Bonding

Topic MainIdeas
Sizeofatoms
vsions

PositiveionsaregenerallySMALLERthantheatomsfromwhichtheyareformed.
ThisisbecauseinformingapositiveionaSHELLOFELECTRONSisloste.g.Na
(2,8,1)Na+(2,8)
ThereforetheoutermostelectronisCLOSERtothenucleusintheionmakingitsradius
SMALLER
NegativeionsaregenerallyLARGERthantheionfromwhichtheyareformed.
Thisisbecauseinforminganegativeion,anelectron/sisaddedtotheSAMESHELL
(sameprotons).
MoreelectronsinthesameshellREPELMOREandarethusFURTHERAPART
ThereforethedistancefromthenucleustotheouterelectronisLARGERintheION
Periodic
Trends

ACROSSAPERIOD
moreprotonsareaddedANDmoreelectronsareaddedTOTHESAMESHELL
Thismeansthatthevalenceelectronshaveagreaterattractionforthenucleus,whichin
turnmeans:
1. aSMALLERatomicradius
2. aLARGERionisationenergy
3. aGREATERelectronegativity

DOWNAGROUP
anextraSHELLOFELECTRONSisadded
ThismeansthatthevalenceelectronsareFURTHERfromthepullofthenucleusAND
aremoreshieldedfromthenucleusbymoreinnershells,whichinturnmeans:
1. aLARGERatomicradius
2. aSMALLERionisationenergy
3. aLOWERelectronegativity

ALSOLEARNDEFINITIONS:

1. atomicradiusisthedistancefromthenucleustotheoutermostelectron(scholarship
peoplelookuphowitismeasuredinmolecules,metalsandions)
2. ionisationenergyistheENERGYrequiredtoremovetheleasttightlyheldelectronfrom
amoleofatomsintheirGASEOUSSTATE
3. Electronegativityistheattractionofanatomforapairofbondedelectrons
Intermolecular
forces

WIFexistbetweenMOLECULES(compoundsformedfromnonmetals)
Allmoleculescanformtdtd(fromatemporary/instantaneousimbalanceintheecloud).
Alargerecloud(largermolarmass)=strongertdtd=highermpt/bpt
NONPOLARmoleculeshavetdtdONLY
POLARmoleculescanformpdpd.thisis(obviously)fromPERMANENTDIPOLESie
thepermanentunevensharingofebetween2covalentlybondedatoms(check
symmetrytoomoleculemustbepolarnotjustpolarbond).Strongerdipoles(from
moreENelements)havestrongerpdpd(egHCl>HBr)
POLARmoleculescontainingaHcovalentlybondedtoF,OorNcanformHBonds
BETWEENMOLECULES.ThestrongestWIF.

PACKING!!!!linearchainspackcloserthanbranchedchainmolecules,closerpacking=
strongertdtd=higherboilingpoint
Electron
configurations
rememberhowtheyequateto2,8,8,2(mainenergylevels)
makesureyoudontmixupSUBLEVEL(1s,2petc)withORBITALoneofthelines(_)
thatrepresentsanareaofspacewhichcanhold0,1or2electrons.
asyougoupinmainenergylevels,alsoaddasublevel.1has1s.2has2sand2p.3
has3s,3pand3d.
HOWEVER,fill4sBEFORE3dANDwhenformingionsremove4selectronsFIRST
ExceptionsareCrandCuwhichhave3d5and3d10and4s1.
rememberthatapartiallyfilled3dsublevelisresponsiblefortransitionmetalshaving
COLOUREDCOMPOUNDSandMULTIPLEOXIDATIONSTATES(andalsofor
anythingafterNabeingabletoholdMORETHAN8ELECTRONSwhendoingLewis
diagrams
Lewis
diagramsand
polarity
basicallyfollowthesamerulesaslastyear,butcanhavemoleculeswithuptoSIX
areasofelectrondensityaroundthecentralatom
useONLYandALLvalenceelectronstodrawdiagrams
LEARN3DrepresentationPROPERLY(alsofororganic)
concentrateontheNEWSHAPES(tshaped,seesaw,trigonalbipyramidal,octahedral,
squareplanarandsquarepyramid)
Theexplanationisthesameaslastyearmolecularpolaritydependson(1)the
presenceofPOLARBONDS(duetoENdifference)and(2)thesymmetryofthe
moleculesandwhetherthedipolescancel.
Summary:octahedral,trigonalbipyramidalandsquareplanarareallSYMMETRICAL
Thermochemi
cal
calculations

Firstly,youmustmemorisetheDIFFERENTTYPESofENTHALPYCHANGEandhowtowrite
EQUATIONSforthemall.ThesearecH,fH,fusH,vapHandrH.LEARNalsothe
definitionsforthese.

THEN:makesureyouareCLEARonwhichEQUATIONyouarefindingtheHfor.Writethis
atthetop.ThemethodyouusetofindtheanswerONLYDEPENDSontheDATAyouthen
have.

1. EXPERIMENTALDATA.Youmustuse2equations.
a)energygained(bywater)=CxTxm(allforWATERprobably)
C=specficheatcapacityforwater=4.18Jg
1
degC
1
(youwillbegiventhisnumberbutnotthe
equation).
THENchangethisanswertokJbydividingby1000
andb)n=m/Morn=cv(somewayofworkingoutthemolesrememberifyouhave2different
moles,usetheSMALLESTastherestWONTreact)
FINALLYtakekJanddividebymolestogetkJmol
1

2. fHDATA
UsetheequationsumofthefHofproductssumofthefHofreactants

3. MIXEDDATA
UseHESSSLAW.Multiply,divideandreverseequationsuntiltheyCANCELtogiveyouthe
desiredequation.DOTHESAMETOTHENUMBERSasyoudidtotheequations.(reversing=
changethesign).STATESMATTER.
Entropy Entropyisthetendencyfortheuniversetobecomemoredisorderedthinkofyourbedroom,if
youdonotdoanything,itwillgetmoremessy,nottidier!

Intheabovetable,DH=enthalpyandDS=entropy

Youcanlookatitmathematically: G= HT S
Spontaneousreactionshaveanegative G(Gibbsfreeenergy)

Organic
Topic MainIdeas
Namingand
drawing
Learnthis!ChecktoseeifNUMBERSareneeded(mostlikely,yesexceptaldehydesand
carboxylicacidsmustbeoncarbon#1).DRAWEXTENDED!!!!(easiertoseereaction
mechanismsandlesslikelytomakeerrors)
Isomers Cis/trans,constitutional(branchedandstraightchain)andoptical.Concentrateonoptical
(enantiomers)3Ddrawingsofthe2mirrorimagesandthesimilarities(mostthings)and
differences(rotationofplanepolarisedlightandreactionwithenzymesinbiologicalsystems)
Reactiontypes

Substitution:oneatom(orgroup)isremovedandreplacedbyanotheratomorgroup.SPECIFY
whichatomisremovedandwhatitisreplacedwith

Addition:aCtoCdoublebondisbrokenandtwonewatoms/groupsareaddedtothe
previouslydoublebondedCatoms.Theunsaturatedcompoundbecomessaturated.

Elimination:2atoms(usuallyanHandahalogenoranOH)areremovedfromadjacentC
atomsandadoublebondformsbetweenthose2Catoms.Asaturatedcompoundbecomes
unsaturated.

Oxidation:Oxygenisadded

Reduction:Hydrogenisadded/oxygenisremoved

Acid/base:aprotonisexchanged(donatedbytheorganicacid,COOHandacceptedbythe
organicbase,amine)

Hydrolysis:amoleculeissplitapartbythereactionwithwater(usuallywithanacidorbase
catalyst)usuallyamidesandestersarehydrolysed(ofteninpolymers)
Keyreactions

UseyourREACTIONOVERVIEWsheet(plusyournotesforothersegreactionsofacids.)
Suggestion:

Divideyourreactionsinto2groups:

1. thoseyoucanWORKOUTbylookingattheformulaorthoseyouEASILYREMEMBER
and
2. thosewhicharemoredifficulttoremember.

NowmakeaLISToftheHARDONES.Leaveaspaceblankforeachanswer.Theanswer
maybethePRODUCToraREAGENT/REQUIREMENT
FillintheanswersWITHOUTLOOKINGatyoursheet
Markthem.Redotheonesyougotwrongbyputtingacleansheetofpaperoverthe
answers.Repeatthisuntilyougetthemallright.
Nowrepeatthisexerciseacoupleofdayslater.Andagain.3or4timesshouldhaveyou
conqueringthereactions!

Distinguishing

Distinguishingbetween:
Aminesandcarboxylicacids.UseWETLITMUS/UI.
Aminesandamides.UseWETREDLITMUS/UI.AminesareBASIC.Amidesarenot
appreciablybasic.
Alkenesandalkanes.UseBrominewater.Theorangebrominewater(Br
2
)decolourises
quicklywiththealkaneduetoanadditionreaction.ItwilldecolouriseslowlywithUVfor
alkanes(andanyothercompoundwithaCbondedtoanH).
Ketonesandaldehydes.UseTollens(silvermirrorforaldehyde),Benedicts/Fehlings
(bluesolutiontored/brownprecipitateforaldehydes),orCr2O7
2
/H+ORMnO4/H
+
.Orange
dichromatewillturngreenORpurplepermanganatewilldecolourisethealdehyde.
AlwaysbecauseALDEHYDEScanbeOXIDISEDandketonescant.
Primary,secondaryandtertiaryalcohols.UseLUCASreagent(ZnCl
2
andconcHCl).
Tertiaryreactsinstantly,secondaryafterashorttimeandprimarynotatall.The
reactionisseenbyturningCLOUDYashaloalkanesaremadewhichareLESSPOLAR
andINSOLUBLEinwater.
Haloalkanesandacylchlorides.Usewater.HaloalkanesWILLNOTREACT,butwill
form2LAYERS.AcylchlorideswillreactVIOLENTLYproducingWHITEFUMESofHCl.

DontforgettoonlyuseREAGENTSTHATGIVEOBSERVATIONS.

ThenTICKOFFtherequirementsinthequestionbalancedequation,reasonsforreaction(talk
aboutREACTIONTYPEShere),specialconditionsetc

IfitisaBIGQUESTION(i.emorethan2compounds)dontforgettobeLOGICALinyourorder.
i.e.addreagentXtoasampleofall5substances.Theonethatturnstheredlitmusblueisthe
amineaminoethaneasaminesarebases.Labelthisandsetaside.Totheremaining4....blah
blah.
Techniques Reflux:forheatingreactionstoincreasetheyield(usedforexampleinoxidisingalcoholsand
makingesters)
Distillation:Usedforseparatingliquidsbyboilingpoints(egifyouwantedtoseparatean
aldehydeasyouwereoxidisinganalcoholbeforeitwouldturnintoacarboxylicacid)
Separatingfunnels:usedforseparatingliquidsofdifferentpolarities
Condensation
polymerisation
andhydrolysis

Polymers:MACROMOLECULES(vlarge)wheremillionsofmonomersarejoined,eachbond
involvingtheremovalofasmallmolecule(HClorH
2
O)

CondensationpolymerscanbePOLYAMIDESorPOLYESTERS.

Polyamides:comefromjoiningmonomerswithanAMINEgroupandeitheracarboxylicacidor
anacylchloride.PROTEINSarepolyamides.TheAMIDEbondisshown:(theexamplebelowis
adipeptideora2aminoacidprotein):

Polyesters:comefromjoiningmonomerswithanALCOHOLgroupandeitheracarboxylicacid
oranacylchloride.

Both:caneithercomefromONEorTWOmonomers.

Onemonomer:.....AAAAAAA....
ThemonomerMUSThaveTWOdifferentfunctionalgroupsoneoneachend(iefora
polyamide,oneendshouldhaveanaminegroup(NH
2
)andtheotherendofthemonomer
shouldhaveacarboxylicacid(COOH)oranacylchloride(COCl).Forapolyesteroneend
shouldhaveanalcoholgroup(OH)andtheotherendofthemonomershouldhaveacarboxylic
acid(COOH)oranacylchloride(COCl).)

Twomonomers:....ABABABABAB......
ThemonomersmusteachhaveTWOOFTHESAMEfunctionalgroupsoneachend(iefora
polyamide,onemonomershouldhaveTWOaminegroups(NH
2
)andtheothermonomer
shouldhaveTWOcarboxylicacidgroups(COOH)orTWOacylchloridegroups(COCl).Fora
polyesteronemonomershouldhaveTWOalcoholgroups(OH)andtheothermonomershould
haveTWOcarboxylicacidgroups(COOH)orTWOacylchloridegroups(COCl).)

HYDROLYSIS.
Bothpolyamidesandpolyesterscanbehydrolysed(splitbyreactingwithwater)byreacting
withDILUTEACIDorDILUTEBASE.

WhenhydrolysingwithACID,theproductswillbeFULLYPROTONATED(iethegroupsthat
canaccept/donateprotonswillhavetheMAXIMUMPROTONSATTACHED.Thismeans:
OH(notacidic/basicneverchanges)
NH
2
isintheformNH
3
+
COOHisCOOH
NBCOClisNOTFORMEDinhydrolysis(wherewouldtheClcomefrom?)

WhenhydrolysingwithBASE,theproductswillbeUNPROTONATED(iethegroupsthatcan
accept/donateprotonswillhavetheLEASTPROTONSATTACHED.Thismeans:
OH(notacidic/basicneverchanges)
NH
2
isintheformNH
2

COOHisCOO

(orCOONaorCOONa+)
NBCOClisNOTFORMEDinhydrolysis(wherewouldtheClcomefrom?)

Physical
properties
Carboxylicacids,aminesandalcoholscanallformHbondsthismeanstheyaremore
solubleinwater(canformHbondswithwater)andhavehigherboilingpointsthansimilarsized
moleculeswithouttheabilitytoHbond

Aqueousequilibria
DateandTopic MainIdeas
Solubility
calculations

Solubilityistheamountofthatcompoundthatwilldissolveinasetvolumeofwater,usually
measuredingL
1
ormolL
1
.Thevalueisdifferentatdifferenttemperaturesgenerallymoresolid
dissolvesatahighertemperature.Asolutioninwhichnomoresolidcanbedissolvediscalleda
SATURATEDsolution.
CalculationsinvolvingKs(SOLUBILITYPRODUCT)andsolubility(molL1)
1. FirstdecideifthecompoundisAB,AB
2
orA
2
Btype.
2. WriteanequilibriumequationandaKsexpressionforthecompound.
3. Decideontheconcentrationofeachionusingthesolubility
4. SubstitutetheionconcentrationsintotheKsexpressionandsolve.
e.g.
1. CalculatetheKsforBaSO
4
givenitssolubility=3.87x10
5
molL
1
2. CalculatetheKsforCaF
2
givenitssolubility=2.2x10
4
molL
1
Answers:1.50x10
9

4.26x10
11

Tobeuseful,youhavetobeabletousesolubilitydatatoPREDICTPRECIPITATION.E.g.What
ifweaddedfluorideionstoourwatersupplywouldanythingprecipitateoutproducinganasty
solidfloaterinourdrinkingwater?
WeneedtousetheIONICPRODUCT.Theionicproductistheproductoftheionsinsolution,
raisedtotheappropriatepower
ItiscalculatedinthesamewayasKs
HOWEVER,THEYAREDIFFERENT!!!!!
Ksiscalculatedwhenyoumakeasaturatedsolutionofasparinglysolublecompoundonly(i.e.
dissolvestuffinwatertosaturation)
IPiscalculatedfromanysourceofions(e.g.Addtwodifferentsolutionstogetherdontforgetto
takeintoaccounttheDILUTIONFACTORwhenmixingsolutionsmostsimplyifthevolumesare
EQUAL,theconcentrationsHALVE)

Fromthepreviouspage:Willaprecipitateforminthewatersupply?
CompareIPtoKs
IfIP>Ks,thenconcentrationofionsexceedssolubilitysoaPRECIPITATEFORMS
IfIP<Ks,thenconcentrationofionsislessthansolubilitysoNOPRECIPITATEFORMS
Commonioneffect
Thepresenceofacommoniondecreasesacompoundssolubilitye.g.KClislesssolublein
waterthanitisinanNaClsolution.Thisisbecausethesaltsolutioncontainsoneoftheionsyou
aretryingtodissolve
KClK
+
+Cl

ThepresenceofClinthesolutionpushestheequilibriumtotheleft,thusprecipitatingKCl

Complexions
Rememberthese?
Ag(NH
3
)
2
2+
Zn(NH
3
)
4
2+
Pb(OH)
4
2
Zn(OH)
4
2
Al(OH)
4

Cu(NH
3
)
4
2+
Complexionsmadefromacentralmetalionandanumberofligands.Thesearesoluble.The
presenceofoneoftheseligandscanallowcomplexionstoform,whichcanINCREASEthe
solubilityofsomesparinglysolublecompounds
SupposewehaveasaturatedsolutionofAgBr,withsomeAgBr(s)leftundissolvedatthebottom
ofthebeaker.Wenextaddsomeaqueousammoniatothesystem.Itsmoleculesarestrong
ligandsforsilverions,sotheybegintoformAg(NH
3
)
2+
ionsfromthetraceamountofAg
+
(aq)
initiallypresentinsolution.
Ag
+
(aq)+2NH
3
(aq)<==>Ag(NH
3
)
2+
(aq)
Theammoniarepresentsanupsettotheequilibriumpresentinthesaturatedsolutionof
AgBr(s)<===>Ag
+
(aq)+Br

(aq)
BypullingAg
+
ionsoutofthisequilibrium,theequilibriummustshifttotherighttoreplacethem
asbestitcan.i.e.moreAgBr(s)mustgointosolution.Thesolubilityofaslightlysolublesalt
increaseswhenoneofitsionscanbechangedtoasolublecomplexion.
pHcanalsoaffectthesolubilityofsomesubstancesuseLeChateliersprincipletoexplain
these.
Buffers

Buffersare:
ApproximatelyequalconcentrationsofaWEAKacidanditsCONJUGATEbase
(composition)
BuffersmaintainaREASONABLYCONSTANTpHwhenexternalH+andOHareadded
(function).
Commonbuffersarefoundinhuman(andotheranimal)BLOOD(HCO
3

andCO
3
2
)andin
everyRESEARCHLABORATORY
YoumustbeabletowriteEQUATIONSshowinghowbufferswork.Forexample:

IfthebufferisNH
3
/NH
4
+
:(NB=isanequilibriumarrowasIcantfindoneingoogledocs)
AddedOH

:
NH
4
+
+OH

=NH
3
+H
2
O
AddedH
3
O
+
:
NH
3
+H
3
O
+
=NH
4
+
+H
2
O

Buffercalculations:
1. FigureoutwhichWEAKACIDyouhave.(egHCO
3

).(Clue:youwillhaveaKaforthis(orbe
abletofigureitout).
2. Writeanequationfortheweakacidreactingwithwater(ieaweakacidequilibrium)andthen
aKaexpressionforthis.
3. SubinthevaluesthatyouaregivenandSOLVEfortheanswer.(rememberH
3
O
+
willbein
yourequationandyoucangetthephfromthisORgettheH
3
O
+
fromthepH

Salts

SALTSareIONIC(mostlymetalsalts).Commonexamplesare:
NaCl
CH
3
COONa
NH
4
ClandNH
4
NO
3
HCOOK

THESEsaltsDISSOCIATEcompletely.WriteONEEQUATIONtoshowthis.
NH
4
NO
3
NH
4
++NO
3

ThendecideifanyoftheionsREACTwithwater(bydonating/acceptingaproton).Ifyes,WRITE
ANOTHER(equilibrium)equation!!
NH
4
++H
2
O=NH
3
+H
3
O+

Thiscannowbeusedto:
decideifsomethingisagoodelectrolyteornot(highconcofionsinsolution=good
conductor)
decidethepHofthesalt(checkthe2ndequationandseeifOHorH
3
O+ismade)
CalculatethepHofthesalt(includingofthepHatequivalencepointofatitration)

WhenImavailable!AllinJ112orIwillputupanotesayingwhereIam.Feelfreetojustgoinandstudy!
Date: Period1 Period2 Period3 Period4 Period5
FridayNovember
7
Available Available Available Available Available
Monday
November10
Mostlikely
available
Available Available Available
Tuesday
November11
Available Available

Goodlucklovelystudents.

Itsbeenfun!

Bestofluckforyourexams!
:)