Module1:PolyanilineNanofibers

TeacherPreparationandLaboratory
Guide
Inthisactivity,studentswill:
examinethesynthesisofpolyanilinenanofibersusingaverysimpleaqueous
acid,aniline,andoxidantmixtureshakentoproducethecolloidalnanofibers.
Theywillusesynthesizedmaterialtoinvestigatethechemicalandoptoelectrical
propertiesofconductivepolymers,specificallypolyaniline.

Thismodulewillfocuson:

preparationofsolutions
largeorganicmolecules(polymersmacromolecules)
nanotechnology
electricalconductivityasafunctionofpH
Principlesofalternatingdoubleandsinglebondsandtheorbitalorientationsthat
theyrepresent/bondingpatternsoforganicstructures

CurriculumConnections
(
http://bit.ly/1H1Uy2Y
)

TeacherPreparationTime:
20mins

LaboratoryTimeRequired:
Part1:
10mins
Part2a:
30min
Part2b:
20mins

TutorialVideo:
http://tiny.cc/52l44x

SafetyConcerns,SafetyDataSheets,andDisposal(ClickLinks):
Anilinehydrochloride
Ammoniumperoxydisulfate
Disposal
ammoniumoxidantisveryreactivewithanilinehydrochloride,usecaution
nanofiberscangodownthedrainwithexcesswater

TeacherPrelabMaterialPrep:
Lab1:Setoutreagentbottlesandequipment(scales,scoopulas,weigh
paper/boats)
Lab2Aand2B:Setoutpapertowelsandpipettesforeachpairofstudentsand
reagentsfordoping(vinegarandammonia)

Classroomsetuprecommendations:
Lab1:
Setuptwoweighstations(oneforanilinehydrochloride,otherfor
ammoniumperoxydisulfate)
LabPar2B:

 ControlTestStation2StationswithMultimetersandcrocclipstotest
resistanceinpresenceofcontrolsample(novapors)
BaseTestStation2StationswithMultimetersandcrocclipstotest
resistanceinpresenceofacidvapors
AcidTestStation2StationswithMultimetersandcrocclipstotest
resistanceinpresenceofbasicvapors
LabPart2C:
ExtensionExercisesetup9VbatteriesatMultimeterstationswith2croc
clips

Tips:
Increasingtheconcentrationofthereagentswillexpeditethepolymerization
process(decreasethetimeneededforLab1).

MaterialsinKit:
(4uses)
Reuseablematerialsdenotedwitha*
24gAnilineHClsaltseparatedinto4amberbottleswithparafilm,approx6gper
bottle
46gAmmoniumperoxydisulfatein1largeplasticcontainer
20disposableplasticpipettes
*
smallamountofcoppertapeforelectrodesforalteringvariables
20plasticconicalswithlids(greenlid)
*
Crocclipswithleads
*
Notprovided
weighpaper/weighboat
scale
scoopula
glassstirrods

Materialsperstudentgroup(inpartners),peruse:
+
0.259gAnilinehydrochloridepowder(C
H
NH
)
6
5
3Cl

0.571gAmmoniumperoxydisulfate((NH
)
S
O
)powder
4
2
2
8
2smallbeakers(approx.30mLvolume)*
scale*
weighingpaperorweighboat*

 20mLdeionizedwater*
glassstirringrod*
plasticcontainerwithlid

StudentPolyanilineNanofiberProcedure
(
http://bit.ly/1O0ewCY
)

PrelabQuestions:Answers
Thechartbelowshowsthestructuresofdifferentcoloredformsofthepolymer
polyaniline
.

RoyalSocietyofChemists.ElectrochromicPolymersOutreach.2007.RoyalSocietyofChemistrywww.rsc.org/outreach
http://www.rsc.org/images/RSCelectro_tcm18159224.pdf

InquiryInvestigationofPolyaniline(PAni):

TeacherExplanations:
Lookatthestructureofeachofthefourformsofpolyanilineinthetable.Takenoteof
theirchemicalstructuresandtheirproperties.

Question1:
Whatarethestructuraldifferencesbetweeneachofthem?
a. Hint:specificallylookatthepatternofconjugation!
Answer1:
Therearedifferentfunctionalgroups(amines,imines),conjugationof
doubleandsinglebonds,anddifferentamountsofhydrogensonthepolymer
backbone.Thereisadifferenceinconductivityduetothedifferencein
delocalizationofelectroncloudsthroughoutthemolecule,bandgapenergies,
andchargelocalization.

Question2:
Makeahypothesisastowhythesestructuralfeaturesleadtothespecific
conductiveproperties.Usingyourknowledgeofacidbasechemistryand/or
oxidationreduction,comparethefollowingpairsandexplainhowthesechanges
occurred.
Answer2:
LeucoemeraldinecomparedtoEmeraldineSalt
:
Leucoemeraldineisthefully
protonatedform.Itisnonconductivebecauseitdoesnthaveconjugated
structure(meaning,itdoesnthaveconsecutivealternatingsingleanddouble
bonds).AstheLeucoemeraldineformbecomespartiallyoxidized,itlosesan
electronfromhalfoftheNatomslonepairs(formalchargeof0changesto+1),
whichcauseselectrondensityrearrangementthroughoutthemolecule.This
leaveslonepositivechargesonthepolymerintheEmeraldineSaltform.
**ThisexplainswhyEmeraldineSaltisconductivebecausethereare
areasofthepolymerthathaveahighaffinityforelectrons(thepositively
chargedNatoms),andaconjugatedstructure(alternatingsingleand
doublebonds)whichallowsforthemovementoffreeelectronsdownthe
carbonchainbackbone.
EmeraldineSaltcomparedtoEmeraldineBase:AstheEmeraldineSaltbecomes
furtheroxidizedanddeprotonated,thereisalossoftwoHatomsfromthe
polymer.ThislossofHatomsresultsinanoverallneutralpolymer,leavingit
nonconductive(insulating).
EmeraldineBasecomparedtoPernigraniline:AstheEmeraldineSaltbecomes
fullyoxidizedtoPernigranilineform,theremainingHatomsareremovedasitis
exposedtobasicsolution.Thisleavesonlyaconjugatedstructurewithno
localizedcharges.

Part1:InLabQuestionsApplyingyourknowledge
1. Explainthebasisofthepolymerizationreactionabove(thiscanbeadescription).
a. Answer:
Anilineandtheoxidizingreagentexchangeelectronsinthe
reaction,causingspecificallytheelectronsinvolvedin
bondingthesubunitstobealtered,initiatingapolymerization
process.
2. Whatistheempiricalformulaofaniline?Drawananilinemonomer
andlistthehybridizationateachatom.
2
3
a. Answer
:eachCissp
hybridizedNissp
hybridized

3. Convertreactantmassestomolesanddeterminetheratioinwhichtheyreactto
formpolyaniline(Assumetheyarestoichiometricallyequivalentaslimiting
reagentsatthequantitiesnoted).
a. Answer:
0.001998molanilinehydrochloride,0.0025molammonium
peroxydisulfate.Therefore,reactsinaratioof4:5
4. Thinkingahead:Howarethethreevariablesrelated?Current,Voltage,
Resistance
a. Answer:

Voltage(V)
isthedifferenceinchargebetweentwopoints
Current(I)
istherateatwhichchargeisflowing
Resistance(R)
isa
materialstendencytoresisttheflowofcharge.Thesevariablesare
relatedthroughOhmsLaw:V=IR(Vinvolts,Iinamps,Rinohms)
Hint:
FillintheBlank:Averyconductivematerialhas_______resistancetoflow
ofelectrons.
b. Answer:
lowresistance

Part2AInLabQuestions:Makingconnectionsandpredictions
1. Iftheelectricalresistanceofthesensorincreases,whathappenstoelectrical
conductivity?
a. Whatform(s)ofPAnidoesthispropertycorrelatewith?
b. Answer:
Theelectricalconductivitywilldecrease.Correlateswith
Leucoemeraldine(colorless),Emeraldinebase(blue),andPernigraniline
(purple).
2. Iftheelectricalresistanceofthesensordecreases,whathappenstothe
electricalconductivity?
a. Whatform(s)ofPAnidoesthispropertycorrelatewith?
b. Answer:
Theelectricalconductivitywillincrease.Correlateswith
Emeraldinesalt(green).

Part2BAnalysisQuestions:
1. Whathappenstotheresistanceaftersensorisexposedtoabase?
a. seeexpecteddatabelow
2. Whathappenstotheresistanceaftersensorisexposedtoanacid?
a. seeexpecteddatabelow

3. IsthedopingdedopingprocessofPAnireversible?Howdoyouknow?
a. Answer:
Yes,becauseinStep6thesamePAnipapersensorchangedin
resistancefromtheacidtesttothebasetest,theresistanceincreased
initially,thendecreasedonceexposedtobasevapors.
4. Whatisthechemicalformulaofvinegarandammonia?Writeoutabalanced
chemicalequationofeachofthesechemicalsactingasanArrheniusacidand
base,respectively.
a. Answer:
i.
ii.

CH
COOH+H
OH
O
+CH
COO
3
2
3
3
+

NH
+H
ONH

3
2
4+OH

Part2CAnalysisQuestions:
1. WhatistheresistanceofPAniwhenmultimeterleadswereheldonthePAni
sensorclosetogether?
a. Answer:
lowresistance
2. Howdidtheresistancechangewhenthedistancebetweenleadsincreased?
a. Answer:
highresistance
3. Whatrelationshipcanyoumakebetweenresistanceanddistance?
a. Answer:
increasedistance,increaseresistance
4. Whatobservationdidyoumakeaboutconductivitybetweenthetwosamplesof
PAniyouused?
a. Answer:
dilutedsamplehadincreasedresistance
5. Wherecouldyouseethisscienceortechnologybeingusedintherealworld(use
thetitleofthisportionofthelabforinspiration)?
a. Answer:answerswillvary.Mayincludeapplicationsrelatedto

TypicalResults/Data
Lab1:Synthesis
Oncereagentsarecombined,youwillseeacolorchangeoccurfromcleartoblue,to
darkblue,topurple.Afterabout510minutes,thesolutionwillbethickerandviscous.
Thetemperatureofthesolutiondoesincreaseslightly.

Lab2:TestingHandheldsniffingdevice
Part2B:

 ControlSampleExampleData:68kiloOhms
Detectionofacidvaporsresistancedecreases(dopedincreasesconductivity)
ExData:76kiloOhms
Detectionofbasicvaporsresistanceincreases(dedopeddecreases
conductivity)ExData:87kiloOhms
FunFact!
Detectionofmethanolvaporsresistancedecreasesbecauseitcausesthe
polyanilinechainstoalign,whichcanincreasechargetransferasitdecreases
theresistance.
Electricalresistancewillgoupifexposedtovaporsfromabaseordownif
exposedtoacid.

FurtherDiscussionQuestionsandAnswers:
Whenmeasuringtheresistancebetweenthetapesatvariousdistances,howdoesthe
resistancechangewhenincreasingdistance,andwhy?
Answer:
Resistanceshouldincreasewithincreasingdistance,because
conductanceisafunctionofthelengththattheelectricalcurrentmusttravel.

Howdoestheresistancechangewhenthedopedpolyanilinenanofibersareexposedto
ammoniavaporsforoneminute?
Answer:
Theresistancewillincreasebecausethebase(ammonia)deprotonates
thepolyaniline,removingtheeffectofaciddopingwhichchangesthebandgap
andthustheconductivityofthematerial.

Howdoestheresistancechangewhendedopedpolyanilinenanofibersareexposedto
acidvaporsforoneminute?
Answer:
Theresistancewilldecreasebecausetheacidprotonatesthe
polyaniline,addingchargesalongthepolymerchainthatcantraveltocreatea
moreconductingmaterial.

AdditionalResources:
UCLAExampleprocedureofPAnisensor
https://www.youtube.com/watch?v=0WBF54K8APM