Hanna Instruments HI 4102 User manual

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HI 4002HI 4002
HI 4002HI 4002
HI 4002
HI 4102HI 4102
HI 4102HI 4102
HI 4102
Bromide Ion
SelectiveElectrode
Instruction Manual
Half-cell
Combination
BROMIDE
HI 4002
HI 4102
BROMIDE
COMBINATION

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HI4002BromideHalf-cellHI4002BromideHalf-cell
HI4002BromideHalf-cellHI4002BromideHalf-cell
HI4002BromideHalf-cell
HI 4102 Bromide Combination ElectrodeHI 4102 Bromide Combination Electrode
HI 4102 Bromide Combination ElectrodeHI 4102 Bromide Combination Electrode
HI 4102 Bromide Combination Electrode
I.I.
I.I.
I. Introduction:Introduction:
Introduction:Introduction:
Introduction:
The Hanna HI 4002and HI 4102 are ion selective elec-
trodes designed for the measurement of Bromide ions in
aqueous solutions. The HI 4002 is a solid state half-cell
sensorthatrequiresaseparatereference.TheHI4102isa
combinationionselectiveelectrode.
IIII
IIII
II. SpecificationsSpecifications
SpecificationsSpecifications
Specifications
Type: SolidStateelectrodewith
aSilverBromidepellet.
Ion(s)measured: Bromide(Br--
--
- )
Measurementrange: 1.0Mto1X10-6M
79,910to0.08ppm
Interferingions: Cyanide, and Mercury
mustbeabsent.Ratioof
interferingiontoBr--
--
-must
belessthantheratio
indicated below:
0.01 forI--
--
-iodide
0.01 forCN--
--
-cyanide
50 forCl--
--
-Chloride
Operating Temperature: 0-80°C
Operating pH: 2-12.5pH
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:::::
TheHI4002orHI4102Bromideelectrodesarepotentio-
metricdevicesusedfortherapiddeterminationoffreeBro-
mideionsinfoodproducts,beverages,plants,soilsandas
anindicatorintitrations.Theelectrodefunctionsasasen-
sor or ionic conductor. The HI 4002 requires a separate
referenceelectrodetocompleteitselectrolyticcircuit. The
HI4102incorporates areferenceelectrode.ThesilverBro-
mide pellet is practically insoluble in the test solutions
being measured and produces a potential change due to
changesinthesample’sionactivity.Whentheionicstrength
ofthesampleisfixedbytheadditionofISA,thevoltageis
proportionalto theconcentration ofbromide ionsinsolu-
tionandtheelectrodefollowstheNernstequation.
E=Ea +2.3RT/nFlogAion
E=observedpotential
Ea=Referenceandfixedinternal voltages
R=gasconstant(8.314J/KMol)
n= Chargeonion(1-)
A i=ion activity in sample
T=absolutetemperature inK
F=Faradayconstant(9.648x104C/equivalent)

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IV.IV.
IV.IV.
IV. Design elements of the HI 4002 and HI 4102Design elements of the HI 4002 and HI 4102
Design elements of the HI 4002 and HI 4102Design elements of the HI 4002 and HI 4102
Design elements of the HI 4002 and HI 4102
electrodeselectrodes
electrodeselectrodes
electrodes
BROMIDE
HI 4002
Cap
Sensing
Membrane
Sensor
Handle
UpperCap
Spring
O-Ring
CeramicJunction
onInnerStem
FillHole
O-Ringand
Plug
Sensing
Membrane
OuterSleeve
Upper
Threads
Liquidjunction

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V.V.
V.V.
V. Equipment required:Equipment required:
Equipment required:Equipment required:
Equipment required:
•HannaHI5315DoubleJunctionReferenceElectrode
withHI7072FillSolutionforHI4002.
•Hanna HI 4222 pH/ISE/mV meter or other suitable
ionorpH/mVmeter.(Note:log/lineargraphpaperis
usefulifan ISE(ion) meteris notavailable).
•HannaHI180MagneticStirrerorequivalentwithTFE
coatedstirringbars(HI731320). Note:isolatebea-
kers from stirrer motor heat by placing insulating
materialsuchasfoamorcorkbetweenthem.
•HannaHI76404ElectrodeHolderorequivalent.
•Plasticbeakers(HI740036P)orothersuitablemea-
surementvessel.
VI.VI.
VI.VI.
VI. Solutions RequiredSolutions Required
Solutions RequiredSolutions Required
Solutions Required for Bromide Measurementsfor Bromide Measurements
for Bromide Measurementsfor Bromide Measurements
for Bromide Measurements
0.1M BromideStandard,500mL HI4002-01
ISA,500mL HI4000-00
ForMolarsolutions:
Usingvolumetricpipettesandglasswaremakeserialdilu-
tions to approximately bracket the concentration of the
samples. Standardswithconcentrations <10-3Mshould
be prepared daily.
TwomLofHannaISAforHalideelectrodes (HI4000-00)
shouldbe addedto 100mLof sampleorstandard.
Forppmsolutions:
Prepare 799 ppm bromide standard by diluting HI4002-
01:Pipette100mL standardtoa 1litervolumetric flask.
Adddeionizedwatertovolume.Usingadditionalvolumet-
ricpipettesandglasswaremakeserialdilutionsofthis799
ppm standard to approximately bracket the concentration
ofthesamples. Standardswithconcentrations<80ppm
should be prepared daily.
TwomLofHannaISAforHalideelectrodes (HI4000-00)
shouldbe addedto 100mLof sampleorstandard.

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VIIVII
VIIVII
VII. General GuidelinesGeneral Guidelines
General GuidelinesGeneral Guidelines
General Guidelines
•Calibration standards and sample solutions should
havethesameionicstrength.ISAshouldbeaddedto
bothsamplesandstandardsinthesameratio.1part
ISAto50partsstandardisthenormaldosing.
•Concentrated samples (>1 M) should be diluted
beforemeasurement. Multiplythefinalresultbythe
correspondingdilutionfactor.
•For high ionic strength samples, prepare standards
with similar ionic strength by increasing the ISA
addiiton.
•Calibration standards and sample solutions should
beatsametemperature.
•The magnetic stirrer may generate heat. Thermally
insulate beaker containing standard or sample from
magnetic stirrer by placing cork or other insulative
sheetbetweenbeakerandstirrerplate.
•Calibration standards and sample solutions should
be stirred at the same rate using identical sized TFE
coatedstirbars.
•Rinseelectrodepairwithdistilledordeionizedwater
between samples and gently dab dry with soft dis-
posableabsorbenttoweling.Donotrubelectrodes.
•Presoaking bromide sensor in a dilute standard will
optimizeresponse.Useconcentrationsapproximately
10-3Morless.
•A scratched, pitted, or tarnished pellet surface can
causedrift,alossoflowlevelresponse,orpoorrepeat-
ability. Optimumresponsecanberestoredbyremov-
ingthedamagedsurfacewiththemicroabrasivestrip
HI4000-70.
•Avoidlargechanges intemperature (thermalshock)
asit maydamagethesensor.
•Gasbubblesmayformfromsolutionout-gassingdue
totemperaturechange. Gentlytapbodyofsensorto
dislodgethem frommembranesurface.

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HI4002
•Removeprotectivecoverfromsensortip.
•PrepareHI5315referenceelectrodebyfillingelectro-
lytereservoirwithHI7072fillsolution.
•Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
HI4102
•Remove the protective plastic wrap that covers the
ceramicjunctionbeforeassemblingsensorforthefirst
time.
•HI7072referencefillsolutionshouldbeaddeddaily
toelectrolytereserviorbeforeelectrodeuse.
•During measurement always operate electrode with
thefillholeopen.
•Duringnormal use,fill solutionwillslowlydrainout
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 refillwith freshfill solution.

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VIII.VIII.
VIII.VIII.
VIII. Electrode PreparationElectrode Preparation
Electrode PreparationElectrode Preparation
Electrode Preparation
HI4002
1. Removeprotectivecoverfromsensortip.
2. Preparereferenceelectrodebyfillingouterelectrolyte
reservoirwithHI7072.
3. Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
HI4102
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,addafew drops
HI7072fillsolutionto theelectrode,wetting theo-
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-
trodebodyuntilfillsolutionvolume isjustbelowfill
hole.
8. Position electrode in a Hanna HI 76404 electrode
holder (orequivalent)andconnect plugto meter.
HI 4102
BROMIDE
COMBINATION

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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.
•Placeelectrodesintopreparedsample.
•Add 1 mL of a standard (0.1 M or 1000 ppm stan-
dard)tobeaker.RecordthemVvaluewhenstable.
•Addanadditional10mLofstandardtothesolution.
Record the mV when reading has stabilized. This
value should be less than the previous noted (more
negative).
•DeterminethedifferencebetweenthetwomVvalues.
Anacceptablevalueforthisslopeis-56±4mV.
X.X.
X.X.
X. Corrective actionCorrective action
Corrective actionCorrective action
Corrective action
•Verifyprotectivecaphasbeenremoved(HI4002).
•Verifyplasticfilmhasbeenremovedfrominnerstem
(HI4102).
•Verifyelectrodesareconnectedproperlytometerand
meterispowered.
•Verify dilute standards are freshly made and stored.
Remakesolutionsifappropriate.
•If the sensor slope just misses the suggested slope
window,soakingthesensorinadilutestandardmay
solvethe problem.(<10-3Mbromide or <80ppm
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. Ifdarkdepos-
itsappearon polishingstrip movethepaperslightly
and continue polishing.