Hanna Instruments HI 4104 User manual

1
Instruction Manual
SENSOR HANDLE
HI
4000-50
HI 4004HI 4004
HI 4004HI 4004
HI 4004
HI 4104HI 4104
HI 4104HI 4104
HI 4104
CalciumIon
SelectiveElectrode
Half-cell
Combination
HI 4104
CALCIUM
COMBINATION

2
HI4004CalciumHalf-cellHI4004CalciumHalf-cell
HI4004CalciumHalf-cellHI4004CalciumHalf-cell
HI4004CalciumHalf-cell
HI 4104 Calcium Combination ElectrodeHI 4104 Calcium Combination Electrode
HI 4104 Calcium Combination ElectrodeHI 4104 Calcium Combination Electrode
HI 4104 Calcium Combination Electrode
I.I.
I.I.
I. Introduction:Introduction:
Introduction:Introduction:
Introduction:
The Hanna HI 4004 and HI 4104 are ion selective elec-
trodes designed for the measurement of calcium ions in
aqueoussolutions.Theyutilizeareplaceablesensingmod-
ule that contains an organic polymer membrane that is
sensitivetocalciumions. TheHI 4004is ahalf-cell elec-
trodethatrequiresaseparatereference.TheHI4104isa
combinationionselectiveelectrode.
IIII
IIII
II. SpecificationsSpecifications
SpecificationsSpecifications
Specifications
Type: PVC membrane with
organicionexchanger
Ionmeasured: Calcium (Ca2+)
Measurementrange: 1.0Mto3X10-6 M
40080to0.12ppm
Interference:
Organicsolvents andcationic detergentsmust beabsent.
RatioofinterferingiontoCa2+ mustbelessthanthe
ratioindicated below:
15000 forNa+sodium
7000 forMg3+ magnesium
700 forNi2+ nickle
300 forFe2+ ferrous
250 forAl3+ aluminum
200 forNH4+ammonium
35 forCu2+ cupric
0.001 forPb2+-lead
Operating Temperature: 0-40°C
Operating pH: 4 to10pH(seeSection
XIII)
Dimensions: 12mm(OD)X120mm
nominal insertion
(0.47”X4.72”)
Connection: BNC

3
III.III.
III.III.
III. Theory of OperationTheory of Operation
Theory of OperationTheory of Operation
Theory of Operation:::::
TheHI4004andHI4104calciumelectrodesarepotentio-
metricdevicesusedfortherapiddeterminationoffreecal-
ciumionsinwater,seawaterandbeverages. Theelectrode
functions as a sensor or ionic conductor. The HI 4004
requiresaseparatereferenceelectrodetocompleteitselec-
trolyticcircuit. The HI4104isacombinationelectrodewith
aAg/AgClreferenceelectrodewithgelstabilizedCl-electro-
lyteinit’sinnerchamber. Theexternalreferencechamber
is refillable. The PVC membrane used on the sensor is
impregnated with the organic ion exchanger.
Thisorganicionexchangerisconsideredacarrierionophore
inthat itiscapable ofshielding andcarryingthe charged
calcium ion in it’s polar cage freely through the apolar
regionsofthe membrane. Acharge imbalancedevelopes
betweenthetestsolutionandinternalcellofthesensor.
Thisvoltagechangesinresponsetothesampleísionactiv-
ity. When the ionic strength of the sample is fixed, the
voltageisproportionaltotheconcentrationofnitrateionsin
solution.ThesensorfollowstheNernstEquation:
E =Ea +2.3RT/nFlogAion
E =observedpotential
Ea=Referenceandfixedinternalvoltages
R =gasconstant(8.314J/KMol)
n =Chargeonion (2+)
A ion= ionactivity insample
T =absolutetemperatureinK
F =Faradayconstant(9.648x104C/equivalent)

4
IV.IV.
IV.IV.
IV. Design elements of the HI 4004 and HI 4104Design elements of the HI 4004 and HI 4104
Design elements of the HI 4004 and HI 4104Design elements of the HI 4004 and HI 4104
Design elements of the HI 4004 and HI 4104
electrodeselectrodes
electrodeselectrodes
electrodes
UpperCap
Spring
O-Ring
CeramicJunction
onInnerStem
FillHole
O-Ringand
Plug
SensingModule
OuterSleeve
Upper
Threads
Liquidjunction
SENSORHANDLE
HI
4000-50
Cap
Sensing
module
Sensor
Handle
O-Ring

5
V.V.
V.V.
V. Equipment required:Equipment required:
Equipment required:Equipment required:
Equipment required:
•The HI 4004 requires the Hanna HI 5315 Double
junctionreferenceelectrodewithHI7082asexternal
electrolyte.
•Hanna HI 4222 pH/ISE/mV meter or other suitable
ionorpH/mVmeter(Note:log/lineargraphpaperis
usefulifan ISE(ion) meteris notavailable).
•Hanna HI 180 magnetic stirrer or equivalent with
magneticstirringbars(Note:Isolatebeakersfromstir-
rermotorheatbyplacinginsulatingmaterialsuchas
foamorcorkbetweenthem).
•HannaHI76404electrodeholderorequivalent.
• Plasticbeakers(HI740036P)orothersuitablemea-
surementvessel.
VI.VI.
VI.VI.
VI. Solutions RequiredSolutions Required
Solutions RequiredSolutions Required
Solutions Required
Standardsfor CalciumMeasurements
0.1M calciumstandard,500 mL HI4004-01
IonicStrengthAdjuster
ISA,500mL HI4004-00
Conditioning and Storage Solution
Calciumstoragesolution,500mL HI4004-45
Usingvolumetricpipettesandglasswaremakedilutionsto
brackettheconcentrationofthesamples.Storesamplesin
plastic bottles. Standards with concentrations < 10-3 M
should be prepared daily.
TwomLofHannaISAHI4004-00shouldbeaddedto
100mL sampleor standard.
VIIVII
VIIVII
VII. General GuidelinesGeneral Guidelines
General GuidelinesGeneral Guidelines
General Guidelines
•Ensuretheo-ringisinstalledon modulesbefore
screwingintothesensorhandleorinnerstem.
O-Ring

6
•Duetoshippingorstoragetheinternalsolutioninside
thePVC modulesmayhavedevelopedanairpocket
nearthemembrane.Gentlyshakingthesensordown
(liketheoldstylemercurythermometer)willplacethe
internalsolutionnexttothemembrane.
•PresoakingtheCalciumsensorinHI4004-45
solution for at least half-hour before calibration will
helptooptimizethesensorresponse.
•Donotleaveyoursensorsinstandardorsamples
withISA forlongperiodsoftime.
•Calibration standards and sample solutions should
havethesameionicstrength.ISAshouldbeaddedto
both samples and standards.
•Calibration standards and sample solutions should
beatsametemperature.
•Thermallyinsulatesolutionvesselfrommagneticstir-
rer.
•Calibration standards and sample solutions should
be stirred at the same rate using identical sized TFE
coatedstirbars.
•Rinseelectrodeswithdistilledordeionizedwaterbe-
tween samples and gently dab dry with lab wipe or
othersoftdisposableabsorbenttoweling.Donotrub
thesensingsurface.
•Check for gas bubbles that may form near sensing
surface (due to solution temperature changes). Tap
offgently.
•Avoidlargechanges intemperature (thermalshock)
asit maydamage thesensor.
Note:Theelectrodemembranewilldevelopaopaque
appearancewhenitbecomeswetted.Thisisnormal.

7
Additional HI 4104 guidelines
•Remove the protective plastic wrap that covers the
ceramicjunctionbeforeassemblingsensorforthefirst
time.
•Add reference HI 7082 fill solution to bottom of fill
hole or empty and refill fill solution daily before us-
ing.
•During measurement always operate electrode with
thefillholeopen.
•Duringnormal use,fill solutionwill slowlydrainout
ofthetaperedconejunctionatthelowerportionofthe
electrode.Excessiveloss(>4cmdropwithin24hours)
isnotnormal.Ifthisoccursverifycapistightenedand
the interface between the internal cone and outer
bodyisfreeofdebris.
•Add filling solution daily to maintain a good head
pressure.Foroptimumresponse,thislevelshouldbe
maintainedandnotbeallowedtodropmorethan2-
3cm(1-inch)belowfillhole.
•Donotuseanelectrodeifcrystallizedsaltsarevisible
insidetheelectrode.Drainelectrode,disassembleand
rinseinternalbodywithdeionizedwater.Reassemble
andrefillwithfreshfillsolution.
•Ifanerraticmeasurementoccurs,checktoseeiffor-
eign matter is seen trapped near the internal cone.
Drainbydepressingtheelectrodecapthenrefillwith
freshfillsolution.
VIII.VIII.
VIII.VIII.
VIII.Electrode PreparationElectrode Preparation
Electrode PreparationElectrode Preparation
Electrode Preparation
HI4004
The Hanna HI 4004 is a 2 piece design comprised of a
sensor handle (HI4000-50) and a sensing module (HI
4004-51).
1. Remove sensing module from shipping vial. Do not
touchthesensingmembranewiththe“H”holepat-
ternonit.
2. Screwthemoduleintothesensorhandlefingertight.
Donotovertighten.

8
3. Holding the assembled electrode at the cable end,
shake the sensor to ensure internal fill solution that
may have separated during shipping is in contact
withinner membranesurface.
4. PrepareHI5315referenceelectrodebyfillingelectro-
lytereservoirwithHI7082 fillsolution.
5. Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
6. SoaktheCalciumelectrodesmembraneinHI4004-45
conditioningsolutionoracalciumstandard (0.01M)
withoutISAbeforecalibration.
SENSORHANDLE
HI
4000-50
HI4104
TheHannaHI 4104is shippeddisassembled. The
sensing module is found in the glass storage vial.
1. UnwrapParafilm®sealfoundoverceramicjunction
oninnerstemanddiscard.Thisisonlyusedforship-
pingorlongtermstorage.
2. Removesensingconefromshippingvial.Donottouch
thesensingmembranewiththe “H” holepatternon
it.
3. Screwtheconeintotheinnerstemfingertight. Donot
overtighten.

9
4. Rinseinnerstemwithdeionizedwatermakingcertain
toweto-ringfoundontheinnerstem.
5. Reassemble electrode by gently pushing the inner
assembly into the outer body, sliding spring down
cable, and screwing cap into place.
6. Removefillholecoverando-ringonfillholespout.
Usingthe dropperpipetteprovided, addafew drops
HI7082fillsolutiontotheelectrode.Invertthe elec-
trodetowettheo-ringandrinsethefillsolutioncham-
ber.
Deionized
Water
Remove
Parafilm
Install
sensing
module

10
7. Holdingthebodyoftheelectrodegentlypressupper
capwithyourthumb.Thispermitsthefillsolutionto
drain out of the body. Release cap and verify elec-
trodereturnstoitsoriginalposition.(Youmayneedto
gentlyassistforthistooccur).
8. Tightentheelectrodecapontothebodyandfillelec-
trodebodyuntil fillsolutionvolumeisjust belowfill
hole.
9. Position electrode in a Hanna HI 76404 electrode
holder(orequivalent)andconnectBNCconnectorto
meter.
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
•Connectelectrode(s)topH/mV/ISEmeter
•PlacemeterinmVmode.
•Place100 mLof deionizedwater intoa beakerwith
stirbar.
•Placereferenceandmeasuringhalf-cellorcombina-
tionelectrodeintopreparedsample.
•Add 1 mL of a standard to beaker. Record the mV
value when stable.
• Addanadditional10mLofstandardtothe solution.
HI 4104
CALCIUM
COMBINATION
RecordthemVwhenreadinghasstabilized. This

11
•DeterminethedifferencebetweenthetwomVvalues.
Anacceptablevaluefor thisslope is
26±4mV(20-25°C).
X.X.
X.X.
X. Corrective actionCorrective action
Corrective actionCorrective action
Corrective action
•Verifymodulehasbeenscrewedintosensorhandleor
innerstem.
•Verify Parafilm®seal has been removed from ce-
ramicjunction(HI4104orHI5315reference).
•Verifyfillsolutionhasbeenaddedtoreferencecham-
ber.
•Verifyelectrodesareconnectedproperlytometerand
meterispowered.
•Verify dilute standards are freshly made and stored.
Remake solutions if appropriate. Store in plastic
bottles.
•If the reading is jumpy or unstable, shake sensor
down(seesectionVII).
•If the sensor slope just misses the suggested slope
window, soaking the sensor in a standard solution
withoutISAmaysolvetheproblem.
•Ifthemembraneisdamaged,theresponsebecomes
extremelysluggish, orthe slopeof theelectrode has
decreased significantly, and procedures above have
not helped, the module should be replaced.
ForHI4004
1. Dry offmodule andsensor handle.
2. Unscrewsensingmoduleandreplacewithanewone.
(HI4004-51).
3. Soaknew moduleincalciumsolution tocondition it
beforecalibration.
ForHI4104
1. Drainthe fillsolution bydepressingcap.Rinse elec-
trodewithdistilledordeionizedwater.Drain.
valueshouldbemorepositivethantheprevious
value noted.

12
2. Unscrewuppercapandslidedowncabletowardcon-
nector.
3. Movespringandouterbodydowncablealso.
4. Dryoffinnerstemandmodulewithasofttissue.
5. Hold inner stem and unscrew module and replace
withanewone.(HI4104-51).
6. Reassembleelectrode(seesectionVII),andrefillwith
electrolyte. Soaknewmembraneincalciumsolution
withoutISAtoconditionbeforecalibration.
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. AdirectreadingISEmeter(HI4222orequiva-
lent)determinesconcentrationoftheunknownbyadirect
readingaftercalibratingthemeterwiththestandards.Add
HI4004-00toadjustionicstrengthatadoseof2mLofper
100mLsampleorstandard. Themeteriscalibratedusing
freshlymadestandards thatareinthemeasurementrange
oftheunknowns. Unknownsarereaddirectly.Intheregion
wherethe electrodecalibrationbecomeslesslinear,more
calibrationpointsareneeded,andcalibrationwillneedto
berepeatedmorefrequently.
A pH/mV meter in mV mode and 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.

13
Procedure:
Followsections VIIIand IXtoprepare electrodesformea-
surement.
1) Follow sectionVItopreparestandards/solution. Stan-
dards should bracket and fall within the range of
interest. Standards and solutions should be at the
sametemperature.
2) 2 mL of HI 4004-00 is added to 100 mL of both
samples and standards.
Addstir barand mixbefore takingmeasurements.
3) FollowsectionVII;GeneralGuidelinestooptimizetest
set-up.
4) Duringcalibrationitisbesttostartwithlowerconcen-
trationsamplesfirst. Waitforastablereadingbefore
reading/ recording values. Permit longer equilibra-
tiontimesattheselevels(3or4minutes).
Topreventcarryoverandcontaminationofsamples,rinse
sensors with deionized water and remove moisture with
absorbanttissue betweensamples.
Typical HI 4004 and HI 4104 Linearity
-80
-60
-40
-20
0
20
40
60
80
100
0123456
-Log of Molar Concentration
mV

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XII.XII.
XII.XII.
XII. Other Measurement TOther Measurement T
Other Measurement TOther Measurement T
Other Measurement Techniquesechniques
echniquesechniques
echniques
Known additionKnown addition
Known additionKnown addition
Known addition
Anunknownconcentrationcanbedeterminedbyaddinga
known volumeandconcentrationofCa2+ standardtothe
sample.mVvaluesarenotedbeforeandaftertheaddition
ofstandard(∆E). Anidealsensorslopecanbeusedinthe
equationbutactualdeterminedslopesatthetemperature
ofmeasurementshouldbeusedifknown(S). Thismethod
ispreprogrammedintheHannaHI4222pH/ISE/mVmeter,
which simplifies the method greatly.
Example:
Calcium ion determination with known addition.
1. A 50 mL sample of unknown (VSAMPLE) is placed in a
cleanplasticbeakerwithanelectrode(s). OnemLof
ISAisaddedtothesampleandpermittedtomix. mV
1isrecorded.
2. 10mL(VSTANDARD)of 10-1M(CSTANDARD)standardisadded
tothebeakerandthemVvalueincreases.(Note:for
other concentration samples, add a known volume
and concentration of standard to produce approxi-
mately 30 mV change).
The unknown calcium concentration in the original
sample(CSAMPLE)canthenbedeterminedbyusingthe
equationthatfollows.
3. Theprocedurecanberepeatedwithsecondstandard
additiontoverifyslopeandoperationofthemethod.
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’
XIII.XIII.
XIII.XIII.
XIII. pH and InterferentspH and Interferents
pH and InterferentspH and Interferents
pH and Interferents
HI4004/HI4104calciumelectrodescanoperateovera

15
pHrangeof4-10. Theelectroderespondstofreecalcium
ionsonly. Precipitates withoxalate,carbonate,phosphate
and complexes with hydroxide, sulfate, and bicarbonate
reducemeasureable calciumfromsolution. Using Known
Addition (section XII) with complexing reagents and pH
adjustmentsmaypermitstotalcalcium tobe measured.
Limitingthelengthoftimeofexposuretosamplescontaining
interferences will prolong useful life of your electrode. If
sensorhasbeenexposedtoionsaboverecommendedlevels,
soakinginpurecalciumsolutionswithoutISAorHI4004-
45 willaidrecoveryoffunction.
XIV.XIV.
XIV.XIV.
XIV. Storage and Care of the HI 4004 andStorage and Care of the HI 4004 and
Storage and Care of the HI 4004 andStorage and Care of the HI 4004 and
Storage and Care of the HI 4004 and
HI 4104 electrodesHI 4104 electrodes
HI 4104 electrodesHI 4104 electrodes
HI 4104 electrodes
TheHI4004sensorcanbestoredinHI4004-45forshort
timeperiods.Forlongtermstorage,unscrewsensingmod-
ulefrom sensorhandleand storedryin theshippingvial.
ThemodelHI4104combinationelectrodecanbeleftin
HI4004-45forshorttimeperiods.Iftheelectrodewillbe
usedfrequentlyand needstobereadyforuse,take mea-
sures to prevent evaporation of fill solution. Top off fill
solution,replaceo-ring,fillholecoveronthefillholeopen-
ing, and place sensor in HI 4004-45 storage and condi-
tioningsolution.Storeelectrodeupright.Priortouse,drain
electolytechamberand refillwith freshHI 7082fill solu-
tion.
For long term storage, the electrode should be drained,
disassembled and washed of salts with deionized water.
Wrap the ceramic junction in Parafilm®or other sealing
wrap. Unscrew the module and store dry in the shipping
vial.Refrigerationofmodulewillextenditslife.Storedis-
assembledelectrodeinstorageboxprovidedwithelectrode.
XV.XV.
XV.XV.
XV. Conversion tablesConversion tables
Conversion tablesConversion tables
Conversion tables Multiply byMultiply by
Multiply byMultiply by
Multiply by
Moles/L(M)Ca
2+ toppm Ca 2+(mg/L) 40080
ppm(mg/L)toM(moles/L) 2.49X10-5

16
MAN4104 07/06R1
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.