PrecipitationTitration:DeterminationofChloridebytheMohrMethod

byDr.DenizKorkmaz

Introduction

Titrationisaprocessbywhichtheconcentrationofanunknownsubstanceinsolutionis
determinedbyaddingmeasuredamountsofastandardsolutionthatreactswiththe
unknown.Thentheconcentrationoftheunknowncanbecalculatedusingthestoichiometryofthereactionand
thenumberofmolesofstandardsolutionneededtoreachthesocalledendpoint.
Precipitationtitrationsarebaseduponreactionsthatyieldioniccompoundsoflimited
solubility.Themostimportantprecipitatingreagentissilvernitrate.Titrimetricmethods
baseduponsilvernitratearesometimestermedargentometricmethods.Potassium
chromatecanserveasanendpointindicatorfortheargentometricdeterminationof
chloride,bromideandcyanideionsbyreactingwithsilverionstoformabrickredsilver
chromateprecipitateintheequivalencepointregion.
TheMohrmethoduseschromateionsasanindicatorinthetitrationofchlorideionswithasilvernitrate
standardsolution.Afterallthechloridehasbeenprecipitatedaswhitesilverchloride,thefirstexcessoftitrant
resultsintheformationofasilverchromateprecipitate,whichsignalstheendpoint(1).Thereactionsare:

Byknowingthestoichiometryandmolesconsumedattheendpoint,theamountof
chlorideinanunknownsamplecanbedetermined.Thisreportdescribesexperiments
aimedatdeterminingtheconcentrationofchlorideinasolidsample
Discussion
ThewellknownMohrsmethodinwhichalkalineoralkalineearthchloridesreactwith
silvernitrateinthepresenceofafewdropsofpotassiumchromatesolutionasindicatorisasimple,directand
accuratemethodforchloridedetermination.
Inthisexperiment,theamountofchlorideinanunknownsamplewasdeterminedby
Mohrtitration.ThetitrationwascarriedoutatapHbetween7and10becausechromate
ionistheconjugatebaseoftheweakchromicacid(2,3).Therefore,whenthepHislowerthan7,chromate
ionisprotonatedandthechromicacidformpredominatesinthe
solution.Consequently,inmoreacidicsolutionsthechromateionconcentrationistoo
lowtoproducetheprecipitateattheequivalencepoint.IfthepHisabove10,brownish
silverhydroxideformsandmaskstheendpoint.AsuitablepHwasachievedby
saturatingtheanalytesolutionwithsodiumhydrogencarbonate.
Sincethesolubilitiesofsilverchlorideandsilverchromatedependontemperature,all
tirationswerecarriedoutataboutthesametemperature.Goodstirringduringtheaddition
ofthesilvernitrateisalsorequiredforasharpandreproducibleendpoint;otherwise,
silverchromatethatformslocallybeforetheendpointcanbecomeoccludedinthesilver
chlorideprecipitateinsteadofredissolving.
Standardsilvernitratesolutionandthesilverchlorideprecipitatesformedwereprotectedfromlightatall
timesbecausesilverchloridedecomposesaccordingto:
2AgClAg(s)+Cl(g)

Thesilverionconcentrationatchemicalequivalenceinthetitrationofchloridewith
silverionsisgivenby:
[Ag]=
=
=1.35x10M
+
5

Thechromateionconcentrationrequiredtoinitiateformationofsilverchromateunder
thisconditioncanbecomputedfromthesolubilityproductconstantforsilverchromate:
4

[CrO]=
=
=6.610M
2
3

Inprinciple,anamountofchromatetogivethisconcentrationshouldbeadded,inorder
todeveloptheredprecipitateaftertheequivalencepoint.However,achromateion
concentrationof6.6x103Mimpartssuchanintenseyellowcolortothesolutionthat
formationoftheredsilverchromateisnotreadilydetected.Thus,lowerconcentrationsof
chromateionaregenerallyused.Anexcessofsilvernitrateisthereforerequiredbefore
precipitationbegins.Anadditionalexcessofthereagentmustalsobeaddedtoproduce
enoughsilverchromatetobeseenovertheheavywhiteprecipitateofsilverchloride.
ThesetwofactorscreateapositivesystematicerrorintheMohrmethodthatbecomes
significantinmagnitudeatreagentconcentrationslowerthanabout0.1M.Acorrection
forthiserrorwasmadebyablankdetermination.Inablankdetermination,allstepsof
theanalysisareperformedintheabsenceoftheanalyte.Inthisexperiment,blankwas
determinedbytitratingasolutionofasmallamountofchloridefreecalciumcarbonate
andindicatorpotassiumchromatewithstandardsilvernitratesolution.Calcium
carbonatewasusedtoimitatethewhitesilverchlorideprecipitate.Reagentvolumeswere
correctedforblankinthecalculations.

CHLORIDE ION DETERMINATION

This test measures the soluble chloride Ion concentration in the mud filtrate. The Chloride can come from sodium chloride,
calcium chloride or potassium chloride. Also, for the titration to work correctly the pH of the filtrate needs to be only weakly
basic (pH = 8.3). This is the reason for the first step in the procedure. There are two chemical reactions
taking place simultaneously during the titration:
1.
Ag (+) + Cl ----------AgCL 2. 2 Ag
(+) + CrO4 ----Ag2CrO4
The first reaction, the formation of silver chloride, accounts for the appearance of the white specs or milky appearance during
the titration. The formation of the silver chromate, which is red, will not start until all the chloride Ions are tied up as silver
chloride. The silver nitrate will then react with the chromate from the potassium chromate indicator to form silver chromate.
So, for the above two reactions to occur, the filtrate needs to be weakly basic (pH = 8.3). High pH will precipitate silver oxide.

PROCEDURE
1.
2.
3.
4.

5. 6.

.0 ml of filtrate or sample to be tested into titration dish. Add 2 - 3 drops

of phenolphtahalein indicator to the filtrate.
If a pink color appears, titrate with N/50 sulfuric acid until the color changes from pink to that of the original
sample. If no pink color appears, the test can be continued.
If needed, add 25 - 50 mls of distilled water. This serves to dilute the dark color of a deeply colored filtrate. It does
not influence the test in any way if there are no chlorides present in the distilled water. If any water other than
distilled water is used, the chloride in it must be accounted for by titration before adding the filtrate to it.
Add 10 - 15 drops of potassium chromate indicator to give the filtrate a bright yellow color.
Add silver nitrate from a pipette dropwise, stirring continuously with a stirring rod, until the sample just turns
from yellow to an orange-red.

P
i
p
e
t
t
e
1

CALCULATION
1.
2.
3.

Parts per million (ppm) chloride = mls of silver nitrate used x 1,000 (If 0.0282N Silver Nitrate, lml = 1,000
ppm Cl is used)
Parts per million (ppm) chloride = mls of silver nitrate used x 10,000 (If 0.28N Silver Nitrate, lml = 10,000
ppm Cl is used)
ppm (NaCl) = ppm Chloride x 1.65

REMARKS
1.

The chloride test may be run on the same samples used in the Pf determination if the Mf test was not
performed.

2.

Avoid contact with silver nitrate. Wash immediately with water if silver nitrate gets on skin or clothing.

3.

4.
5.

The end point of the reaction is when the silver chromate is first formed. It is reddish in color. When using
the weak silver nitrate, the end point is approached very gradually. Therefore, the formation of the silver
nitrate can be seen by a color change from yellow to orange-red. If the strong silver nitrate is used, the end
point is approached much more rapidly. Hence the early formation of the silver chromate and its orange-red
color may be missed due to the larger amounts of silver nitrate being added. So the color change will go from
yellow to red, as soon as the red color is seen, the titration is complete.
White lumps of silver chloride form when titrating high concentrations of salt. This should not be taken for the
end point.
If the chloride Ion concentration is less than about 10,000 ppm, the weak silver nitrate solution should be used. If
it is greater than 10,000, the strong silver nitrate solution should be used.

ALKALINITY DETERMINATIONS
I.

MUD ALKALINITY (Pm)

This test measures the alkalinity of the whole mud. When used along with the filtrate alkalinity
determination, the amount of excess line present in lime muds can be determined.

PROCEDURE
1.
2.

3.
4.
5.
6.

Measure 1 ml of a freshly stirred sample of mud into a titration dish using a syringe.
The syringe should have a capacity of at least 3 mls. Draw at least two mls and preferably three mls of mud into
the syringe. Remove any air bubbles from the sample. Then inject a one ml sample by pushing the plunger from
the 3 ml graduation to the 2 ml graduation or the 2 ml graduation to the 1 ml graduation, but never from 1 ml to
the bottom of the syringe.
Dilute the mud in the dish with 25 - 50 mls of distilled water. Add no
more than 4 or 5 drops of phenolphthalein.
If the sample does not change color, report the Pm as 0.
If the sample turns pink, titrate rapidly with N/50 sulfuric acid until the pink color disappears.

CALCULATIONS
Report the phenolphthalein alkalinity of the mud, (Pm) as the number of mls of N/50 sulfuric acid added to discharge all the
pink color.

REMARKS
1.

If the mud sample is deeply colored from chemical thinners and the color change is hard to see, use ml of
mud and report the Pm as the volume of N/50 sulfuric acid added to discharge the pink color doubled. 2.
If 0.1N sulfuric acid is used, the Pm is reported as volume of N/50 sulfuric acid added to 1 ml of mud
times 5.

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OFI Testing Equipment - 144-50 Instructions - Chloride and Alkalinity Determination

II.

Page 4 of 5

FILTRATE ALKALINITY (Pf, Mf)

These tests are designed to measure the alkalinity contributions from soluble mud constituents. The Pf and
Mf test together can be used to get an estimate of the hydroxide Ion (OH-), the bicarbonate Ion (HCO3-)
and the carbonate Ion (CO3 -2) concentration. Also the Pf can be used with the Pm to determine the excess
amount of lime present in a lime base mud.

PROCEDURE (Pf)
1.
2.

Pipette 1 ml of filtrate into a clean titration dish. (Do not dilute with distilled water.)
Add more than 2 - 3 drops of Phenolphthalein. If no color develops, the Pf is 0 (and pH is less than 8.3). If
a pink color develops, add N/50 sulfuric acid through a pipette until the color changes pink to that of the original
sample.

CALCULATIONS (Pf)
1.

The Pf is the amount of N/50 sulfuric acid required to discharge the pink color. 2.
Excess lime content, lb/bbl = Pm - Pf
4

PROCEDURE (Mf)
1.
2.

To the same sample used for the Pf determination, add 2 -3 drops of Brom cresol green-methyl red
indicator.
Again add N/50 sulfuric acid until the color changes from a blue-green to a light pink color.

CALCULATIONS (Mf)
1. Report the Mf alkalinity of the filtrate as the total volume of N/50 sulfuric acid required to reach the end point,
including the volume required to reach the Pf end point.
2. An estimation of hydroxide Ion, bicarbonate Ion and carbonate Ion concentrations can be determined using the
following table.

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Date 02-27-03

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OFI Testing Equipment - 144-50 Instructions - Chloride and Alkalinity Determination

Page 5 of 5

CALCULATIONS OF ALKALINITY
Test Results
Where Pf = Mf
(indicates OH only)
Where 2 Pf-Mf is a positive number
(indicates OH- & CO3-2)
Where 2 Pf = M
(indicates CO3-2 only)

Calculations
Pf x 340 = Mg/L OH-

(2pf-Mf) x 340 = Mg/L OH2(mf-Pf) x 600 = Mg/L CO3-2

Mf x 600 = Mg/L CO3-2

Where 2Pf-Mf is a negative number

(indicates CO3-2 & HCO3-)

2 Pf x 600 = Mg/L co3-2

(Mf-2Pf) x 1220 = Mg/L HCO3-

Where no Pf reading or very low Pf

(indicates HCO3 - only)

Mf x 1220 = Mg/L HCO3-

NOMENCLATURE
Pf = Pnenolphtbalein end point of the filtrate sample using N/50 sulfuric acid
Mf = Methyl Orange or Brom Cresol Green-Methy red end point of filtrate sample using N/50 Sulfuric Acid
OH = Hydroxide Ion
CO3-2 = Carbonate Ion
HCO3- = Bicarbonate Ion

Introduction
Thismethoddeterminesthechlorideionconcentrationofasolutionbytitrationwithsilvernitrate.Asthe
silvernitratesolutionisslowlyadded,aprecipitateofsilverchlorideforms.

Ag+(aq)+Cl(aq)AgCl(s)

Theendpointofthetitrationoccurswhenallthechlorideionsareprecipitated.Thenadditionalchloride
ionsreactwiththechromateionsoftheindicator,potassiumchromate,toformaredbrownprecipitateof
silverchromate.

2Ag+(aq)+CrO42(aq)Ag2CrO4(s)
Thismethodcanbeusedtodeterminethechlorideionconcentrationofwatersamplesfrommanysources
suchasseawater,streamwater,riverwaterandestuarywater.Seawaterisusedastheexamplehere.
ThepHofthesamplesolutionsshouldbebetween6.5and10.(Refertotheadditionalnotes(3)forthe
explanation).Ifthesolutionsareacidic,thegravimetricmethodorVolhardsmethodshouldbeused

ResultCalculations
1.Determinetheaveragevolumeofsilvernitrateusedfromyourconcordanttitres.
2.Calculatethemolesofsilvernitratereacting.
3.Usethefollowingreactionequationtodeterminethemolesofchlorideionsreacting.

Ag+(aq)+Cl(aq)AgCl(s)

4.Calculatetheconcentrationofchlorideionsinthedilutedseawater.
5.Calculatetheconcentrationofchlorideionsintheoriginalundilutedseawater.
6.CalculatetheconcentrationofsodiumchlorideintheseawaterinmolL1,gL1andg/100mL(%).

AdditionalNotes
1.Silvernitratesolutionwillstainclothesandskin.Anyspillsshouldberinsedwithwaterimmediately.
2.Residuescontainingsilverionsareusuallysavedforlaterrecoveryofsilvermetal.Checkthiswithyour
teacher.
3.TheMohrtitrationshouldbecarriedoutunderconditionsofpH6.59.AthigherpHsilverionsmaybe
removedbyprecipitationwithhydroxideions,andatlowpHchromateionsmayberemovedbyanacid
basereactiontoformhydrogenchromateionsordichromateions,affectingtheaccuracyoftheendpoint.
4.Itisagoodideatofirstcarryoutaroughtitrationinordertobecomefamiliarwiththecolourchangeat
theendpoint.
5.TheMohrtitrationissensitivetothepresenceofbothchlorideandbromideionsinsolutionand
willnotbetooaccuratewhenthereisasignificantconcentrationofbromidepresentaswellasthe
chloride.However,inmostcases,suchasseawater,thebromideconcentrationwillbenegligible.Forthis
reason,themethodcanalsobeusedtodetermineeitherthetotalconcentrationofchlorideandbromide
insolution,ortheconcentrationofbromidewhenthechlorideconcentrationisknowntobenegligible.
http://intro.chem.okstate.edu/ChemSource/Seawater/act2.htm
Activity2:DeterminationoftheSalinityofSeawater
Introduction
Thismethodinvolveschemicalvolumetricanalysis.Asilvernitrate(AgNO3)solution
ofknownconcentrationisusedtoprecipitateoutthechloridesinaseawatersample.
Theprocedureiscomplicatedbythefactthatthedensewhiteprecipitate,silver
chloride(AgCl),doesnotsettlerapidly.Itisimpossibletotellwhenallthechlorides
havebeenremovedfromtheseawaterunlessanindicatorisusedtosignalcomplete
precipitationbyavisualcolorchange.Theindicatorintheanalysisischromateion.
Whenallofthechlorideionisexhausted,thechromateionreactswithsilverionsand
producessilverchromate,whichisred.Theinstantapermanentorangetinge
appearsinthesolution(onethatdoesntvanishwithmixing),theadditionofsilver
nitrateisstopped.Thefinalsolutioncolorshouldlooklikethatoforangejuice.
Thechemicalreactionsare:
Thetitrationiscarriedoutina150mLErlenmeyerflask,usingawhitebackground
andgoodlighting,butawayfromdirectsunlight.Constantbutgentlestirringis
essential,sincethesilverchloridetendstoformclots,whichtrapsomeofthe
reagents.Amagneticstirrerisveryhelpful.Thesilvernitrateisaddeduntilthefaint
reddishororangetingeremainsafterstirringfor45s.Atthispointonedropshould
givethedesiredendpoint.Observableflocsofsilverchloridewillobscuretheend
point,sincethesolutionsthattheycontainintheirintersticeswillleakoutslowly
andcausetheendpointtobeimpermanent.Astirringrodleftpermanentlyinthe
flask,especiallyifamagneticstirrerisnotused,willhelptobreakupthesecurds.
Purpose
1.Todeterminethechlorinity(andthusthesalinity,sincetheyaredirectly
related)ofasampleofseawater.
2.Tousethetitrationtechniquewithareactiondifferentfromanacid/base
reaction.
Safety
Wearprotectivegogglesthroughoutthelaboratoryactivity.AvoidgettingAgNO3on
handssinceitstainstheskin.
Procedure

1.Withapipetdeliver5.0mLseawaterintoa150mLErlenmeyerflask.
2.Usinga10mLgraduatedcylinder,add5.0mLpotassiumchromateindicator
solution,andbegintoaddthesilvernitratesolutionfromaburetwhile
constantlystirring.
3.Whenthesolutionturnsorange,stopaddingsilvernitrate.Thecolorshould
persistforlessthan20sec.Continueaddingsilvernitratedropwise,mixingall
thewhile,untilorangecolorpersists.Recordthevolumeofsilvernitrateadded.
4.Thoroughlywashyourhandsbeforeleavingthelaboratory.
DataAnalysisandConceptDevelopment
Fromasimplealgebraicproportiononecandeterminethechlorinityoftheseawater
becauseithasbeenshownexperimentallythatthesalinityisaconstant1.80655
timeshigherthanthechloridelevel.Thus,thesalinity(S)canbecalculated(using
theequationSppt=1.80655Clppt;thechlorinity(Cl)oftheartificialseawater
shouldbeabout19.05ppt).
1.Whatisthenumberofmolesofsilverusedinthetitration(AgNO3is0.2184M)?
2.Determinethenumberofmolesofchlorideinthesample.
3.Determinethegramsofchloridepresentinthesample.
4.Whatisthechlorinityof10gofsample?(Thedensityofseawaterisabout
1.05g/mL1).
5.Whatisthesalinityofthesampleinppt?