2/12/2014

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Galvaniccells
Pleaseturnonyourclicker.
2
Au(s)
Au
3+
Au
3+
Au
3+
1.09
voltmeter
Galvaniccells
Halfreactions
Cathode,Reduction
Au
3+
(aq)+3e

Au(s)
Anode,Oxidation
Cu(s)Cu
2+
(aq)+2e

3
Standardreduction potentials(25
o
C)
REACTION E
o
(V)
Au
3+
(aq)+3e

Au(s) 1.42
Cu
2+
(aq)+2e

Cu(s) 0.3402
ThehalfcellreactionwiththelargerE
o
isthecathode.
Theanodeiswrittenontheleft:
Cu|Cu
2+
Au
3+
|Au
E
o
= E
o
(cathode) E
o
(anode)=1.42 0.3402=1.08V
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Clickerquestion
Agalvaniccelliscomposedofastandardhalf
cellwithareductionpotentialof1.00Vanda
secondstandardhalfcellwithareduction
potentialof0.100V.Whichhalfcellcontains
thecathode?
A)E
o
=1.00V
B)E
o
=0.100V
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Thevoltageinthediagramiscloseto1.08V,but
slightlydifferent.Why?
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Au(s)
Ag
3+
Au
3+
Au
3+
Au
3+
1.09
voltmeter
2/12/2014
2
Concentrationdependence
Nernstequation:
Q
nF
RT
o
ln E E
m
n
] [reactants
[products]
Q
Au
3+
(aq)+3e

Au(s)cathode,reducon
Cu(s)Cu
2+
(aq)+2e

anode,oxidation
2Au
3+
(aq)+3Cu(s)2Au(s)+3Cu
2+
(aq)
2 3
3 2
] [Au
] [Cu

Q
2 3
3 2
] [Au
] [Cu
ln
6
08 . 1

F
RT
E
2{ }
7
3{ }
Experimentalconcerns
Connecttocom side
ofvoltmeter.
Anode
Doesthereaction
produceorconsume
electrons?
Connectto+V
sideof
voltmeter.
cathode
Thescaleonthevoltmetershouldbesettomaximum
sensitivityforanonscalereading.Itshouldbesetto
readadirectcurrentvoltagesource(not)
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1.09
voltmeter
Au(s)
Au3+
Au3+
Au3+
Au3+
Experimentalconcerns
Thescaleonthevoltmetershouldbesettomaximum
sensitivityforanonscalereading.Itshouldbesetto
readadirectcurrentvoltagesource(not)
Connectionsneedtobetight.
Donotinsertthe
probeintotheend
ofthealligatorclip.
MakesketchesinyournotebookforALL cellsshowing
whichconnectionsarenecessarytoobtainapositive
voltage.
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Safety
Allofthemetalsaltsaretoxic.
TheyhaveanMSDSHealthratingof2 moderate
or3 severe(poison)
Somearealsostrongoxidants.
ThenitrateshaveanMSDSReactivityratingof
3 severe(oxidizer)
Theywilldamageyourskin.
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PartA
Youwillmakeacopper/leadgalvaniccell.
Youwillneedtomakecoppersulfateand
leadnitratesolutions.
Youcalculatetheamountofeachthatyou
needfortheprelabhomework.Youshould
bringthosenumberswithyoutolab.
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Clickerquestion
Ifyouweremakingasolutionina50ml
volumetricflask,howmuchwaterwouldyou
usetoinitiallydissolvethesolid?
A)10ml
B)25ml
C)50ml
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2/12/2014
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PartB unknowns
Youwillbegivenasheetwith3unknowns.
AskyourTAtogiveyouthe3metalsforelectrodes
andthe3matchingsolutions.
Youwillmakeagalvaniccellwitheachofthe
unknownscomparedtocopper.
Fromthevoltages,youwillbeabletoidentifythe
unknowns.(Youllneedtodothisbeforeyouleavethe
lab.)
Theunknownelectrodeswillbefromalistof5
possibilities(Ag,Sn,Zn,Al,orMg).
Theconcentrationsofthesolutionsaresuchthatthelog
termintheNernstequationwillnotcontributetothe
potentialdifference.
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6wellplate
PartA PartB
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V
1
2
3
1
2
3
Connecttheelectrodestothevoltmeter
betweenthecopperandeachunknown
togetapositive reading.
PartC Concentrationcell
Cu
2+
(aq)+2e

Cu(s)Cu(s)Cu
2+
(aq)+2e

cathode(reduction) anode(oxidation)
V
Cu
2+
(0.05M) Cu
2+
(<0.05M)
Cu(s)
Cu(s)
saltbridge
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Thecathodehalfcellwillbethecopperhalfcell
fromthesolutionyoumadeforPartA.
Theanodehalfcellwillcontainaverylow
concentrationofCu
2+
.
Thisismadebyaddingoxalicacid,whichcausesmost
ofthecoppertoprecipitate.
Youmaynotseeanyprecipitatefalltothebottom the
solutionjustgetsalittlecloudy.
Thedifferenceinconcentrationcausesavoltage
tobeproduced.
Inyourexperiment
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[Cu
2+
]inthecathodeisdeterminedfromthehalf
cellsolutionthatyoumadeinPartA.
SinceyoumeasureE,youcanusetheNernst
equationtosolvefor[Cu
2+
]
anode
(copperoxalate
cell).
K
sp
=[Cu
2+
][C
2
O
4
2
]forcopperoxalate.
[C
2
O
4
2
]canbedeterminedfromtheionization
constantsofH
2
C
2
O
4
asdescribedinthemanual.
cathode
anode
Cu
Cu
F
RT
] [
] [
ln
2
0
2
2

E
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Clickerquestion
WillEbepositiveornegativeforaconcentration
cell?(HINT:Thecellwiththelowerconcentration
istheanode.)
A)E willbepositive.
B)E willbenegative.
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cathode
anode
Cu
Cu
F
RT
] [
] [
ln
2
0
2
2

E
2/12/2014
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H
2
C
2
O
4
(aq) H
+
(aq)+HC
2
O
4

(aq) K
a1
=5.9x10
2
HC
2
O
4

(aq) H
+
(aq)+C
2
O
4
2
(aq) K
a2
=6.4x10
5
NearlyalltheH
+
comesfromthefirststepsincethe
equilibriumconstantis3ordersofmagnitudelarger.
[H
+
][HC
2
O
4

]
K
a2
=6.4x10
5
=[H
+
][C
2
O
4
2
]/[HC
2
O
4

]
[C
2
O
4
2
]
K
sp
=[Cu
2+
][C
2
O
4
2
]
Warning:TheKspyoucalculateisverydifferentfrom
thevalueinthetext.Youwillnotneedtofigureouta
percentdeviation.However,youwillbeaskedfor
somepossiblereasonsforanydiscrepancyandyou
willbeaskedtosuggestexperimentstotestwhether
thosereasonscouldaccountforthediscrepancy.
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Experimentalconcerns
Makesketchesinyournotebookofeach
setup.
Youwillbeabletodeterminewhichisthecathode
andwhichistheanodebytheconnectionthat
resultsinapositivevoltage.
Bepreparedtodothisinthelab youllneedto
knowhowtodoittodetermineyourunknowns.
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Excesschemicaldisposal
Thesolutionsareneutralexceptfortheones
containingoxalicacid.
Theneutralsolutionscanjustbeputinthebig
drumswithoutneedingtoaddbakingsoda.
Anysolutionscontainingoxalicacidneedtobe
neutralizedwithbakingsodaandthenputin
thedrums.
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Similarities
GalvanicCells
Oxidationoccursattheanode.
Reductionoccursatthe
cathode.
Electronstravelinthewires.
Ionstravelinsolution.
Thesolutionsareelectrically
neutral
Acompletecircuitis
necessary.
ElectrolyticCells
Oxidationoccursattheanode.
Reductionoccursatthe
cathode.
Electronstravelinthewires.
Ionstravelinsolution.
Thesolutionsareelectrically
neutral.
Acompletecircuitis
necessary.
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Differences
GalvanicCells
Twoconnectedhalfcells
produce voltage.
Theidentityofthecathodeand
anodeisdeterminedbythe
reductionpotentials.
Theelectricalneutralityofthe
solutionsaremaintainedwith
thesaltbridgesincethe
reactionstakeplaceinseparate
beakers.
Galvaniccellpotentialsare
dependentontheconcentration
ofthesolutions.(Nernsteqn.)
ElectrolyticCells
Abatteryorpowersupplyis
required.
Theidentityofthecathodeand
anodeisdeterminedbythe
battery,NOT bythereduction
potentials.
Theelectricalneutralityofthe
solutionismaintainedby
simultaneousreactionsatthe
cathodeandanodesincethe
reactionstakeplaceinthesame
beaker.
Theconcentrationofthesalt
doesnotchangetheamount
plated,aslongasthereis
sufficientsaltpresent.
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Reminders
Prelabhwonexperiment3duenextweek
Experiment2postlabassignmentisduenext
week
Remembertobringyoursketchoftheelectrolytic
cellapparatustolabnextweek.
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