100ppm Chloride standard, 500mL HI4007-02
1000ppmChloridestandard,500mL HI4007-03
ISA,500mL HI4000-00
Usingvolumetricpipettesandglasswaremakedilutionsto
brackettheconcentrationofthesamples. Standardswith
concentrations <10-3 M (35.5 ppm) should be prepared
daily.
TwomLofHanna ISAforHalideelectrodes(HI4000-00)
shouldbeaddedto100mLofsampleorstandard.
A user prepared acetate pH buffer may also be used to
adjustsamplestoapproximately4pH. Add10mLper100
mL sample or standard. Prepare 250 mL by dissolving
19.5 g ammonium acetate and 15.0 mL glacial acetic
acid in 200 mL deionized water and diluting to volume.

6
Auser supplied oxidizingreagent may be used tosupress
interferences such as hydroxide, sulfide, bromide, ammo-
niaorcyanide. Add10mLto100mLstandardorsample.
Permitsampletomix10minutesbeforemeasurementsare
taken. Discard samples and standards promptly as the
chloridein these will oxidizeuponstanding making them
unrelible.Donotpermit electrodestoremaininthissolu-
tionforlongperiodsoftime. Work in ahoodandprotect
eyesandskin.Prepareoxidizingreagentbydiluting6.25
mL analytical grade concentrated nitic acid into approxi-
mately800mLdeionizedwater.Mixcarefully.Diluteto1
liter.
VIIVII
VIIVII
VII. General GuidelinesGeneral Guidelines
General GuidelinesGeneral Guidelines
General Guidelines
•Calibration standards and sample solutions should
havethesameionicstrength.ISA,acetatebuffer or
oxidizing reagent should be added to both samples
and standards in the same ratio.
•Calibration standards and sample solutions should
beatsametemperature.
•Thermally insulate beaker with standard or sample
frommagneticstirrer.
•Calibration standards and sample solutions should
be stirred at the same rate using identical sized TFE
coatedstirbars.
•Rinseelectrodepairwithdistilledordeionizedwater
between samples and gently dry off using soft dis-
posable absorbent toweling. Do not rub sensor sur-
face.
•Presoaking chloride sensor in a dilute standard will
optimize response. Do not use concentration above
10-3M.
•A scratched, pitted, or tarnished pellet surface can
causedrift,alossoflowlevelresponse,orpoorrepeat-
ability. Optimumresponsecanberestoredbyremov-
ingthedamagedsurfacewiththemicroabrasivestrip
HI4000-70.

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HI4007
•Removeprotectivecoverfromsensortip.
•PrepareHI5315referenceelectrodebyfillingelectro-
lytereservoirwithHI7072fillsolution.
•Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
HI4107
•Remove the protective plastic wrap that covers the
ceramicjunctionbeforeassemblingsensorforthefirst
time.
•HI7072referencefillsolutionshouldbeaddeddaily
toelectrolytereserviorbeforeelectrodeuse.
•During measurement always operate electrode with
thefillhole open.
•Duringnormaluse, fill solution will slowlydrainout
ofthetaperedconejunctionatthelowerportionofthe
electrode.Excessiveloss(>4cmdropwithin24hours)
isnotnormal.Ifthisoccursverifycapistightenedand
the interface between the internal cone and outer
bodyisfreeofdebris.
•Addfillsolutiondailytomaintainagoodheadpres-
sure.Foroptimumresponse,thislevelshouldbemain-
tainedandnotbeallowedtodropmorethan2-3cm
(1-inch) below fill hole. It must cover the ceramic
foundontheinnerstem.
•Ifanerraticmeasurementoccurs,checktoseeiffor-
eign matter is seen trapped near the internal cone.
Drainand refill with freshfillsolution.
•Avoidlarge changes intemperature (thermal shock)
asitmaydamage the sensor.

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VIII.VIII.
VIII.VIII.
VIII. Electrode PreparationElectrode Preparation
Electrode PreparationElectrode Preparation
Electrode Preparation
HI4007
1. Removeprotectivecoverfromsensortip.
2. Preparereferenceelectrodebyfillingouterelectrolyte
reservoirwithHI7072.
3. Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
HI4107
1. Unwrapplasticfilmsealfoundoverceramicjunction
oninnerstemanddiscard.Thisisonlyusedforship-
ping and long term storage.
2. Rinseinnerstemwithdeionizedwatermakingcertain
towettheo-ringfoundontheinnerstem.
3. Reassemble electrode by gently pushing the inner
assembly into the outer body, sliding spring down
cable, and screwing cap into place.
4. Removefillholecoverando-ringonfillholespout.
5. Usingthedropperpipetteprovided,addafewdrops
HI7072fill solutiontotheelectrode,wettingtheo-
ring and rinsing out the fill solution chamber.
Deionized
Water
Remove
Parafilm

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6. Holdingthebodyoftheelectrodegentlypress upper
capwithyourthumb.Thispermitsthefillsolutionto
drain out of the body. Release cap and verify elec-
trodereturnstoitsoriginalposition.(Youmayneedto
gentlyassistforthistooccur).
7. Tightentheelectrodecapontothebodyandfillelec-
trodebodyuntilfill solutionvolumeisjustbelowfill
hole.
8. Position electrode in a Hanna HI 76404 electrode
holder (orequivalent)and connect plugtometer.
HI 4107
CHLORIDE
COMBINATION

10
IX.IX.
IX.IX.
IX. Quick Check of Electrode SlopeQuick Check of Electrode Slope
Quick Check of Electrode SlopeQuick Check of Electrode Slope
Quick Check of Electrode Slope
•ConnectsensorstopH/mV/ISEmeter
•PlacemeterinmVmode.
•Place100mLofDIWintoabeakerwithstirbar.
•Placereferenceandmeasuringhalf-cellintoprepared
sample.
•Add 1 mL of a standard (0.1 M or 1000 ppm stan-
dard)tobeaker.RecordthemVvaluewhenstable.
•Addanadditional10-mLofstandardtothesolution.
Record the mV when reading has stabilized. This
value should be less than the previous noted (more
negative).
•Determinethedifferencebetweenthetwo-mVvalues.
Anacceptablevalueforthisslopeis-56±4mV.
X.X.
X.X.
X. Corrective actionCorrective action
Corrective actionCorrective action
Corrective action
•Verifyprotectivecaphasbeenremoved.(HI4007)
•Verify plastic film has been removed from inner
stem.(HI4107)
•Verifyelectrodesareconnectedproperlytometerand
meterispowered.
•Verify dilute standards are freshly made and stored.
Remakesolutionsifappropriate.
•If the sensor slope just misses the suggested slope
window,soakingthesensorinadilutestandardmay
solve the problem. (Choose 10-3 M chloride or 100
ppm standard).
•A scratched sensing surface can be polished with HI
4000-70 polishing strip. Cut off approximately 1
inchofthemicro-abrasivestrip.Wetthefrostedside
with deionized water and place against damaged
membraneoftheelectrode. Placeyourthumbagainst
the shiny backing and slowly rotate back and forth
while applying gentle pressure. Continue polishing
untilyouaresatisfiedwiththesurface.

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Ifdark deposits appearson polishing stripmovethe
paper slightly and continue polishing.
•If the sensor slope just misses the suggested slope
window,soakingthesensorinastandardmaysolve
theproblem.
•Ifthemembraneisdamaged,theresponsebecomes
extremelysluggish,or the slope oftheelectrode has
decreased significantly, and procedures above have
nothelped,thesensor shouldbereplaced.
XI.XI.
XI.XI.
XI. Direct Calibration and MeasurementDirect Calibration and Measurement
Direct Calibration and MeasurementDirect Calibration and Measurement
Direct Calibration and Measurement
This method is a simple procedure for measuring many
samples. A direct reading ISE meter (HI 4222 or equiva-
lent)determinesconcentrationoftheunknownbyadirect
readingaftercalibratingthemeterwiththestandards.The
meter is calibrated with two or more freshly made stan-
dards that are in the linear measurement range of the
unknowns. Morecalibrationstandardsarerequiredinnon-
linear regions. Unknowns are read directly. At very low
levelsofchloride,specialprecautionsmustbeemployedfor
reproduciblemeasurements. Waterusedforstandardsmust
bechloridefreeandsensorsandglasswaremustberinsed
repeatedly with this water to prevent carry over. In the
regionwheretheelectroderesponseappearscurved,more
calibration pointsareneeded,andcalibrationwillneedto
berepeatedmorefrequently.
A pH/mV meter in mV mode with semi log graph paper
mayalsobeused. Twoormorefreshlypreparedstandards
that are in the measurement range of the unknowns are
measuredinmVmodeonthemeter.
These values are plotted on the semi-log paper and the
points are connected to form a straight-line curve. When
samples are measured, their mV values are converted to
concentrationbyfollowingthemVtotheconcentrationaxis
onthesemi-logplot.

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Procedure
1) Follow sections VIII and IX to prepare sensors for
measurement.
2) Follow sectionVItopreparestandards/solution. Stan-
dards should bracket and fall within the range of
interest.
TwomLHI4000-00ISA,or10mLacetatepHbuffer
or10mLofoxidizingreagentisaddedto100mLof
both samples and standards. Add stir bar and mix
before taking measurements. Measurements using
theoxidizingreagentmustbemade10minutesafter
mixingandnotpermittedreactlonger.
3) Follow sectionVII;GeneralGuidelinestooptimizetest
set-up.
4) Duringcalibrationitisbesttostartwithlowerconcen-
trationsamplesfirst. Waitforastablemeasurement
before recording values. Slightly longer equilibra-
tionsarerequiredatlowerconcentrations.
5) Topreventcarryoverandcontaminationofsamples,
rinsesensorswithDIWandblotdrybetweensamples.
0
50
100
150
200
250
300
01234567
-Log of Concentration
mV
Typical Linearity for HI 4007 and HI 4107 Chloride

13
XII.XII.
XII.XII.
XII. Other Measurement TOther Measurement T
Other Measurement TOther Measurement T
Other Measurement Techniquesechniques
echniquesechniques
echniques
KnownAddition (forCl-)
Anunknownconcentrationcanbedeterminedbyaddinga
known amount (volume and concentration) of measured
ion to a known volume of the sample. This technique is
called Known Addition. The method can use an ideal
sensorslope,butactualdeterminedslopesatthetempera-
tureofmeasurementshouldbeusedifknown. Thismethod
ispreprogrammedintheHannaHI4222pH/ISE/mVmeter,
which simplifies the method greatly.
Example:Chlorideiondeterminationwithknownaddition.
1. A50mLsampleofunknown (Vsample) is placed in
a clean plastic beaker with a chloride sensor. Add 2
mLofacetatepHbufferorHI4000-00ISA(VISA) ORif
chloride l electrode interferences are known to exist,
add 50 mL oxidizing reagent (VISA). Mix well. and
recordthestablemVvalue.(mV1)
2. 5mL(Vstd)of10-3M(Cstd)standardisaddedtothe
beaker and the mV value decreases. The unknown
chloride concentration in the original sample
(Csample) can then be determined by the following
equation.
3. The procedure can be repeated with a second stan-
dard addition to verify slope and operation of the
method.
C
sample
=(V
T
)10
∆E/S
- (V
S’
)
C
standard
V
standard
V
sample
V
S’
(V
sample
+V
standard
+V
ISA
)= V
T
(V
sample
+V
ISA
)= V
S’

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Achlorideelectrodemaybeusedasanindicatortofollow
the progress of a chloride tiration with silver nitrate. The
electrode can be used in colored samples where other
indicatorssufferfrominterferences.Duringthetitrationthe
sensorfollowsthedecreaseinchlorideconcentrationwhile
smalladditionsofsilvernitatetitrantareadded.Thesilver
reactswiththechlorideionsformingaprecipitateof silver
chloride. Atthestoichiometricendpoint,alargechangein
mV occurs. Measurements may be automated by use of
theHannaTitratorHI901ortitratedmanually.
XIII.XIII.
XIII.XIII.
XIII.pHpH
pHpH
pH
The HI 4107 and HI 4007 electrodes may be used in
solutionswithpHvaluesbetween2and11. Samplesthat
fallbeyondthisrangeshouldbeadjustedwithacetatepH
buffer.SeeSectionVI.
TitrationTitration
TitrationTitration
Titration
XIV. SXIV. S
XIV. SXIV. S
XIV. Storage and Care of the HI 4007 andtorage and Care of the HI 4007 and
torage and Care of the HI 4007 andtorage and Care of the HI 4007 and
torage and Care of the HI 4007 and
HI 4107 sensorsHI 4107 sensors
HI 4107 sensorsHI 4107 sensors
HI 4107 sensors
TheHI4007sensorcanbestoredinverydilutestandards
(<10-4 M)forshortperiodsoftimeandshouldbestored
drywiththeprotectivecaponwhennotinuse.
The model HI 4107 combination electrode can be left in
dilutestandards(<10-4 M)forshorttimeperiods.
Forlongtermstorage,theelectrodeshouldbedrainedand
washedofsaltswithdistilledotdeionizedwater.Unscrew
theuppercapandmoveoutersleeveupcable. Wrapthe
ceramic junction on the inner stem with Parafilm®or
othersealingwrap.Placetheprotectivecapprovidedover
thesensormembrane. Storedrydisassembledelectrodein
storageboxprovidedwithelectrode.

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XV.XV.
XV.XV.
XV. Conversion tablesConversion tables
Conversion tablesConversion tables
Conversion tables
For ClFor Cl
For ClFor Cl
For Cl--
--
-MultiplybyMultiplyby
MultiplybyMultiplyby
Multiplyby
Moles/L(M)toppm(mg/L) 3.500x104
ppm(mg/L)toM(moles/L) 2.857x10-5

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MAN4107 05/08
WARRANTYWARRANTY
WARRANTYWARRANTY
WARRANTY
HannaInstrumentsIonSelectiveElectrodesarewarranted
to be free of defects in material and workmanship for 6
monthsfromdateofpurchasewhenusedfortheirintended
purposeandmaintained accordingtoinstructions. Ifthey
failtoworkwhenfirstusedcontactyourdealerimmediately.
Damageduetoaccidents,misuse,misapplication,tampering
orlackofprescribedmaintenanceisnotcovered.
HannaInstrumentsreservestherighttomodifythedesign,
constructionorappearanceofitsproductswithoutadvance
notice.