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15.16HydrogenDeficiencyIndex:DegreesofUnsaturation
Thischapterexplainedhowmassspectrometrycanbeusedtoascertainthemolecularformulaofanunknown
compound.Forexample,itispossibletodeterminethatthemolecularformulaofacompoundisC6H12O,butthatis
stillnotenoughinformationtodrawthestructureofthecompound.Therearemanyconstitutionalisomersthatshare
themolecularformulaC6H12O.IRspectroscopycantelluswhetherornotadoublebondispresentandwhetheror
notan
bondispresent.But,onceagain,thatisnotenoughinformationtodrawthestructureofthe
compound.InChapter16,wewilllearnaboutNMRspectroscopy,whichprovidesevenmoreinformation.Butbefore
wemoveontoNMRspectroscopy,thereisstillonepieceofinformationthatcanbegleanedfromthemolecular
formula.Acarefulanalysisofthemolecularformulacanoftenprovideuswithalistofpossiblemolecularstructures.
Thisskillwillbeimportantinthenextchapter,becausethemolecularformulaaloneoffershelpfulcluesaboutthe
structureofthecompound.Toseehowthisworks,let'sbeginbyanalyzingthemolecularformulaofseveralalkanes.
Comparethestructuresofthefollowingalkanes,payingspecialattentiontothenumberofhydrogenatomsattachedto
eachcarbonatom:

Ineachcasetherearetwohydrogenatomsontheendsofthestructures(circled),andtherearetwohydrogenatoms
oneverycarbonatom.Thiscanbesummarizedlikethis:

where isthenumberofcarbonatomsinthecompound.Accordingly,thenumberofhydrogenatomswillbe
.Inotherwords,allofthecompoundsshownhaveamolecularformulaof
.Thisistrueevenfor
compoundsthatarebranchedratherthanhavingastraightchain.

Thesecompoundsaresaidtobe saturatedbecausetheypossessthemaximumnumberofhydrogenatomspossible,
relativetothenumberofcarbonatomspresent.
Acompoundwitha bond(adoubleortriplebond)willhavefewerthanthemaximumnumberofhydrogenatoms.
Suchcompoundsaresaidtobe unsaturated.

Acompoundcontainingaringwillalsohavefewerthanthemaximumnumberofhydrogenatoms,justlikea
compoundwithadoublebond.Forexample,comparethestructuresof1hexeneandcyclohexane.

BothcompoundshavemolecularformulaC6H12becausebotharemissingtwohydrogenatoms[6carbonatoms
require
hydrogenatoms].Eachofthesecompoundsissaidtohaveone degreeof
unsaturation.The hydrogendeficiencyindex(HDI)isameasureofthenumberofdegreesofunsaturation.A
compoundissaidtohaveonedegreeofunsaturationforeverytwohydrogenatomsthataremissing.Forexample,a
compoundwithmolecularformulaC4H6ismissingfourhydrogenatoms(ifsaturated,itwouldbeC4H10),soithas
twodegreesofunsaturation
.
Thereareseveralwaysforacompoundtopossesstwodegreesofunsaturation:twodoublebonds,tworings,one
doublebondandonering,oronetriplebond.Let'sexploreallofthesepossibilitiesforC4H6(Figure15.33).

FIGURE15.33
AllpossibleconstitutionalisomersofC4H6.
Withthisinmind,let'sexpandourskillsset.Let'sexplorehowtocalculatetheHDIwhenotherelementsarepresent
inthemolecularformula.
1.Halogens:
Comparethefollowingtwocompounds.Noticethatchlorinetakestheplaceofahydrogenatom.Therefore,
forpurposesofcalculatingtheHDI,treatahalogenasifitwereahydrogenatom.Inotherwords,C2H5Cl
shouldhavethesameHDIasC2H6.

2.Oxygen:
Comparethefollowingtwocompounds.Noticethatthepresenceoftheoxygenatomdoesnotaffectthe
expectednumberofhydrogenatoms.Therefore,wheneveranoxygenatomappearsinthemolecularformula,
itshouldbeignoredforpurposesofcalculatingtheHDI.Inotherwords,C2H6OshouldhavethesameHDIas
C2H6.

3.Nitrogen:
Comparethefollowingtwocompounds.Noticethatthepresenceofanitrogenatomchangesthenumberof
expectedhydrogenatoms.Itgivesonemorehydrogenatomthanwouldbeexpected.Therefore,whenevera
nitrogenatomappearsinthemolecularformula,onehydrogenatommustbesubtractedfromthemolecular

formula.Inotherwords,C2H7NshouldhavethesameHDIasC2H6.

Insummary:
Halogens:
AddoneHforeachhalogen.
Oxygen:
Ignore.
Nitrogen:
SubtractoneHforeachN.
TheseruleswillenableyoutodeterminetheHDIformostsimplecompounds.Alternatively,thefollowingformula
canbeused:

whereCisthenumberofcarbonatoms,Nisthenumberofnitrogenatoms,Histhenumberofhydrogenatoms,and
Xisthenumberofhalogens.ThisformulawillworkforallcompoundscontainingC,H,N,O,andX.
CalculatingtheHDIisparticularlyhelpful,becauseitprovidescluesaboutthestructuralfeaturesofthecompound.
Forexample,anHDIofzeroindicatesthatthecompoundcannothaveanyringsor bonds.Thatisextremely
usefulinformationwhentryingtodeterminethestructureofacompound,anditisinformationthatiseasilyobtained
bysimplyanalyzingthemolecularformula.Similarly,anHDIof1indicatesthatthecompoundmusthaveeitherone
doublebondoronering(butnotboth).IftheHDIis2,thenthereareafewpossibilities:tworings,twodouble
bonds,oneringandonedoublebond,oronetriplebond.AnalysisoftheHDIforanunknowncompoundcanoften
beausefultool,butonlywhenthemolecularformulaisknownwithcertainty.
InChapter16,wewillusethistechniqueoften.Thefollowingexercisesaredesignedtodeveloptheskillof
calculatingandinterpretingtheHDIofanunknowncompoundwhosemolecularformulaisknown.

SKILLBUILDER

15.4 CALCULATINGHDI

LEARN THE SKILL

CalculatetheHDIforacompoundwithmolecularformulaC4H8ClNO2,andidentifythestructuralinformation
providedbytheHDI.

SOLUTION

STEP1Identifythemolecular
formulaofa
hydrocarbon(a
compoundwithonlyC
andH)thatwillhave
thesameHDI.
STEP2Determinehowmany
hydrogenatomsare
missingandassignan

HDI.

Thecalculationis:
NumberofH's:
Add1foreachCl:
IgnoreeachO:

8
+1
0

Subtract1foreachN: 1
Total:

ThiscompoundwillhavethesameHDIasacompoundwithmolecularformulaC4H8.Tobefullysaturated,
fourcarbonatomswouldrequire
H's.Accordingtoourcalculation,twohydrogenatomsare
missing,andtherefore,thiscompoundhasonedegreeofunsaturation:

Alternatively,thefollowingformulacanbeused:

Withonedegreeofunsaturation,thecompoundmustcontaineitheroneringoronedoublebond,butnotboth.
Thecompoundcannothaveatriplebond,asthiswouldrequiretwodegreesofunsaturation.

PRACTICE THE SKILL

15.31Calculatethedegreeofunsaturationforeachofthefollowingmolecularformulas:
(a)C6H10
(b)C5H10O2
(c)C5H9N
(d)C3H5CIO
(e)C10H20
(f)C4H6Br2
(g)C6H6
(h)C2Cl6
(i)C2H4O2
(j)C100H200Cl2O16
15.32Identifywhichtwocompoundsshownherehavethesamedegreeofunsaturation.
C3H8O
C3H5ClO2
C3H5NO2
C3H6

APPLY THE SKILL

15.33ProposeallpossiblestructuresforacompoundwithmolecularformulaC4H8Othatexhibitsasignalat
initsIRspectrum.
15.34ProposeallpossiblestructuresforacompoundwithmolecularformulaC4H8Othatexhibitsabroad

signalbetween3200and
1600and

initsIRspectrumanddoesnotcontainanysignalsbetween

15.35ProposetheonlypossiblestructureforacompoundwithmolecularformulaC4H6thatexhibitsasignal
at
initsIRspectrum.
15.36WhatstructuralfeaturesarepresentinacompoundwithmolecularformulaC10H20O?
15.37Eachpairofcompoundsbelowhasthesamenumberofcarbonatoms.Withoutcountingthehydrogen
atoms,determinewhetherthepairofcompoundshasthesamemolecularformula.Ineachcase,simply
determinetheHDIofeachcompoundtomakeyourdecision.Then,countthenumberofhydrogen
atomstoseeifyouranalysiswascorrect.
(a)

(b)

(c)

NEED MORE PRACTICE?

TryProblems15.48b,15.5415.55

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