General Chemistry Week of 11/30

IsThereExperimentalEvidenceforYourInterpretationoftheSpectrumofAnAged
AqueousSolutionof[Co(NH3)5Cl]2+?
Experiment 7
(workinpairs)

Prelab

1) Howmanygramsofsodiumnitratedoyouneedtomake100mLofa4.5M
aqueoussolution?
2) Writethebalancedequationfortheionexchangereactionbetween
[Co(NH3)5Cl]2+andacarboxylicacidresinwhere=resin.
(-CO 2H)
3) Includeadatatableforthemaximumwavelengthvaluesyouwilldetermine.

BackgroundandSummary

Chemistsoftenhavetodevisetheoriestoexplaintheirchemicalobservations.For
question5fromtheexperiment5reportsheet(Investigationofcobaltcomplexes),you
devisedahypothesistoexplainwhatoccurredwhenthe[Co(NH3)5Cl]2+complexwas
dissolvedinaqueoussolutionovertheperiodofoneweek.

2+
NH3
H3N NH3
Co H2 O
H3N NH3
Cl

Thefollowingareexamplesofthemanypossiblecomplexesthatcouldbepresentin
yourreactionmixture:
2+ 3+ + 2+
NH3 NH3 NH3
NH3 H3N NH3
H3 N H3N NH3 H3N NH3
NH3
Co Co Co
Co
H3N NH3 H3N Cl H3N OH2
H3N NH3
OH2 Cl Cl
Cl

Yourtheorywasbasedonthechangeinthevisibleabsorptionspectrumafter
recordingthemax before AND after it was dissolved in water over the course of a week.

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Todayyouwillgivesupporttoyourtheorybycarryingoutanexperimentinwhichyou
willphysicallyisolatethecomplex(es),andidentifyeachindividualcomplexbythe
maximumwavelengthinitsabsorptionspectrum.
Theissuebecomes:howdoweseparatesuchchemicallysimilarspecies?One
possiblestrategyliesintakingadvantageofthedifferenceinthecharges;wewill
attempttoaccomplishthisusingIonExchangeChromatography.Youmightrecallthat
youusedachromatographictechniqueearlierthissemester(thinlayerchromatography)
toanalyzethemixtureofyouraspirinproduct.Thatseparationtechniqueinvolveda
stationaryphase(silicagel)andamobilephase(amixtureoforganicsolvents)withthe
basisfortheseparationbeingdifferencesinpolarityofthetwocompoundsanalyzed.A
similarstrategypromisestobeusefulhereexceptthattheprimarybasisforthe
separationwillbedifferencesincoulombicattraction,notpolarity.

Ionexchangechromatographycanpurifysmallmolecules(aminoacids,orinorganic
complexionssuchastheonesyouwilluseinthisexperiment)orverylargemolecules
likeproteins.Thestationaryphaseconsistsofapolymericmaterialcalledaresinwhich
iscommerciallyavailableandcontainsalargenumberofchargedfunctionalgroups.

Theresinsincationexchangechromatographyarecomposedofnegativelycharged
functionalgroups,typicallysulfonatesor
carboxylates,thatcanseparatepositively s a m p le
p la c e d
chargedspecies.Anionexchangeresinsare o n to p o f
r e s in
f ille d
w ith
( m o b ile
madeofpositivelychargedfunctionalgroups b y p ip e tte phase)
M o b ile p h a s e
likequaternaryaminesandthereforecan F r it
m o b ile p h a s e
tr a v e llin g
d o w n th e
separatenegativelychargedspecies. s ta tio n a r y p h a s e
( r e s in )
tr a v e llin g
d o w n th e
c o lu m n

c o lu m n
F ir s t c o m p o u n d

Thesampleisplacedonthetopofthe S a m p le w ill
s e p a r a te
e lu te s f r o m th e c o lu m n

columnontoafritwhichprovidesalevelsurfaceon
topoftheresin,andismadeofaporousmaterialthat
doesnotallowsolidmaterialtopassthrough.The
samplewillgothroughthefritandadheretothe
stationaryphaseasittravelsdownthecolumn.Inion
exchangechromatography,thelargerthecoulombic
attraction,thestrongerthebindingcapacitythe
samplewillhaveforthestationaryphase.
Specificallyincationexchangechromatography,
thehighlychargedpositiveionswillbindtothe
negativelychargedresintightly,andwillthereforetraveldownthecolumnataslower
rate.Thus,cationexchangesystemscanseparatepositivelychargedspecieswhichbind
withdifferentstrengthstothenegativelychargedresin.
Thesampleiselutedwithamobilephase.Themobilephaseisgenerallyanaqueous
solutioncontaininganelectrolyte.Theelectrolyteconcentrationisdependentonthe
particularspeciesyouaretryingtoseparate.

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 Atypicalcationexchangeprocessisillustratedbythefollowing:

- (CO 2-, H+)n + Mn+ ( -CO2-)n, Mn+ + nH+
solidresin insolnsolidresin insoln

Thecationassociatedwiththeresiniscalledthemobileion.Itsidentityis
determinedbytheelectrolyteconcentrationwithwhichtheresinisincontact.The
identityofthemobileionisimportantbecausetheseparationofcationsbythisprocess
dependsupontheaffinityoftheresinforonecationoveranother.

Intodaysexperiment,theresinhascarboxylicacidfunctionalgroups
attachedtoit.Thehydrogenofthecarboxylicacidisacidic,andis
thereforeeasilydissociated.Thecationsofthecobaltcomplexesthat
+
youwillrunthroughthecolumnwillthenexchangewithH ions,and
formionicbondswiththecarboxylicacidfunctionalgroupsontheresin.
Thecomplexeswilltraveldownthecolumnatdifferentratesbecauseofthe
differenceinthecoulombicchargebetweenthetwocomplexes.Inordertothenremove
thecobaltcomplexesfromthestationaryphase(rememberanionicbondispresent),
anotherionwillbeaddedtotheresinandwillexchangewiththecobaltcomplex.The
mobilephaseusedwillbeaconcentratedaqueoussolutionofNaNO3;thehigh
concentrationoftheNa+ionswillaidinelutingthecobaltcomplexesfromthecolumn
bycompetingwiththecomplexesforbindingsitesontheresin.Theconcentrationof
themobilephaseisimportantbecauseiftheconcentrationoftheelectrolyteistoolow,it
maybedifficulttofullyremovethesamplefromthecolumn.Iftheconcentrationistoo
highhowever,thechargedspeciesofthesamplemaynotsufficientlyinteractwiththe
column.

Materials

Column Testtuberack
Testtubes Disposablepipet

Procedure (working in pairs)

Apply the mixture: The column will be filled with resin and ready for you to apply
your mixture. Remove the cap from the bottom of the column, and drain the liquid until
it reaches just above the topsurfaceofthefrit. Using a pipette carefully add 1 mL of
your aged 0.02Mcobaltcomplexsolutionto the top of the resin.Allowthecobalt
solutiontodraintothetopsurfaceofthefrit.Thencarefullyadd1mLH2Oandallowit

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 todraintojust above the top of the resin.Alwaysmakesurethesolventlevelisabove
thetopoftheresin.Donotallowanysectionoftheresintobecomedry!

Running the column

You will use 4.5 M NaNO3 as your mobile phase (eluant). Place the first rack of test
tubes underneath the column. Add NaNO3 and collect each colored band into different
test tubes. Continue to add NaNO3 until both the colored bands have come off the
column. Collect only the colored bands in your test tube.Changetesttubesjustbefore
andaftereachcoloredbandelutesoffthecolumntoensureagoodseparationof
thetwocomplexes.

Analysis

Fill a cuvette with 4.5 M NaNO3 and run a baseline. Fill a cuvette full with the 0.02
M [Co(NH3)5Cl]Cl2solutionthatyoupreparedpreviouslyanddilutetothemarkwith4.5
M NaNO3.CoverwithParafilmandinvertseveraltimestomix.Record a spectrum
(from600nmto400nm)anddeterminethemaximumwavelength.Record a spectrum
of each colored fraction (undiluted) to determine the maximum wavelength for each.
Add a caption (it may be hand written) and print an overlay of the three spectra.

Cleaningthecolumn

Theresinisrecyclableandshouldbecleanedforthenextlab.Draintheeluantdown
tojustabovetheresin.Addapproximately40mLofwaterandallowthistodraininto
anemptyflask.Replacethecapatthebottomofthecolumn.

Wastedisposal

Allcoloredcobaltsolutionsmustgointotheheavymetalwastecontainer.Anytest
tubeswithcolorlesssolutionsmaygodownthesink.

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