Hanna Instruments HI 4113 User manual

1
Instruction Manual
SENSOR HANDLE
HI
4000-50
HI 4113
NITRATE
COMBINATION
HI 4013HI 4013
HI 4013HI 4013
HI 4013
HI 4113HI 4113
HI 4113HI 4113
HI 4113
Nitrate Ion
SelectiveElectrode
Half-cell
Combination

2
HI4013NitrateHalf-cellHI4013NitrateHalf-cell
HI4013NitrateHalf-cellHI4013NitrateHalf-cell
HI4013NitrateHalf-cell
HI 4113 Nitrate Combination ElectrodeHI 4113 Nitrate Combination Electrode
HI 4113 Nitrate Combination ElectrodeHI 4113 Nitrate Combination Electrode
HI 4113 Nitrate Combination Electrode
I.I.
I.I.
I. Introduction:Introduction:
Introduction:Introduction:
Introduction:
The Hanna HI 4013 and HI 4113 are ion selective elec-
trodes designed for the measurement of nitrate ions in
aqueoussolutions.Theyutilizeareplaceablesensingmod-
ule that contains an organic polymer membrane that is
sensitivetonitrateions.TheHI4013isahalf-cellelectrode
thatrequiresaseparatereference.TheHI4113isacombi-
nationionselectiveelectrode.
IIII
IIII
II. SpecificationsSpecifications
SpecificationsSpecifications
Specifications
Type: PVC membrane with or-
ganic ion exchanger
Ionmeasured: Nitrate(NO3-)
Measurementrange: 0.1Mto1X10-5 M
6200to0.62ppm
Interference:
Organic solvents and cationic detergents must be absent.
RatioofinterferingiontoNO3
-mustbelessthantheratio
indicated below:
300 forF-fluoride
100 forCl-chloride
4 forCO32- carbonate
2 forNO2
-nitrite
0.01 forI-iodide
0.0045 forClO4-perchlorate
Operating Temperature: 0-40°C
Operating pH: 3 to8pH(seeSection
XIII)
Dimensions: 12 mm (OD) X 120 mm
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:::::
TheHI4013andHI4113nitrateelectrodesarepotentio-
metricdevicesusedfortherapiddeterminationoffreeni-
trate ions in water, emulsified foods and plant samples.
Theelectrodefunctionsasasensororionicconductor. The
HI4013requiresaseparatereferenceelectrodetocomplete
itselectrolyticcircuit. The HI4113isacombinationelec-
trodewithaAg/AgClreferenceelectrodewithgelstabilized
Cl-electrolyteinit’sinnerchamber. Theexternalreference
chamber is refillable. The PVC membrane used on the
sensorisimpregnatedwiththeorganicionexchanger.This
organicionexchanger isconsideredacarrierionophorein
that it is capable of shielding and carrying the charged
nitrate ion in it’s polar cage freely through the apolar
regionsof themembrane. Acharge imbalancedevelopes
between the test solution and internal cell of the sensor.
Thisvoltagechangesinresponsetothesample’sionactiv-
ity. When the ionic strength of the sample is fixed, the
voltageisproportionaltotheconcentrationofnitrateionsin
solution.ThesensorfollowstheNernstEquation:
E =Ea +2.3RT/nFlogAion
E =observedpotential
Ea=Referenceand fixedinternalvoltages
R =gasconstant(8.314J/KMol)
n =Chargeonion (-1)
A ion= ion activity in sample
T =absolutetemperatureinK
F =Faradayconstant(9.648x104C/equivalent)

4
IV.IV.
IV.IV.
IV. Design elements of the HI 4013 and HI 4113Design elements of the HI 4013 and HI 4113
Design elements of the HI 4013 and HI 4113Design elements of the HI 4013 and HI 4113
Design elements of the HI 4013 and HI 4113
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 4013 requires the Hanna HI 5315 Double
junctionreferenceelectrodewithHI7078asexternal
electrolyte.
•Hanna HI 4222 pH/ISE/mV meter or other suitable
ionorpH/mVmeter(Note:log/lineargraphpaperis
usefulif an ISE (ion)meter is not available).
•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
StandardsforNitrateMeasurements
0.1Msodiumnitratestandard,500mL HI4013-01
100ppmnitrate standard, 500 mL HI4013-02
1000ppm nitrate standard,500mL HI4013-03
IonicStrengthAdjuster
ISA,500mL HI4013-00
ISISA,500mL HI4013-06
Usingvolumetricpipettesandglasswaremakedilutionsto
brackettheconcentrationofthesamples.Storesamplesin
plastic bottles. Standards with concentrations < 10-3 M
should be prepared daily.
TwomLofHannaISAHI4013-00shouldbeaddedto100
mL sample or standard.
HI4013-06ISISA is Interferent suppressent ISA. Prepare
bydissolving17.32gAl2(S04)3.H20,3.43.g Ag2SO4,1.28g
H3BO4, 2.52g H2NSO3H in approximately 800 mL deion-
izedwater. AdjustpHto3with0.1NNaOH. Diluteto1
liter.Storeinadarkcoloredcontainer.
Fordrinkingwater:10mLofISISAshouldbeaddedtoeach
50mLsample or standard.
VIIVII
VIIVII
VII. General GuidelinesGeneral Guidelines
General GuidelinesGeneral Guidelines
General Guidelines
•Ensuretheo-ringisinstalledonmodulesbeforescrew-
ingintothesensorhandleorinnerstem.

6
•Duetoshippingorstoragetheinternalsolutioninside
thePVCmodules may have developed an airpocket
nearthemembrane.Gentlyshakingthesensordown
(liketheoldstylemercurythermometer)willplacethe
internalsolutionnexttothemembrane.
•Presoaking the Nitrate sensor in a 10-2 M standard
without ISA for at least half-hour before calibration
willhelptooptimizethesensorresponse.
•Donotleaveyoursensorsinstandardorsamples
withISAorISISAforlongperiodsoftime.
•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.
•Avoidlarge changes in temperature(thermal shock)
asitmay damage the sensor.
O-Ring

7
Additional HI 4113 guidelines
•Remove the protective plastic wrap that covers the
ceramicjunctionbeforeassemblingsensorforthefirst
time.
•Addreference HI 7078 fill solution to bottomof fill
holeor empty andrefill fill solution daily before us-
ing.
•During measurement always operate electrode with
thefillholeopen.
•Duringnormaluse,fillsolutionwillslowlydrainout
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
HI4013
The Hanna HI 4013 is a 2 piece design comprised of a
sensor handle (HI 4000-50) and a sensing module (HI
4013-51). The sensor is shipped with two HI 4013-51
modules.
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
withinnermembrane surface.
4. PrepareHI5315referenceelectrodebyfillingelectro-
lytereservoirwithHI7078 fillsolution.
5. Place sensor and reference electrodes into electrode
holderandconnectcableconnectorstometer.
6. SoaktheNitrateelectrodesmembraneinaNitrate
containing standard (0.001M) without ISA before
calibration.
HI4113
TheHannaHI4113isshippeddisassembled.Thesensoris
shippedwithtwoHI4113-51modules.
1. UnwrapParafilm®sealfoundoverceramicjunction
oninnerstemanddiscard.Thisisonlyusedforship-
pingorlongtermstorage.
2. Removesensingconefromshippingvial.Donottouch
thesensingmembranewiththe“H”holepatternon
it.
3. Screwtheconeintotheinnerstemfingertight. Donot
overtighten.
SENSORHANDLE
HI
4000-50

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 dropper pipette provided,addafewdrops
HI7078fillsolutiontotheelectrode.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-
trodebodyuntilfill solutionvolumeisjustbelow fill
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
•Placemeterin mVmode.
•Place100mLofdeionizedwater into a beaker with
stirbar.
•Placereferenceandmeasuringhalf-cellorcombina-
tionelectrodeintopreparedsample.
•Add 1 mL of a standard to beaker. Record the mV
value when stable.
• Addan additional 10 mLof standard to the
solution.RecordthemVwhenreadinghas
HI 4113
NITRATE
COMBINATION

11
stabilized. Thisvalueshouldbe lessthanthe
previousvaluenoted(morenegative).
•DeterminethedifferencebetweenthetwomVvalues.
Anacceptable valueforthis slope is
56±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(HI4113orHI5315reference).
•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,ortheslope of the electrode has
decreased significantly, and procedures above have
not helped, the module should be replaced.
ForHI4013
1. Dry off moduleand sensor handle.
2. Unscrewsensingmoduleandreplacewithanewone.
(HI4013-51).
3. Soak new module in nitrate solution to condition it
beforecalibration.
ForHI4113
1. Drain the fill solution by depressing cap. Rinse elec-
trodewithdistilledordeionizedwater.Drain.

12
2. Unscrewuppercapandslidedowncabletowardcon-
nector.
3. Movespringandouterbodydowncablealso.
4. Dryoffinnerstemandmodulewithasofttissue.
5. Hold inner stem and unscrew module and replace
withanewone.(HI4113-51).
6. Reassembleelectrode(seesectionVII),andrefillwith
electrolyte. Soak new membrane in nitrate solution
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
HI4013-00toadjustionicstrengthatadoseof2mLper
100mLsampleorstandard.ISISA*mayalsobeusedata
doseof10mLfor50mLofsampleorstandard.Themeter
iscalibratedusingfreshlymadestandards thatareinthe
measurementrangeoftheunknowns. Unknownsareread
directly. In the region where the electrode calibration be-
comeslesslinear,morecalibrationpointsareneeded,and
calibrationwillneedtoberepeatedmorefrequently.
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.
*Note:ISISAistherecommendedISAusedforprocedure
4500-NO3-D. published in Standard Methods for the Ex-
aminationofWaterandWastewaterandisaEPAaccepted
methodfordrinkingwater analysis.

13
Procedure:
Followsections VIII andIXtoprepare electrodes formea-
surement.
1) Follow sectionVItopreparestandards/solution. Stan-
dards should bracket and fall within the range of
interest. Standards and solutions should be at the
sametemperature.
•2mLofHI4013-00isaddedto100mLofboth
samplesand standards. OR
•10mLofISISAareaddedto50mLbothsamples
orstandards.
Addstirbarandmixbeforetakingmeasurements.
2) FollowsectionVII;GeneralGuidelinestooptimizetest
set-up.
3) Duringcalibrationitisbesttostartwithlowerconcen-
trationsamplesfirst. Waitforastablereadingbefore
reading/ recording values. Permit longer equilibra-
tiontimesattheselevels(3or4minutes).
Topreventcarryoverandcontaminationofsamples,rinse
sensors with deionized water and remove moisture with
absorbanttissuebetween samples.
Typical HI 4013 and HI 4113 Linearity
0
50
100
150
200
250
300 01234567
-Log of Molar Concentration
mV

14
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 volumeandconcentrationofNO3-standardtothe
sample.mVvaluesarenotedbeforeandaftertheaddition
ofstandard(∆E). Anidealsensorslopecanbeusedinthe
equationbutactualdeterminedslopesatthetemperature
ofmeasurementshouldbeusedifknown(S). Thismethod
ispreprogrammedintheHannaHI4222pH/ISE/mVmeter,
which simplifies the method greatly.
Example:
Nitrateion determination with knownaddition.
1. A 50 mL sample of unknown (VSAMPLE) is placed in a
cleanplasticbeakerwithanelectrode(s).Add50mL
of ISISA*tosample.Mix. mV1isrecorded.
2. 5mL(VSTANDARD)of 10-1M(CSTANDARD)standardisadded
tothebeakerandthemVvaluedecreases.(Note:for
other concentration samples, add a known volume
and concentration of standard to produce approxi-
mately 30 mV change).
The unknown Nitrate 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’
*Note:ISISAisInterferentsuppressentISAseeSection IV.

15
XIIIXIII
XIIIXIII
XIII. pH and InterferentspH and Interferents
pH and InterferentspH and Interferents
pH and Interferents
HI4013/HI4113Nitrateelectrodescanoperateovera pH
range of 3 to 8 but better results are found if pH is kept
constant throughout calibration and test. Sulfuric acid or
NaOHcanbeusedforpHadjustmentoruseISISAtosurpress
interferencesandbufferpH.Limitingthelengthoftimeof
exposure to samples containing interferences will prolong
usefullifeofyourelectrode.Ifsensorhasbeenexposedto
ions above recommended levels, soaking in pure nitrate
solutionswithoutISAwillaidrecoveryoffunction.
XIV.XIV.
XIV.XIV.
XIV. Storage and Care of the HI 4013 andStorage and Care of the HI 4013 and
Storage and Care of the HI 4013 andStorage and Care of the HI 4013 and
Storage and Care of the HI 4013 and
HI 4113 electrodesHI 4113 electrodes
HI 4113 electrodesHI 4113 electrodes
HI 4113 electrodes
TheHI4013sensorcanbestoredinstandardsthat donot
contain ISA for short time periods. For long term storage,
unscrewsensingmodulefromsensorhandleandstoredry
in the shipping vial.
The model HI 4113 combination electrode can be left in
dilute standards that do not contain ISA for short time
periods.Iftheelectrodewillbeusedfrequentlyandneeds
tobereadyforuse,takemeasurestopreventevaporationof
fill solution. Top off fill solution, replace o-ring, fill hole
cover on the fill hole opening, and place sensor in dilute
nitratesolution that does not containISA.Storeelectrode
upright. Prior to use, drain electolyte chamber and refill
withfreshHI7078fillsolution.
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
For NOFor NO
For NOFor NO
For NO33
33
3--
--
-Multiply byMultiply by
Multiply byMultiply by
Multiply by
Moles/L(M)NO3
-toppmNO3 -(mg/L) 62000
ppm(mg/L)toM(moles/L) 1.61X10-5

16
MAN411308/11
WARRANTYWARRANTY
WARRANTYWARRANTY
WARRANTY
HannaInstrumentsIonSelectiveElectrodesarewarranted
to be free of defects in material and workmanship for 6
monthsfromdateofpurchasewhenusedfortheirintended
purposeandmaintainedaccording toinstructions.Ifthey
failtoworkwhenfirstusedcontactyourdealerimmediately.
Damageduetoaccidents,misuse,misapplication,tampering
orlackofprescribedmaintenanceisnotcovered.
HannaInstrumentsreservestherighttomodifythedesign,
constructionorappearanceofitsproductswithoutadvance
notice.