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Mystery of solubility: Retrograde

[Temperature Inverse] solubility: Why
does it happen?
Published on May 20, 2016

Nikhilesh Mukherjee
Author and Consultant

Abstract
Theretrogradeorinversesolubility,existswhenasalt'sdissolutionisexothermic
accordingtoLeChatelier'sprinciple,extraheatwillcausetheequilibriumforan
exothermicprocesstoshifttowardsthereactants.Sodiumchlorideandammonium
nitrateabsorbheatwhiledissolvinginwater.Theyshowdirectsolubilityinwater
withtemperature.Calciumphosphateandcalciumsulfatearetwotypicalsalts
whichshowretrogradesolubility.BothCalciumphosphateandcalciumsulfate
evolveheatwhentheyaredissolved.
Letusstartwithbasics.
Whatissolubility?
Solubilityisanabilityofasubstancetodissolve.Thesubstancewhichisbeing
dissolvediscalledasoluteandthesubstanceinwhichthesoluteisdissolvediscalleda
solvent.Amixtureofsoluteandsolventiscalledasolution.Itismeasuredintermsof
themaximumamountofsolutedissolvedinasolventatequilibriumatagiven
temperatureandpressure.Whenthereisnomoredissolutionofsoluteinthesolventthe
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solutioniscalledasaturatedsolution.Solubilityisexpressedusuallyasgramsofsolute
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per100gramsofsolvent.
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Whatmakesthingsdissolve?
Intheprocessofdissolving,moleculesofthesoluteareinsertedintoasolventand
surroundedbyitsmolecules.Inorderforthisprocesstotakeplace,intermolecular
bondsbetweenmoleculesofsoluteandmoleculesofsolventhavetobebrokenandnew
molecularbondsbetweensoluteandsolventhavetobeformed.
Roleoftemperature?
Generally,thesolubilityofagivensoluteinagivensolventtypicallydependson
temperature.Manysaltsshowalargeincreaseinsolubilitywithtemperature.Thiscan
beexplainedlikethis.Asthetemperatureofasolutionisincreased,theaveragekinetic
energyofthemoleculesthatmakeupthesolutionalsoincreases.Thisincreasein
kineticenergyallowsthesolventmoleculestomoreeffectivelybreakapartthesolute
moleculesthatareheldtogetherbyintermolecularattractions.Theaveragekinetic
energyofthesolutemoleculesalsoincreaseswithtemperature,anditdestabilizesthe
solidstate.Theincreasedvibration(kineticenergy)ofthesolutemoleculescausesthem
tobelessabletoholdtogether,andthustheydissolvemorereadily.
Thereare,however,exceptions.Somesolutesexhibitsolubilitythatisfairly
independentoftemperature.Theresomesoluteswhichbecomelesssolublewith
increaseintemperature.
Whatisretrogradesolubility?
Afew,soluteslikecalciumcarbonate,calciumphosphate,calciumsulfatemagnesium
silicateetc.,becomelesssolubleinwaterastemperatureincreases.Thisinverse
temperaturedependenceissometimesreferredtoasretrogradeorinversesolubility,

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Implicationsofretrogradesolubility
Oneofthemostimportantimplicationsofretrogradesolubilityisthedepositofscale
formingsaltslikecalciumcarbonate,calciumphosphate,calciumsulfate,magnesium
silicateetc.,onheattransfersurfaceswhentheyprecipitateaftertheirsolubilityhave
exceededeitherinthebulkwateroratthesurfacebecauseofincreasedtemperature.
Thesaltswiththe"normal"solubilityincreasetheirsolubilitywithincreasing
temperatureandthuswillfoulthecoolingsurfaces.Thesaltswith"inverse"or
"retrograde"solubilitywillfoultheheatingsurfaces.
Whydoessomesaltsshowretrogradesolubility?
ThiscanbebestexplainedbytheLeChatelierprinciple
WhatisLeChatelierprinciple?
Itstatesthatifadynamicequilibriumisdisturbedbychangingtheconditions,the
positionofequilibriummovestocounteractthechange.
Whatdoesitmean?
Letustakeareaction,A+2B<>C+D,DeltaH=250kj/mol.Assumethat
forwardreactionisexothermic,250kj/molheatisevolvedwhen1moleofAreacts
completelywith2molesofB.Thereversereaction,theconversionofCandDintoA
andB,wouldbeendothermicbyexactlythesameamount.
Letusnowexaminewhathappensifwechangetheconditionsbyincreasingthe
temperature?
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Supposethesystemisinequilibriumat300C,andweincreasethetemperatureto
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500C.HowcanthereactioncounteractthechangewehavemadeaccordingtoLe
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Chatelierprinciple?Howcanitcoolitselfdownagain?Tocooldown,itneedstoabsorb
theextraheatthatwehavejustputin.Inotherwords,thepositionofequilibrium,
therefore,hastomovetotheleft,inthedirectionwhenthereactionisendothermic.The
newequilibriummixturecontainsmoreAandB,andlessCandD.
Letustakethesecondcase.
Whatwouldhappenifwechangetheconditionsbydecreasingthetemperature?
Theequilibriumwillmoveinsuchawaythatthetemperatureincreasesagain.Letus
seehowithappens.Supposethesystemisinequilibriumat500Candwereducethe
temperatureto400C.Thereactionwilltendtoheatitselfupagaintoreturntothe
originaltemperature.Itcanonlydothatbyfavoringtheexothermicreaction.Thatisthe
positionofequilibriumwillmovetotheright.MoreAandBareconvertedintoCand
Datthelowertemperature.
A+2B<>C+D,DeltaH=250kj/mol
Summary
Increasingthetemperatureofasystemindynamicequilibriumfavorsthe
endothermicreaction.Thesystemcounteractsthechangeyouhavemadeby
absorbingtheextraheat.
Decreasingthetemperatureofasystemindynamicequilibriumfavorsthe
exothermicreaction.Thesystemcounteractsthechangeyouhavemadeby
producingmoreheat.
Letusapplythisconcepttosolubility.
Explanationforretrogradesolubility
Inanysolutionprocesswheresoluteandsolvent[water]areindynamicequilibrium
withthesolutionandheatisappliedtothesolution,thedynamicequilibriumwillbe
disturbed.AsperLeChatelierprinciple,thedisturbedequilibriumwillbeopposedbya
shiftinthepositionofequilibrium.Ifthesolutionprocessisexothermicthatisifthe
solutionofsoluteinwatergeneratesheat,thepositionoftheequilibriumwillshiftto
left,thatis,inadirectionwhentheprocessisendothermictocounterthedisturbed
equilibrium.Asaconsequencetothis,thedissolutionprocesswillbesloweddown.
Therewillbemoreundissolvedsoluteinwater.Thesolutewillshowaretrograde
solubilityinwaterwithrespecttotemperature.
Exactlyinthesamemanner,ifthesoluteabsorbsheatwhilegoingintosolutionin
water,inordertocounterthechangeinthethermodynamicequilibrium,youhaveto
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supplymoreheattodissolvemoresoluteinthesolventbyshiftingthepositionofthe
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equilibriumtoright.Inotherwordsthedissolutionprocesswilldependonthesupplyof
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heatandproportionatelyincreasewithtemperature.Thesolutewillshowdirector
progradesolubilitywithrespectwater.
Letustakesomeexamples.
Bothsodiumchlorideandammoniumnitrateabsorbheatwhiledissolvinginwater.
Theyshowdirectsolubilityinwaterwithtemperature.Calciumphosphateandcalcium
sulfatearetwotypicalsaltswhichshowretrogradesolubility.BothCalciumphosphate
andcalciumsulfateevolveheatwhentheyaredissolved.
Itcanbeconcludedthatifdissolutionofasoluteinasolventwouldshowaretrograde
solubilityoradirectsolubilitywithtemperaturedependsontheheatofsolution.While
dissolving,whenasoluteevolvesheat,thesoluteshowsaretrogradesolubilitywith
temperature.Whenasoluteabsorbsheatwhiledissolving,ithasadirectrelationwith
temperature.

Tagged in: solubility,chemistry

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Nikhilesh Mukherjee
Author and Consultant
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Prof. Aiman Eid Al-Rawajfeh

8mo

Full Professor at Tafila Technical University

Very interesting, thank you.

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