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INTERNATIONALCHEMICALSERIES

LouisP.HAMMETT,PH.D.,ConsultingEditor

*

*

*

CALCULATIONSOF

ANALYTICALCHEMISTRY

Thequalityofthematerialsusedinthemanufacture

ofthisbookisgovernedbycontinuedpostwarshortages.

ASELECTIONOFTITLESFROMTHE

INTERNATIONALCHEMICALSERIES

LouisP.HAMMETT,PH.D.,ConsultingEditor

Amsden

Students Chemistry for Prcmedical

Physical

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Lecture Demonstrations in General

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AithurandSmith

SemixuicroQualitativeAnalysis

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AnIntroductiontothePreparationand

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IntroductiontoQuantitativeAnalysis

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CALCULATIONSOF

ANALYTICALCHEMISTRY

FORMERLYPUBLISHEDUNDERTHETITLE

CalculationsofQuantitativeChemicalAnalysis

byLEICESTERF.HAMILTON,S.B.

ProfessorofAnalyticalChemistry

MassachusettsInstituteofTechnology

andSTEPHENG.SIMPSON,PH.D.

AssociateProfessorofAnalyticalChemistry

MassachusettsInstituteofTechnology

FourthEdition

ThirdImpression

McGRAW-HILLBOOKCOMPANY,ING.

NEWYORKANDLONDON

1947

CALCULATIONSOFANALYTICALCHEMISTRY

Formerlypublishedunderthetitle

CalculationsofQuantitativeChemicalAnalysis

COPYRIGHT,1922,1927,1939,1947,BYTHE

McGRAw-HiLLBOOKCOMPANY,INC.

PRINTEDINTHEUNITEDSTATESOFAMERICA

Allrightsreserved. Thisbook,or

partsthereof,maynotbereproduced

w,anyformwithoutpermissionof

thepublishers.

PREFACE

ThetitleofthisbookhasbeenclfangedfromCalculationsof

QuantitativeChemicalAnalysistoCalculationsofAnalyticalChem-

istrybecausethesubjectmatterhasbeenexpandedtocoverthe stoichiometryofbothqualitativeandquantitativeanalysis.

Inordertoincludecalculationsusuallycoveredincoursesin

qualitativeanalysis,somerearrangementsofmaterialhavebeen

made,newsectionshavebeenadded,andchaptersdealingwith

equilibriumconstantsandwiththemoreelementaryaspectsof

analytical.calculationshavebeenconsiderablyexpanded.

Al-

together,thenumberofsectionshasbeenincreasedfrom78to

114andthenumberofproblemsfrom766to1,032.

Thegreaterpartofthebookisstilldevotedtothecalculations

ofquantitativeanalysis. Shortchaptersonconductometricand

amperometrictitrationsandasectiononcalibrationofweights

havebeenadded,andmanyotherchangesandadditionshave

beenmadeatvariouspointsinthetext. Asectionreviewingthe

useoflogarithmshasbeeninserted,andatableofmolecular

weightscoveringmostoftheproblemsinthebookisincludedin

theAppendix.

Itisfeltthateveryphaseofgeneralanalyticalchemistryis

adequatelycoveredbyproblems,bothwithandwithoutanswers,

andthatmostoftheproblemsrequirereasoningonthepartofthe

studentandarenotsolvedbysimplesubstitutioninaformula.

CAMBRIDGE,MASS.,

February,1947.

LEICESTERF.HAMILTON

STEPHENG.SIMPSON

CONTENTS

PREFACE

v

PART I. GENERALANALYSIS

CHAPTERI. MATHEMATICAL,OPERATIONS

1.FactorsInfluencingtheReliabilityofAnalyticalResults

2.DeviationMeasuresasaMeansofExpressingReliability...

3.SignificantFiguresasaMeansofExpressingReliability

.

1

2

3

4.RulesGoverningtheUseofSignificantFiguresinChemicalCom-

putations

6.RulesGoverningtheUseofLogarithms 5.ConventionsRegardingtheSolutionofNumericalProblems....

Problems1-18

....

7.MethodofUsingLogarithmTables

.

.

8.UseoftheSlideRule

Problems19-24

3

7 6

9

13

14

15

CHAPTERII. CHEMICAL,EQUATIONS

10.TypesofChemicalEquations 9.PurposeofChemicalEquations

11.lonizationofAcids,Bases,andSalts

12.IonicEquationsNotInvolvingOxidation

13.OxidationNumber

14.IonicOxidationandReductionEquations

Problems25-43

16

16

17

18

20

21

24

CHAPTERIII. CALCULATIONSBASEDONFORMULASANDEQUATIONS

15.MathematicalSignificanceofaChemicalP^ormula 17.MathematicalSignificanceofaChemicalEquation .

16.FormulaWeights

Problems44-70

CHAPTERIV.CONCENTRATIONOF

SOLUTIONS

^

18.MethodsofExpressingConcentration

19.GrainsperUnitVolume

vii

28

29 28

32

36

3f>

CONTENTS

20.PercentageComposition. .

.

21.SpecificGravity

22.VolumeRatios

.

.

23.MolarandFormalSolutions

24.EquivalentWeightandNormalSolution

36 36 37 37

38

25.SimpleCalculationsInvolvingEquivalents,Milliequivalents,and

Normality Problems71-86

26.LawofMassAction CHAPTERV. P]quiLiBRiUMCONSTANTS

27.IonProductConstantofWater

28.pllValue Problems87-94

29.lonizationConstant

30.CommonIonEffect. BufferedSolution

33.DissociationConstantsofComplexIons 31.lonizationofPolybasicAcids

32.ActivityandActivityCoefficients

Problems95-128

34.SolubilityProduct

35.FractionalPrecipitation

Problems129-159

36.ApplicationofBufferedSolutionsinAnalyticalChemistry

37.ControlofAcidityinHydrogenSulficiePrecipitations

38.SeparationsbyMeansofComplex-ionFormation

Problems160-178

39.DistributionRatio

Problems179-185

39

43

46 47 48 49

50

52

56 55 53

57

60'

62

64 67

68

69

71

73

74

CHAPTERVI. OXIDATIONPOTENTIALS

40.RelationoftheElectricCurrenttoOxidation-reduction("Redox")

Reactions

41.SpecificElectrodePotentials

42.RulesforWritingEquationsforHalf-cellReactions

45.CalculationoftheExtenttoWhichanOxidation-reductionReaction 43.Oxidation-reductionEquationsinTermsofHalf-cellReactions. .

.

44.RelationbetweenElectrodePotentialandConcentration

76

80 76 79

83

CONTENTS

ix

46.CalculationofEquilibriumConstantfromElectrodePotentials

Problems186-218

.

.

87

88

PARTII. GRAVIMETRICANALYSIS

CHAPTERVII. THECHEMICAL,BALANCE

47.SensitivenessoftheChemicalBalance

48.MethodofSwings

49.ConversionofWeightinAirtoWeightinVacuo

50.CalibrationofWeights

Problems219-240

93 95

94

97

99

CHAPTERVIII. CALCULATIONSOFGRAVIMETRICANALYSIS

51. LawofDefiniteProportionsAppliedtoCalculationsofGravimetric

Analysis

52.ChemicalFactors

53.CalculationofPercentages

Problems241-266

54.CalculationofAtomicWeights

Problems267-275

55.CalculationsInvolvingaFactorWeightSample

Problems276-284

102 105

104

109 106

109

110

112

56.CalculationoftheVolumeofaReagentRequiredforaGivenReaction113

Problems285-304

116

57.IndirectAnalyses

118

Problems305-331

121

CHAPTERIX.ELECTROLYTICMETHODS

58.DecompositionPotential

125

59.AnalysisbyElectrolysis

126

Problems332-359

130

CHAPTERX.CALCULATIONSFROMREPORTEDPERCENTAGES

60.CalculationsInvolvingtheEliminationorIntroductionofaCon-

stituent

135

61.CasesWhereSimultaneousVolatilizationandOxidationorReduction

Occur

Problems360-380

136 138

62.CalculationofMolecularFormulasfromChemicalAnalyses....141

x

CONTENTS

64.CalculationofFormulasofMineralsExhibitingIsomorphicRe-

placement

Problems381-424

145

147

PARTIII. VOLUMETRICANALYSIS

CHAPTERXI.CALIBRATIONOFMEASURINGINSTRUMENTS

65.MeasuringInstrumentsinVolumetricAnalysis

66.CalculationofTrueVolume

Problems425-435

153 153

155

CHAPTERXII.NEUTRALIZATIONMETHODS(AOIDIMETRY ANDALKALIMETRY)

67.DivisionsofVolumetricAnalysis

68.EquivalentWeightsAppliedtoNeutralizationMethods

Problems436-456

69.NormalityofaSolutionMadebyMixingSimilarComponents

Problems457-466

.

158

158

160

.

161

162

70.Volume-normality-milliequivalentRelationship

71.AdjustingSolutiontoaDesiredNormality

163 163

Problems467-480 Problems481-492

164

72.VolumeandNormalityRelationshipsbetweenReactingSolutions . 166

166

73.DeterminationoftheNormalityofaSolution

74.ConversionofDatatoMilliequivalents

Problems493-514

168

169

170

75.CalculationofPercentagePurityfromTitratioiiValues

76.VolumetricIndirectMethods

173

176

Problems515-532 Problems533-545

77.ProblemsinWhichtheVolumeofTitratingSolutionBearsaGiven

RelationtothePercentage

177

180

181

78.DeterminationoftheProportioninWhichComponentsArePresent

inaPureMixture Problems546-564

79.AnalysisofFumingSulfuricAcid

80.Indicators

81.EquivalencePoint

82.DeterminationofpHValueattheEquivalencePoint

183 184

186

189 188

191

CONTENTS

xi

84.TitrationofSodiumCarbonate Problems565-591

85.AnalysesInvolvingtheUseofTwoIndicators

86.RelationofTitrationVolumestoCompositionofSample

Problems592-606

87.AnalysisofPhosphateMixtures Problems607-612

199 196

199

204

205

207 209

CHAPTERXIII.OXIDATIONANDREDUCTION("REDOX")METHODS

(OXIDIMETRYANDREDUCTIMETRY)

88.FundamentalPrinciples

89.EquivalentWeightsofOxidizingandReducingAgents

90.CalculationsofOxidationandReductionProcesses

Problems613-630

91.PermanganateProcess

92.BichromateProcess

93.CericSulfateorCerateProcess

Problems631-682

94.lodimetricProcess

Problems683-712

211

211

216

217

225 219

226

227

234

238

CHAPTERXIV.PRECIPITATIONMETHODS(PRECIPITIMETRY)

95.EquivalentWeightsinPrecipitationMethods

Problems713-734

243

245

CHAPTERXV.COMPLEX-IONFORMATIONMETHODS(COMPLEXIMETRY)

96.EquivalentWeightsinComplex-ionMethods

Problems735-751

249

252

PARTIV. ELECTROMETRICMETHODS

CHAPTERXVI.POTENTIOMETRICTITRATIONS

97.PotentiometricAcidimetricTitrations 99.QuinhydroneElectrode

100.GlassElectrode 98.SimplePotentiometricTitrationApparatus

101.Potentiometric"Redox"Titrations

102.PotentiometricPrecipitationTitrations

255

256

257

258

259

261

xii

CONTENTS

CHAPTERXVII.CONDUCTOMETRICTITRATIONS

103.Conductance

104.MobilityofIons

105.ConductometricAcidimetricTitrations

106.ConductometricPrecipitationTitrations

107.ConductometricTitrationApparatus

Problems776-789

266

267 270 266

271

272

CHAPTERXVIII.AMPEROMETRICTITRATIONS

108.PrincipleofanAmperometricTitration

Problem790

275

278

PARTV. GASANALYSIS

CHAPTERXIX.CALCULATIONSOFGASANALYSES

109.FundamentalLaws

110.Gas-volumetricMethods

111.CorrectionforWaterVapor

112.CalculationsofGas-volumetricAnalyses

Problems791-813 Problems814-836

113.AbsorptionMethods

114.CombustionMethods

279

281

282 284 283 286

287

292

PARTVI. COMMONANALYTICALDETERMINATIONS

PARTvii."PROBLEMSONSPECIFICGROUPSAND

DETERMINATIONS

A.QualitativeAnalysis

SilverGroup

HydrogenSulfideGroup

AmmoniumSulfideGroup

AlkalineEarthandAlkaliGroups

AnionGroups

B.QuantitativeAnalysis

Water

Silver,Mercury,Gold,Platinum Sodium,Potassium

Ammonium,Ammonia,Nitrogen

Halogens,Cyanide,Thiocyanate,Halogenacids

309

310

311

312

313

313 313

315 315 314

CONTENTS

xiii

Barium,Strontium,CalciuirifMagnesium

Limestone,Lime,Cement

Iron,Aluminum,Titanium

Cerium,Thorium,Zirconium,Uranium,Beryllium,Bismuth,Boron

Copper,Lead,Zinc,Cadmium,Brass

Tin,Antimony,Arsenic,Bronze

Carbon,CarbonDioxide,Silicon,Tungsten,Molybdenum

Chromium,Vanadium Manganese

Cobalt,Nickel

Phosphorus

Sulfur,Selenium

GeneralandMiscellaneousAnalyses

163

317

317

. .

320

321

323

324

325

327

329

329

331

335

APPENDIX

INDEX

365 379

PARTI

GENERALANALYSIS

CHAPTERI

MATHEMATICALOPERATIONS

arepresent;acompoundormixtureisanalyzedbyquantitative andquantitativeanalysis. 1.FactorsInfluencingtheReliabilityofAnalyticalResults. Acompoundormixtureisanalyzedby

Analyticalchemistryisordinarilydividedintoqualitativeanalysis

qualitativeanalysistodeterminewhatconstituentsorcomponents

analysistodeterminetheproportionsinwhichtheconstituents

orcomponentsarepresent.

Calculationsinqualitativeanalysisarelimitedmostlytothose

pertainingtoequilibriumconstantsandsimpleweightandvolume

relationships. Calculationsinquantitativeanalysisaremoreex-

tensiveandarebaseduponnumericaldataobtainedbycareful

measurementofmassesandvolumesofchemicalsubstances.From

thenumericaldataobtainedfromthesemeasurementsthedesired

proportionscanbecalculated.Itisfound;however,thatduplicate

analysesofthesamesubstance,evenwhenmadebyexperienced

analystsfollowingidenticalmethods,rarelygivenumericalvalues

whichareexactlythesame. Furthermore,thediscrepancybe-

tweenresultsisfoundtodependuponthemethodused,andan

analyticalresultobtainedbyoneproceduremaydifferappre-

ciablyfromasimilarresultobtainedbyanentirelydifferentpro-

cedure. Themostimportantfactorswhichthusinfluencethe

precisionofanalyticalresultsarethefollowing:(1)themanipu-

lativeskilloftheanalyst;(2)theexperimentalerrorsofthepro-

cedureitself,suchastheslightsolubilityofsubstancesassumed

tobeinsolubleorthecontaminationofprecipitatesassumedto

bepure;(3)theaccuracyofthemeasuringinstrumentsused;and

(4)fluctuationsoftemperatureandbarometricpressure.Inorder,

therefore,thatanumericalresultobtainedfromchemicalmeas-

urementsmaybeofscientificortechnicalvalue,theobserver

shouldhaveatleastageneralideaofitsreliability.

l

2

CALCULATIONSOFANALYTICALCHEMISTRY

Inthisconnection,thereshouldbekeptinmindadistinction

betweenaccuracyandreliability. Theaccuracyofanumerical

resultisthedegreeofagreementbetweenitandthetruevalue;

thereliabilityorprecisionofanumericalresultisthedegreeof

agreementbetweenitandothervaluesobtainedundersubstan-

tiallythesameconditions.

Thus,supposeduplicatedetermina-

tionsofthepercentageofcopperinanoregave52.30percent

and52.16percent,andsupposetheactualpercentagewas52.32.

Itcanbeassumedthattheanalystwouldreportthemeanor

averageofthetwovaluesobtained,namely52.23percent. This

differsfromthetruevalueby0.09percent,whichrepresentsthe

absoluteerroroftheanalysis. Expressedinpartsperthousand,

theerrorwouldbe0.09/52.32X1,000=1.7partsperthousand.

Thisisknownastherelativeerroroftheanalysis.

Sinceinmostchemicalanalysesthetruevalueisnotknown,

itfollowsthattheaccuracyofagivendeterminationisseldom

known.Wecanspeakonlyoftheprecisionorreliabilityofthe

numericalresultsobtained.

2.DeviationMeasuresasaMeansofExpressingReliability.

Thenumericalmeasureofthereliabilityofaresultisknownas

itsprecisionmeasure. Atypeofprecisionmeasurewhichisof

particularimportanceincarefulphysicalandchemicalworkis

thedeviationmeasure.Suppose,forexample,repeatedindependent

readingsofaburetgavethefollowingvalues:

(a)43.74

(c) (6)43.76 43.76

(d)43.75

  • (e) 43.77

(/) (h)43.76 43.75

(p)43.75

(i)

43.73

Themostprobablevaluetorthisreadingisobviouslythemean,

43.753,whichisobtainedbydividingthesumofthereadingsby

thenumberofreadingstaken.Thedeviationofeachmeasurement

fromthismean,regardlessofsign,isshowninthefollowing:

(a)0.013

(6)0.007 (d)0.003

(c) 0.007

  • (e) 0.017

(/)0,003

(g)0.003

(h)0.007

(i) 0.023

MATHEMATICALOPERATIONS

3

Themeandeviation,oraverageoftheseninevalues,is0.0092and

representstheamountbywhichanaveragesingleindependent

readingdiffersfromthemostprobablevalue;itisthereforea

measureofthereliabilityofasingleobservation.

Itismoreimportant,however,toknowthereliabilityofthe

meanthanthatofasingleobservation. Itcanbeshownthat

thereliabilityofameanoraveragevalueisnumericallyequalto

theaveragedeviationofasingleobservationdividedbythesquare forthereadingmaybeexpressedas43.753

rootofthenumberofobservationstaken. Intheabove,the

averagedeviationofthemeanis0.0092/V9=0.0031,andthevalue

0.0031.

(Itis

customarytouseonlytwosignificantfiguresinalldeviationmeas-

ures.) Whenseveralsuchmeasurementsareinvolvedinacom-

putation,itispossibletocalculatefromthedeviationmeasure

ofeachmeasurementthedeviationmeasureorprecisionmeasure

ofthefinalresultandthusobtainanumericalmeasureofthe

probablereliabilityofthatresult. Formethodsofsuchcalcula-

tionthestudentisreferredtoGoodwin'sPrecisionofMeasure-

ments.

3.SignificantFiguresasaMeansofExpressingReliability.

Inmostchemicalanalysesrelativelyfewindependentreadingsor

determinationsaremade,sothatnumericalprecisionmeasures

arenotoftenused. Insuchcasesthereliabilityorprecisionofa

numericalvalueisbestindicatedbythenumberofsignificant

figuresusedinexpressingthatvalue. Itistruethatthismethod

ofexpressiongivesonlyanapproximateideaofthereliabilityof

aresult,buttheimportanceoftheretentionofthepropernumber

ofsignificantfiguresinanalyticaldatacannotbeoveremphasized.

Anumericalresultexpressedbyfewerormoresignificantfigures

thanarewarrantedbythevariousfactorsinvolvedmaygiveto

anobserveranimpressionnearlyaserroneousaswouldbegiven

byaresultwhichisinaccurate.

4.RulesGoverningtheUseofSignificantFiguresinChemical

Computations. Thefollowingdefinitionsandrulesaresuggested

bythosegiveninGoodwin'sPrecisionofMeasurements:

Anumberisanexpressionofquantity.

Afigure,ordigit,isanyoneofthecharacters0,1,2,3,4,5,6,

7,8,9,which,aloneorincombination,servetoexpressnumbers.

Asignificantfigureisadigitwhichdenotestheamountofthe

4

CALCULATIONSOFANALYTICALCHEMISTRY

quantityintheplaceinwhichitstands. Inthecaseofthe

number243,thefiguressignifythattherearetwohundreds,four

tens,andthreeunitsandarethereforeallsignificant. Thechar-

figure,oritmaybeusedmerelytolocatethedecimalpoint. isusedintwoways.

acter

Itmaybeusedasasignificant

It

isasignificantfigurewhenitindicatesthatthequantityinthe

placeinwhichitstandsisknowntobenearerzerothantoany

othervalue. Thus,theweightofacruciblemaybefoundtobe

10.603grams,inwhichcaseallfivefigures,includingthezeros,

aresignificant. Iftheweightingramsofthecruciblewerefound

tobe10.610,meaningthattheweightasmeasuredwasnearer

10.610than10.609or10.611,bothzeroswouldbesignificant.

placetotherightofthedecimalpoint. Byanalysis,theweightoftheashofaquantitativefilterpaper Anyothercharacters

isfoundtobe0.00003gram.Herethezerosarenotsignificant

butmerelyservetoshowthatthefigure3belongsinthefifth

exceptdigitswouldservethepurposeaswell. Thesameistrue

ofthevalue356,000inches,whensignifyingthedistancebetween

twogivenpointsasmeasuredbyinstrumentswhichareaccurate

tothreefiguresonly. Thezerosarenotsignificant. Inorderto

avoidconfusion,thisvalueshouldbewritten3.56X105inches.

Ifthedistancehasbeenmeasuredtothenearest100inches,it

shouldbewritten3.560X106inches.

RuleI. Retainasmanysignificantfiguresinaresultandin

dataingeneralaswillgiveonlyoneuncertainfigure. (Forvery

accurateworkinvolvinglengthycomputations,twouncertain

figuresmaysometimesberetained.) Thus,thevalue25.34,rep-

resentingthereadingofanordinaryburet,containstheproper

numberofsignificantfigures,forthedigit4isobtainedbyesti-

matinganungraduatedscaledivisionandisdoubtlessuncertain.

Anotherobserverwouldperhapsgiveaslightlydifferentvaluefor

theburetreading e.g.,25.33or25.35. Allfourfiguresshould

beretained. RuleII. Inrejectingsuperfluousandinaccuratefigures,in-

creaseby1thelastfigureretainedifthefollowingrejectedfigure

is5orover. Thus,inrejectingthelastfigureofthenumber

16.279,thenewvaluebecomes16.28.

RuleIII. Inaddingorsubtractinganumberofquantities,

extendthesignificantfiguresineachtermandinthesumordif-

MATHEMATICALOPERATIONS

5

ferenceonlytothepointcorrespondingtothatuncertainfigure

occurringfarthesttotheleftrelativetothedecimalpoint.

Forexample,thesumofthethreeterms0.0121,25.64,and

1.05782,ontheassumptionthatthelastfigureineachisuncer-

tain,is

0.01

25.64

1.06

26.71

Hereitisseenthatthesecondtermhasitsfirstuncertainfigure

(the4)inthehundredthsplace,thefollowingfiguresbeingun-

known.Hence,itisuselesstoextendthedigitsoftheotherterms

beyondthehundredthsplaceeventhoughtheyaregiventothe

ten-thousandthsplaceinthefirsttermandtothehundred-thou-

sandthsplaceinthethirdterm.Thethirddigitofthethirdterm

isincreasedby1inconformitywithRuleIIabove.

Thefallacy

ofgivingmorethanfoursignificantfiguresinthesummaybe

shownbysubstitutingxforeachunknownfigure. Thus,
cisionoftheproductorquotientcannotbegreaterthantheper- uncertain,is

0.0121*

1.05782

26.7Ixxx

RuleIV. Inmultiplicationordivision,thepercentagepre-

centageprecisionoftheleastprecisefactorenteringintothe

computation. Hence,incomputationsinvolvingmultiplication

ordivision,orboth,retainasmanysignificantfiguresineach

factorandinthenumericalresultasarecontainedinthefactor

havingthelargestpercentagedeviation. Inmostcases,asmany

significantfiguresmayberetainedineachfactorandintheresult

asarecontainedinthefactorhavingtheleastmemberofsignificant

figures.

Forexample,theproductofthethreeterms0.0121,25.64,

and1.05782,ontheassumptionthatthelastfigureineachis

0.0121X25.6X1.06=0.328

for,ifthefirsttermisassumedtohaveapossiblevariationof1

inthelastplace,ithasanactualdeviationof1unitinevery

6

CALCULATIONSOFANALYTICALCHEMISTRY

121units,anditspercentagedeviationwouldbey^rX100=0.8.

Similarly,thepossiblepercentagedeviationofthesecondterm

wouldbe ,,X100=0.04,andthatofthethirdtermwouldbe

lUOj/o^*-QOX100=0.0009. Thefirstterm,havingthelargestper-

figureswhichmaybeproperlyretainedintheproduct,forthe centagedeviation,thereforegovernsthenumberofsignificant

productcannothaveaprecisiongreaterthan0.8percent. That

is,theproductmayvaryby0.8partineveryhundredorbynearly

3partsinevery328. Thelastfigureintheproductasexpressed

withthreesignificantfiguresaboveisthereforedoubtful,andthe

propernumberofsignificantfigureshasbeenretained.

RuleV. Computationsinvolvingaprecisionnotgreaterthan

one-fourthofl.percentshouldbemadewitha10-inchsliderule.

Forgreaterprecision,logarithmtablesshouldbeused. Ifthe
mantissaofthelogarithmofeachfactorasareproperlycon- solutionoftheexamplegivenunderRuleIV,thelogarithmsof

old-stylemethodofmultiplicationordivisionmustberesorted

to,rejectallsuperfluousfiguresateachstageoftheoperation.

RuleVI. Incarryingouttheoperationsofmultiplicationor

divisionbytheuseoflogarithms,retainasmanyfiguresinthe

tainedinthefactorsthemselvesunderRuleIV. Thus,inthe

thefactorsareexpressedasfollows: log25.64

=1.409

log0.0121=8.083-10

log1.05782=0.024

9.516-10=log0.328

5.ConventionsRegardingtheSolutionofNumericalProblems.

Inthecalculationofnumericalresultsfromchemicaldatawhich

havebeenobtainedunderknownconditionsandbyknownmeth-

ods,littledifficultyshouldbeexperiencedinforminganapproxi-

mateestimateofthereliabilityofthevariousfactorsandofthe

resultsobtained. Inthecaseofnumericalproblemswhichare

unaccompaniedbyanydatatoshowtheconditionsunderwhich

thevariousmeasurementsweremadeortheprecisionofthevalues

given,theretentionofthepropernumberofsignificantfiguresin

MATHEMATICALOPERATIONS

7

thefinalcomputedresultsmaybeamatterofconsiderablejudg-

ment. Insuchcasestheruleslistedabovearesubjecttomodi-

fication,butinanycasetheneedforacertainamountofcommon

senseandjudgmentinusingtheminnowaydetractsfromtheir

value.

. Inthesolutionofproblemsinthisbook,itmaybeassumedthat

thegivendataconformtoRuleI,above.Inproblemscontaining

suchexpressionsas"a2-gramsample/ 7 "a25-ml.pipetful,"or

"atenth-normalsolution/'itmaybeassumedthattheweight

ofthesample,thevolumeofthepipet,andthenormalityofthe

solutionareknowntoaprecisionatleastasgreatasthatofthe

otherfactorsinvolvedintheproblem.

Itshouldalsoberememberedthattheatomicweightsofthe

elementsareknownonlytoalimitednumberofsignificantfigures

and,intheabsenceoffurtherdata,itmaybeassumedthatthe

valuesordinarilygiveninatomic-weighttablesconformtoRuleI

above,inthatthelastfigureineachisdoubtful. Itfollows,there-

fore,thatthesameattentionshouldbepaidtotheprecisionof thatsuchvaluesrepresentmeanvaluesobtainedfromduplicate Problems

theatomicandmolecularweightsinvolvedincomputationsasto

thatofanyotherdata.

Itoftenhappensthatindependentcalculationsfromgivendata

giveresultswhichdisagreebyonlyoneqrtwounitsinthelast

significantfigureretained.

Thisisusuallyduetothefactthat

figureshavebeenrejectedatdifferentstagesoftheoperations

involved;butthisisusuallyofnoimportance,since,whenproperly

expressed,thelastsignificantfigureintheresultisdoubtful

anyway.

Analyticaldeterminationsareusuallydoneinduplicate. In

mostoftheproblemsinthisbook,however,dataapparently

coveringonlyonedeterminationaregiven. Itmaybeassumed

determinations.

1.Howmanysignificantfiguresareimpliedinthevalue2.20X10""9?

In

thevalue5,000.002?Inthevalue2.010X105?

Ans. Three.Seven.Four.

2.CalculatethemolecularweightofOsCl4toashighadegreeofprecision

asiswarrantedbytheatomicweightsinvolved.

8

CALCULATIONSOFANALYTICALCHEMISTRY

3.Expressthevelocityoflight,186,000milespersecond,insuchawayas

toindicatethatithasbeenmeasuredtothenearest100milespersecond.

Ans.

1.860X106milespersecond.

4.Samplesweresenttosevendifferentchemiststobeanalyzedforper-

centageofprotein. Thevaluesreportedwere43.18,42.96,42.88,43.21,

43.01,43.10,43.08. Whatisthemeanvalue,theaveragedeviationofasingle

valuefromthemean,andthedeviationofthemean?Ifthecorrectpercentage

is43.15,whatistherelativeerrorofthemeaninpartsperthousand?

Ans. 43.060,0.094,0.036. 2.1.

6.Anoreactuallycontains33.79percentFe2O8. Duplicatedeterminations

give33.80and34.02percent,andthemeanoftheseisreported.Byhowmany

partsperthousanddotheduplicateresultsdifferfromeachother?Whatis

themeanvalue?Whatistheabsoluteerror? Whatistherelativeerrorin

partsperthousand?

Ans.

6.5. 33.91percent. 0.12percent. 3.5.

6.Twoanalysts,workingindependently,analyzeasampleofsteelandre-

portthefollowingresults: 0.041percent

ANALYSTA:

ANALYSTB:

Byhowmanypartsperthousanddothecheckvaluesagreeineachcase? abilityasananalyst? Sulfur=0.042percent

Sulfur=0.04199percent

0.04101percent

Eachmanusesa3.5-gramsampleweighedtothenearesttenthofagram. Is

analystBjustifiedinhisreport? Dohisfiguresnecessarilyindicategreater

Ans. 24parts,24parts. No.No.

7.Itisnecessarytosolvethefollowing:

eachtermbeinguncertaininthelastsignificantfigure. (1.276X0.00047)+(1.7X10~4 )-(0.0021764X0.0121) Shouldyouuse

arithmetic,logarithms,oraslideruleinthemultiplications? Whatisthe

finalanswer? Ans.

0.1133,respectively,istobemultipliedby1.36ml.asmeasuredbyanordinary Sliderule. 7.5X10~