Documente Academic
Documente Profesional
Documente Cultură
Analytical
Chemistry
Eighth Edition
Chapter14 p
CHAPTER
Principles of Neutralization
Titrations
Chapter14 p
Figure 9F-1
Changes in p H of lakes
between 1930 and 1975.
Chapter14 p 260
Figure 9F-2
Effect of pH of lades on their fish population.
Chapter14 p 261
Figure 9F-3
Effect of presence of limestone on pH of lakes in the
United States. Shaded areas contain little limestone.
Chapter14 p 261
Figure 9F-4
Sulfur dioxide emissions from selected plants in the United States Have
dropped below the levels required by law.
Titrimetric Method
Titrimetric methodsofanalysisarecapable
ofrapidandconvenientanalyte
determinationswithhighaccuracyand
precision.
Titrimetric analysisisbasedonthe
completereactionbetweentheanalyte and
areagent,thetitrant.
Chapter14 p
aA +tT products
whereAandTrepresenttheanalyte
andtitrant,respectively,andaandtare
thestoichiometric coefficients.
Titrationsareoftenclassifiedbythe
natureofthistitrationreaction:acid
base,redox,precipitation and
complexation reactions arethemost
commonreactiontypes.
Chapter14 p
Volumetric Titration
Forvolumetrictitrations,theamount,nA,
ofanalyte inthesamplecanbecalculated
using
nA =a/tCTVT
whereCT istheconcentrationofthetitrant,andVT is
thevolumeoftitrant neededtoreachtheendpoint.
Againaandtarethestoichiometric coefficients.
Chapter14 p
Quantitativedeterminationoftheanalyte
concentrationrequiresthefollowing:
Thereisastoichiometric reactionbetweenanalyte and
titrant.Thisreactionshouldbefastandcomplete,and
thevaluesofaandtmustbeknown.
Theconcentrationofthetitrant solution,CT,mustbe
knownaccurately.Thetitrant solutionmustbe
standardized eitherbypreparingitusingaprimary
standardor,morecommonly,titratingitagainsta
solutionpreparedwithaprimarystandard.
Theendpoint volumemustbemeasuredaccurately
usinganappropriatechemicalindicatoror
instrumentalmethod.Ifaninstrumentalmethodis
usedtofollowtheprogressofthetitrationreaction,a
titrationcurvemaybegenerated,whichallowsforthe
analysisofmixturesand/orthedetectionof
Chapter14 p
interferences.
Figure 13-1
The titration process.
Chapter14 p 339
Figure 13-1
The titration process.
Chapter14 p 339
Figure 13-1
The titration process.
Chapter14 p 339
Figure 13-1
The titration process.
Chapter14 p 339
Figure 13-1
The titration process.
Titration end point. The end point is achieved when the barely
perceptible pink color of phenolphthalein persists. The flask on
the left shows the titration less than half a drop prior to the end
point; the middle flask shows the end point. The final reading of
the buret is made at this point, and the volume of base delivered
in the titration is calculated from the difference between the
initial and final buret readings. The flask on the right shows what
happens when a slight excess of base is added to the titration
mixture. The solution turns a deep pink color, and the end point
has been exceeded. In color plate 9, the color change at the end
339
point is much easier to see than in this black-and-white version.
Figure 13-2
Two types of titration curves.
Chapter14 p 351
Chapter14 p 351
Equivalence point -
End point
ExampleApplication:Analysisof
ChlorideinSurfaceWaters
Chloride isfrequentlyamajoranioninsurfaceand
groundwater;certainlyisamajorconstituentof
seawater.
Althoughchlorideinfreshwaterisusuallyof
geologicalorigin,runofffromroadssaltedduringthe
wintermaysignificantlyincreasethechloridecontent
ofsurroundingstreams,riversandlakes.
Ahighchlorideconcentrationmayimpartanoticeably
saltytastetopotablewater,andcanalsodamage
metallicpipesandgrowingplants.
Chapter14 p
ExampleApplication:Analysisof
ChlorideinSurfaceWaters(contd)
Argentometric titration ofwatersamplesisastandard
methodforchloridedetermination;
Concentrationsinthelowppm rangemaybedetected
usingpotentiometric titration.
Chapter14 p
Chapter14 p 354
Equivalence point -
End point
Figure 13-5
Effect of reaction
completeness on
precipitation titration
curves. For each curve,
50.00m of a 0.0500 M
solution of the anon was
titrated with 0.1000 M
AgNO3. Note that smaller
values of Ksp give much
sharper breaks at the end
point.
Chapter14 p 356
EndpointDetection
Avarietyofchemicalindicatorsareusedto
indicatetheendpointofargentometric titrations,
includingtheFajans,Volhard,andMohr methods
Asilverwireorringisasufficientindicator
electrodeforpotentiometric titrationsusing
AgNO3,whileafluorideISEissuitablefor
potentiometric endpointdetectionforfluoride
analysisusingLa3+orPb2+ titrant solutions.
Chapter14 p
adsorption
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
without
()
()
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Thiocyanate.Iron(III) Complex
a. Thiocyanate reacts with iron(III) to produce a deep, red color:
Fe3+ + SCN1-
FeSCN2+ (red)
The red color can be used to detect the presence of iron (III)
In titrations
Chapter14 p
Chapter14 p
adsorption
adsorbed
Indicator fluorescein
Chapter14 p
adsorbed
Chapter14 p
adsorbed
Chapter14 p
adsorption
adsorbed
adsorbed
adsorbed
Chapter14 p
adsorption
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
2-Furoic acid
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Thestandardreagentsusedinacid/base
titrationsarealwaysstrongacidsor
strongbase,mostlycommonlyHCl,
HClO4,H2SO4,NaOH,andKOH.
Weakacidsandbasesareneverusedas
standardreagentsbecausetheyreact
incompletelywithanalytes
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Acid/Base Indicators
HIn + H2O ' In- + H3O+
acid color
base color
acid color
Ka = [H3O+][In-]/[HIn]
[H3O+] = Ka ([HIn]/ [In-])
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Figure 14-2
Indicator color as a function of pH
(pKa=5.0).
Acompletecolorchange
whenthepHofthesolution
inwhichitisdossolved changes
from4to6.
Chapter14 p 371
Chapter14 p
Chapter14 p 372
Figure 14-1
Color change and
molecular model for
phenolphthalein.
Chapter14 p 370
Chapter14
p
Colorless Pink
Magenta
Chapter14 p
Red Yellow
Red
Chapter14 p
Yellow Blue
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
2.28
Chapter14 p
pH 7.00
pH 2.28
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p 374
Figure 14-3
Titration curves for
HCl with NaOH.
Curve A:50.00mL of
0.0500 M HCl with
0.1000 M NaOH.
Curve B: 50.00 mL of
0.000500 M HCl with
0.001000 M NaOH.
Chapter14 p 376
Figure 14-4
Titration curves for
NaOH with HCl.
Curve A:50.00 mL
of 0.0500 M NaOH
with 0.1000 M
HCl. Curve B:
50.00 mL of
0.00500 M NaOH
with 0.0100 M
HCl.
Chapter14 p 377
Chapter14 p
Chapter14 p
HA+H2O H3O+ + A-
Chapter14 p
A-+H2O HA + OH-
Chapter14 p
Henderson-Hasselbalch equation
is used to calculate the pH of
buffer solutions.
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
HA+H2O H3O+ + A-
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
A-+H2O HA + OH-
-5
10-14/6.31x10
Chapter14
p
Chapter14 p
Kb
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p
Chapter14 p 379
Figure 14-5
Curve for the titration
of acetic acid with
sodium hydroxide.
Curve A: 0.1000 M
acid with 0.1000 M
base. Curve B:
0.001000 M acid with
0.001000 M base.
Chapter14 p 381
Figure 14-6
The effect of acid strength (dissociation constant) on
titration curves. Each curve represents the titration of
50.00 mL of 0.1000 M acid with 0.1000 M base. Chapter14 p 382
Figure 14-7
The effect of base strength (Kb) on titration curves.
Each curve represents the titration of 50.00mL of
0.1000 M base with 0.1000 M HCl.
Chapter14 p 385