CH 13 Comments PDF

comments by
Fatemeh Masdarolomoor
Shahrood University of Technology
July 2020
Titrations in
CHAPTER 13 al
Analytical Chemistry
ɧķ Ɖ Ю
ź
ˬΎϫΩϳγ΍ ̵έϳ̳ ϩί΍Ωϧ΍ ̵΍έΑ ϥϭϳγ΍έΗϳΗ ̵ΎϬηϭέ
Ş
ˬ̵ίϠϓ ̵ΎϬϧϭϳ ˬΎϫ ϩΩϧϫΎ̯ ˬΎϫ ϩΩϧγ̯΍ ˬΎϫίΎΑ
έ̴ϳΩ Ω΍ϭϣ ί΍ ̵έΎϳγΑ ϭ Ύϫ ϥϳ΋Ηϭέ̡
Titrations
tions are widelyy used in analytical
analy chemistry to determine acids, bases, oxidants,
oxiidants, reductants,
reducttants,
Ԯ
metal tal ion
ions,
ions
ns, proteins, and
nd many
man
m other species. TTitrations are based on a reaction between the ana-
lyte
tee aand a standard reagent known as the titrant. The reaction is of known and reproducible stoi-
chiometry.
chihii The volume, or the mass, of the titrant needed to react completely with w the analyte is
determined and used to calculate the quantity of analyte. A volume-based titration
de io is shown in this
ffigure in which the standard solution is added from a buret, and the reaction occursoocccc in the Erlen-
ɧƈ Ҏ
meyer flask. In some titrations, known as coulometric titrations, the quantity

mey ntity off charge
ch required
i to
completely consume the analyte is obtained. In any titration, the point of chemical
comp chem
hem equivalence,
eq len
called
lled the end point when determined experimentally, is signaled by an indicator
cat color change
icat chaa orr a
ź
change in an instrumental response. This chapter introduces the titration principle
chang rin and the
thh calcu-
lations that determine the amount of the unknown.
lati own. Titration
Tit curves, which show w theth progress
ogr of the
titration, are also introduced. Such curves will be used in several of the followingg chapters.
cha
ch
chapte
ƸŻ ֌
źƼࣰ
:αΎγ΍
Charles D. Winters Εγ΍ ϡίϻ ΕϳϟΎϧ΁ ΎΑ ϝϣΎ̯ εϧ̯΍ϭ ̵΍έΑ Ϫ̯ ϡϭϠόϣ ΕυϠϏ ΎΑ έ̴ηϧ̯΍ϭ ϥ΍ίϳϣ ϥϳϳόΗ
Ĺ ͇҅Г
Titrationn methodods are
methods
metho
known concentration
ntrat
ra
arre based
terminingg the quantity
qquant
ua ti
b on de-
ti y of a reagent
g of
that is required
q
T itration methods, often called titrimetric methods,
ethods,
ods
surin
of quantitative procedures based on measuring uring
ring
ds include
n the
ng
cchem
concentration that is consumed by an analyte in a chemicalch
hem
inc
th amount
am
a large
rge and
rge a powerful group
of a reagent of known
emical or electrochemical
e reaction.
to react completely with the analyte.
The reagent may be a standard solution Volumetric titrations involve measuring the volumeolume of a so ssolution
solutio
oolut of known concentration
of a chemical or an electric current of nalyte.
yt In Gravimet
that is needed to react completely with the analyte. avi
Gravimetric titrations, the mass of
known magnitude. the reagent is measured instead of its volume. Inn coulomet
coulome
coulometric titrations, the “reagent”
In volumetric titrations, the volume is a constant direct electrical current of known magnitudenitud that consumes the analyte. For
nitude
of a standard reagent is the measured this titration, the time required (and thus the total charge) to complete the electrochemical
quantity.
reaction is measured (see Section 22D-5).
In coulometric titrations, the quantity This chapter provides introductory material that applies to all the different types of
of charge required to complete a reac- titrations. Chapters 14, 15, and 16 are devoted to the various types of neutralization titra-
tion with the analyte is the measured
quantity.
tions in which the analyte and titrants undergo acid/base reactions. Chapter 17 provides
information about titrations in which the analytical reactions involve complex formation
or formation of a precipitate. These methods are particularly important for determining
a variety of cations. Finally, Chapters 18 and 19 are devoted to volumetric methods in
which the analytical reactions involve electron transfer. These methods are often called
redox titrations. Some additional titration methods are explored in later chapters. These
methods include amperometric titrations in Section 23B-4 and spectrophotometric
titrations in Section 26A-4.
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13A Some Terms Used in Volumetric Titrations303
13A SOME TERMS USED IN VOLUMETRIC TITRATIONS1

A standard solution (or a standard titrant) is a reagent of known concentration that A standard solution is a reagent
is used to carry out a volumetric titration. The titration is performed by slowly add- of known concentration. Standard
ing a standard solution from a buret or other liquid-dispensing device to a solution solutions are used in titrations and
in many other chemical analyses.
of the analyte until the reaction between the two is judged
judge complete. T The volume or
mass of reagent needed to complete the titration onn is determined
dete
determ
det
dee from the difference
between the initial and final readings. A volumetrictric titration
lumetric titrat
tittrat on process
ration p oce s iss depicted
proce dep in
Figure 13-1.
Ƹɧķ Ɖ Ю
Şź
It is sometimes necessary to add an excess off the
t standard
standar
st d titrant
rd ti ntt and
a d then
th de-
termine the excess amount by back-titration on with
back-titration
a th a second
s nd d standard
sstan d titrant.
t For Back-titration is a process in which
example, the amount of phosphate in a sample can n be
an b determined
determin
determ by
b adding a mea- the excess of a standard solution used
sured excess of standard silver nitrate to a solution
n of the
th sample,
sam which
wh leads to the to consume an analyte is determined
by titration with a second standard
formation of insoluble silver phosphate:
hate:
te: solution. Back-titrations are often
έ΍ΩϘϣ ϪΑ Ϫ̯ Ε΍έΗϳϧ ϩέϘϧ Ωέ΍ΩϧΎΗγ΍ ϝϭϠΣϣ q d when the rate of reaction
required
͕Ԯ
2 S
3Ag1 1 PO4332
.Ωϭη ̶ϣ ϪϓΎο΍ ΕϳϟΎϧ΁ ϪΑ "̵ΩΎϳί" Ύϣ΍ ϡϭϠόϣ 3Ag Ag3PO s)
O4((s) y and reagent
between the analyte g is slow
or when the standard solution lacks
The excess silver nitratee is the
then back-t
back-titrated
bac
back
ack
ckk with a standard solution of potassium stability.
‫ڢ‬
thiocyanate:
Ε΍έΗϳϧ ϩέϘϧ ̵ΩΎϳί ˬαϭ̰όϣ ϥϭϳγ΍έΗϳΗ έΩ 1
ɧƈ Ĺ Ҏ
2 S
.Ωϭη ̶ϣ έΗϳΗ ΕΎϧΎϳγϭϳΗ Ωέ΍ΩϧΎΗγ΍ ϝϭϠΣϣ ΎΑ Agg 1 SCN AgSCN(s)
The amountunt of silve nitrate

silver n trate
te is chemically
chemic equivalent to the amount of phosphatete
ź
ion plus the amount
am thiocyanate
mount of thi
th ocyanate for the back-titration. The amount of phos-
yanate used fo
phate is then
n the d ren bbetween
difference the amount of silver nitrate and the
tween th he amount
am of
thiocyanate.
ate.
ƸŻ ֌
źƼࣰ
13A-1 Equivalence
A-1 Equivale
1 qu Points and End Points
Ĺ ͇҅Г
Th
The
he equivalence
equiv
uiv
uivaalen point in a titration is a theoretical point reached
ivalenc r when the amount
mount
oun
un he equivalence
The equiv
equiva len point is the point in
ivvalenc
ival
added
of add
adde titrant
tr is chemically equivalent to the amount of analyte in the sample.
dded titr
titr e. For
ple. F
Fo ation
tion when
a titration wh the amount of added
example,
mp e the equivalence point in the titration of sodium chloride with silver nitrate
example nitra
iitrate
it standard d reagent is equivalent to the
am
amount of analyte.
occursr after exactly one mole of silver ion has been added for each mole off ch
urs chlo-
chl
chlo
hlloo-
h
hlo
ride ion in the sample. The equivalence point in the titration of sulfuric acid with h
sodium hydroxide is reached after introducing 2 moles of base for each ach mole
of acid.
We cannot determine the equivalence point of a titration experimentally. Instead,
nstead,
we can only estimate its position by observing some physical change associated with the
condition of chemical equivalence. The position of this change is called the end point The end point is the point in a titra-
for the titration. We try very hard to ensure that any volume or mass difference between tion when a physical change occurs
the equivalence point and the end point is small. Such differences do exist, however, as that is associated with the condition of
chemical equivalence.
a result of inadequacies in the physical changes and in our ability to observe them. The
difference in volume or mass between the equivalence point and the end point is the
titration error. In volumetric methods, the titration
Indicators are often added to the analyte solution to produce an observable physi- error, Et, is given by
cal change (signaling the end point) at or near the equivalence point. Large changes in
the relative concentration of analyte or titrant occur in the equivalence-point region. Et 5 Vep 2 Veq
These concentration changes cause the indicator to change in appearance. Typical
where Vep is the actual volume of reagent
required to reach the end point and Veq
is the theoretical volume necessary to
1 reach the equivalence point.
For a detailed discussion of volumetric methods, see J. I. Watters, in Treatise on Analytical Chemistry,
I. M. Kolthoff and P. J. Elving, Eds., Part I, Vol. 11, Chap. 114. New York: Wiley, 1975.
304CHAPTER 13 Titrations in Analytical Chemistry
Ƹɧķ Ɖ Ю
Charles D. Winters
Winterss
Charles D. Winters
Chharles D. Win
Charles
Typical
picall setup
setu ffor carrying
ying
ing Detail
D et of the buret gradua- Before the titration begins.
o a titration.
out itratio T The ap- tions. Normally, the buret is The solution to be titrated,
͕Ԯ
paratus
pa
parat us consists
aratus consi
con of a buret,
uret,
et, filled with titrant solution an acid in this example, is
a buretet stand
ret sta and clamp to within 1 or 2 mL of the placed in the flask, and the
withh a white
th w porcelain base zero position at the top. indicator is added as shown
‫ڢ‬
provide an appropriate
to pro
provi The initial volume of the in the photo.
ot TheT indicator
background
bac
back
ackg
ack
ac for viewing buret is read to the near- in this case
ase is phenolphtha-
phen
ɧƈ Ĺ Ҏ
indicator
indi
in
indic
dic changes, and a est 0.01 mL. The reference lein, which
whi
hich
hiich
ch turns
tu
t pink in
pin
wide-mouth Erlenmeyer
wide-m
wide-mo
w point on the meniscus and basic
asicc solution.
soluti
solut
lu
ution.
ut
uti
ti
flask containing
sk conta
con a precisely the proper position of the
known volume
n volum
v of the solu- eye for reading are depicted
ted
ź
tion to bbe ttitrated. The so- in Figure 2-21.
lution is normally delivered
intoo the flask using a pipet,
as shown in Figure 2-22.
Ż֌
źƼࣰ
Г
Charles D. Winters
Charles D. Winters
During titration. The titrant Titration end point. The end point is achieved when the
is added to the flask with barely perceptible pink color of phenolphthalein persists.
swirling until the color of The flask on the left shows the titration less than half a
the indicator persists. In the drop prior to the end point; the middle flask shows the
initial region of the titra- end point. The final reading of the buret is made at this
tion, titrant may be added point, and the volume of base delivered in the titration is
rather rapidly, but as the calculated from the difference between the initial and final
end point is approached, buret readings. The flask on the right shows what hap-
increasingly smaller por- pens when a slight excess of base is added to the titration
tions are added; at the end mixture. The solution turns a deep pink color, and the end
point, less than half a drop point has been exceeded. In color plate 9, the color change
of titrant should cause the at the end point is much easier to see than in this black-
Figure 13-1 The titration process.
13-1The indicator to change color. and-white version.
13B Standard Solutions305
indicator changes include the appearance or disappearance of a color, a change in

color, or the appearance or disappearance of turbidity. As an example, the indicator
used in the neutralization titration of hydrochloric acid with sodium hydroxide is
phenolphthalein, which causes the solution to change from colorless to a pink color
once excess sodium hydroxide has been added.
We often use instruments to detect end points.
oints s. These
ts.
ts Th
T instruments respond
to properties of the solution that change in n a characteristic
charac
chara acterist way
ract w during
wa urin the ti-
durin
tration. Among such instruments are colorimeters, ers,, turbidimeters,
orimeters,
ters, turb
t urb
urbidim ter s, spectropho-
bid meters spectr
spect
Ƹɧķ Ɖ Ю
tometers, temperature monitors, refractometers, rs, voltmeters,
ters, voltmet
oltm ers, rss current
rs, ent meters,
c rrent m te and
meters
Şź
conductivity meters.
13A-2 Primary Standards
A primary standard is a highly g purified
rified
fied compound
co d that
th
tha
hatt serves
sserv as
a a reference mate- A primary standard is an ultrapure
her
er analytical
rial in titrations and in other an
a alytical
al methods.
metho
me he accuracy
The accu
acccuracy of a method critically compound that serves as the reference
͕Ԯ
depends on the properties off the th
he p
primary
rimar standard.
d.. Important
Impo
Im requirements for a material for a titration or for another
type of quantitative analysis.
fo wing:
primary standard are the following: ng:
Ϫϳϟϭ΍ ̵ΎϫΩέ΍ΩϧΎΗγ΍ ΕΎϳλϭλΧ
‫ڢ‬
1. High purity. Established
blished
lished methods
meth
ethods
etho
hods for
f confirming purity should be available.
2. Atmospheric stability.ty.
ɧƈ Ĺ Ҏ
3. Absence off hydhydrate water

aterr soo that
th the composition of the solid does not change
riations
ions in h
with variations midity
di y.
humidity.
4. Modestst cost.
ź
5. Reasonable
able
blee solubility
so y iin tthe
hee titration medium.
m
6. Reasonably
ablyy large
largg molar
ola mass
ma so that tha the relative error associated with
h weighing
weigh the
standard
dard
ard is minimized.
min
m nimi
nimiz
nim
mized.
ed
ƸŻ ֌
źƼࣰ
Veryy feww ccompou

compounds meet or even approach these criteria, and only ly a limited
te
mber
ber oof pr
number prima
primary-standard substances are available commercially. As a conse-nse
Ĺ ͇҅Г
quen
ence,
ce le
quence, less
lesss p
pure
pu compounds must sometimes be used in place of a primary standard.
ndard.
n daard
dar
dard
The pu
pur
urity
ity of such a secondary standard must be established by careful analysis.
purity ysis.
s. A secondary
nd standard is a compound
whose
w purity has been determined
by chemical
c analysis. The secondary
standard
stan
stand serves as the working standard
13B STANDARD SOLUTIONS material
m for titrations and for many
Standard solutions play a central role in all titrations. Therefore, we must
ust con- other
ot analyses.
sider the desirable properties for such solutions, how they are prepared, and
d how
their concentrations are expressed. The ideal standard solution for a titrimetric
tric
method will
ϝ΁ ϩΩϳ΍ Ωέ΍ΩϧΎΗγ΍ ϝϭϠΣϣ ΕΎϳλϭλΧ
1. be sufficiently stable so that it is necessary to determine its concentration
only once;
2. react rapidly with the analyte so that the time required between additions of re-
agent is minimized;
3. react more or less completely with the analyte so that satisfactory end points
are realized;
4. undergo a selective reaction with the analyte that can be described by a balanced
equation.
Few reagents completely meet these ideals.

The accuracy of a titration can be no better than the accuracy of the concen-
tration of the standard solution used. Two basic methods are used to establish the
concentration of such solutions. The first is the direct method in which a carefully
determined mass of a primary standard is dissolved in a suitable solvent and diluted to
In a standardization, the concentra- a known volume in a volumetric flask. The second is by standardization in which the
tion of a volumetric solution is deter- titrant to be standardized is used to titrate (1) a known mass of a primary standard,
mined by titrating it against a carefully (2) a known mass of a secondary standard, or (3) a measured volume of another stan-
measured quantity of a primary or sec-
ondary standard or an exactly known
dard solution. A titrantnt that
tran
an tha is standardized is sometimes referred to as a secondary-
th
volume of another standard solution. n. Thee concentration
solution.
standard solutio ion cco
conce ati ti of a secondary-standard solution is subject to
a larger uncertainty
rtainty than
han
an is the
he concentration
is th con
oncent ation of a primary-standard solution. If there
centration
Ƹɧķ Ɖ Ю
is a choice, then,
n, solutions
tio are bbest prepar
aree be prepared
prep d by the direct method. Many reagents,
ared
Şź
however, lack the properties
proper required
req
requir for
re or a primary standard and, therefore, require
standardization.
n
13C VOLUMETRIC
V
VOL METR
ETR
RIIC
RIC
I CALCULATIONS
CA
C
͕Ԯ
A w
As wee ind
indicated in Section
indic Secti 4B-1, we can express the concentration of solutions
in several
n sev
seve
eve
evera
ev ways. For the
h standard solutions used in most titrations, either
th
molar
mola a concentration, c, or normal concentration, c N, is usually
ola
lar ually
al used. Molar
‫ڢ‬
co
conc
concen
concentration is the number of moles of reagent contained in on one lit
liter of solu-
tion
tion,
i
io and normal concentration is the number of equivalents ts of reagent
alents rreagen in the
ɧƈ Ĺ Ҏ
aame vvolume.
same
sam
sa
Throughout this text, we base volumetric calculations
Thro
Throug tionss exclusively
usively
ve y on m mo
molar
olar con-
ar cco
con
on--
rati and molar masses. We have also included
centration ded in Appendixnd 7 a discussion
d
dis
discuussion
ssion
ź
of how vovolumetric calculations are performed based on normal mal concentratio
cconcentration
rat and
nd
equivalent
quiva masses because you may encounter
ounter these terms
ncounter ms and their
heir useses in
i the
th in-
dustrial and health science literature.
ƸŻ ֌
źƼࣰ
13C-1 Some Useful Relationships

ps
❯
mA
Ĺ ͇҅Г
nA 5 Most volumetric calculations are based on two
woo p
pai
pa
pairs
a of simple
mple
ple equations
equ
eqqu
ua
uat that are
MA
llimole,
mo and
derived from definitions of the mole, the millimole, a the mola
mol
molar concentration.
where nA iss the aam
amount
mo of A,
mA is the mass of A, and MA is
asss o For the chemical species A, we can write
the molar mass of A.
mass A (g)
amount A (mol) 5 (13-1)
molar
olar mass A (g/mol)
❯
nA
cA 5 ornA 5 V 3 cA mass A (g)
mass
V amount A (mmol) 5 (13-2)
millimolar mass A (g/mmol)
Any combination of grams,

moles, and liters can be expressed ❯ The second pair of equations is derived from the definition of molar concentration,
that is,
in milligrams, millimoles, and
milliliters. For example, a 0.1 M mol A
solution contains 0.1 mol of a amount A (mol) 5 V (L) 3 cA a b (13-3)
species per liter or 0.1 mmol per L
milliliter. Similarly, the number
of moles of a compound is equal
mmol A
to the mass in grams of that amount A (mmol) 5 V (mL) 3 cA a b (13-4)
compound divided by its molar L
mass in grams or the mass
in milligrams divided by its where V is the volume of the solution.
millimolar mass in milligrams. Equations 13-1 and 13-3 are used when volumes are measured in liters, and
Equations 13-2 and Equations 13-4 when the units are milliliters.
13C Volumetric Calculations307
13C-2 Calculating the Molar Concentration Ωέ΍ΩϧΎΗγ΍ ϝϭϠΣϣ ϪϳϬΗ

of Standard Solutions
The following three examples illustrate how the concentrations of volumetric
reagents are calculated.
EXAMPLE 13-1
Describe the preparation of 2.000 L of 0.0500 M AgNO

A
Ag 3(
(169.87
87 g
g/mol)
mol) from
ƉЮ
the primary-standard-grade solid.
Solution
amount AgNO3 5 Vsoln(L) 3 cAgNO3(mol/L)
0.0500 mol AgNO
0.05 O3
5 2.00
.00 L 3 5 0.
0.100 mol AgNO3
L
To obtain the mass of AgNO3, we rearrange

ear Equation 13-2
3 to give
169.87 g AgNO3
NO3 5 0.1000
mass AgNO 10 mol AgNO3 3
.10
100
mol AgNO3
5 16.987
.987 g AgNO3
ź
Therefore, the solution should
sh ld be prepared
prepa by dissolving 16.987 g of AgNO3 in water
and diluting to the mark
rk in a 2.000 L volumetric
v flask.
ɧƈ
ƸŻ ֌
źࣰ
EXAMPLE
EXA
XAMPLE
E 13-2
Ĺ ͇Г
A standard
tand 0.0100 M solution of Na1 is required to calibrate an ion-selective
nd rd 0. ive
ve
electrode
elec de method to determine sodium. Describe how 500 mL of this solution ion
can
n be
b prepared
p from primary standard Na2CO3 (105.99 g/mL).
Solution
We wish to compute the mass of reagent required to produce a species concentration
ntration
of 0.0100 M. In this instance, we will use millimoles since the volume is in milliliters.
lli
Because Na2CO3 dissociates to give two Na1 ions, we can write that the number ber of
millimoles of Na2CO3 needed is
0.0100 mmol Na1 1 mmol Na2CO3

amount Na2CO3 5 500 mL 3 3
mL 2 mmol Na1
5 2.50 mmol
From the definition of millimole, we write
mg Na2CO3
mass Na2CO3 5 2.50 mmol Na2CO3 3 105.99
mmol Na2CO3
5 264.975 mg Na2CO3
Since there are 1000 mg/g, or 0.001 g/mg, the solution should be prepared by dissolving
0.265 g of Na2CO3 in water and diluting to 500 mL.
EXAMPLE 13-3
How would you prepare 50.0-mL portions of standard solutions that are
0.00500 M, 0.00200 M, and 0.00100 M in Na1 from the solution in Example 13-2?
Solution
The number of mill mol of Na1 taken from the concentrated solution must equal
millimoles
m
the number in thee dilute solutions.
ut Thus,
T ,
Na1 from
amountt N d ssoln 5 amount Na1 in dil soln
om concd
Recall that the number ooff mil

millimoles is equal to the number of millimoles per millili-
ter times the number
er ooff mi
milliliters, that is,
millili
mill
Vconcd 3 cconcd 5 Vdil 3 cdil
wherere Vconcd and Vdil are the volumes in milliliters of the concentrated and diluted
solutions,
ut
utio
ut
uti respectively, and cconcd and cdil are their molar Na1 concentrations. For the
͕
0.00500-M
0.00
000 solution, this equation can be rearranged to
‫ڢ‬
Vdil 3 cdil 50.0 mL 3 0.005 mmol Na1 /mL
ɧƈ Ĺ Ҏ
Vconcd 5 5 5 25.0
2 mL
cconcd 0.0100 mmol Na1 /mL
refo to produce 50.0 mL of 0.00500 M Na1, 25.0 mL of the concentrated

Therefore, conc
onc ed ssolution
tion
ź
should be diluted to exactly 50.0 mL.
Repeat the calculation for the other
Re er ttwo molarities to confirm
firm that
at diluting
d
10.0 and 5.00 mL of the concentrated solutio
solution to 50.0 mL producesces the desired
uces
concentrations.
ƸŻ ֌
Ƽࣰ
Ĺ ͇҅Г
13C-3 Working with Titration Dataa
Two types of volumetric calculations are discussed
cussed
cussed
s here.
here In the first, we compute
concentrations of solutions that have been stand anda
nd
ndard
daar
ardized
standardized d ag
against either a primary-
standard or another standard solution. In the he second,
second
econd nd, we calculate
nd cca the amount of
analyte in a sample from titration data. Both
othh types of calculation
calc
cal
alcu are based on three
algebraic relationships. Two of these are Equations
ations 13-2 and
quations an 13-4, which are based
on millimoles and milliliters. The third relationship
nship is the
th stoichiometric ratio of the
number of millimoles of the analyte to the number er of millimoles of titrant.
Calculating Molar Concentrations from Standardization Data

Examples 13-4 and 13-5 illustrate how standardization data are treated.
EXAMPLE 13-4
A 50.00-mL portion of an HCl solution required 29.71 mL of 0.01963 M

Ba(OH)2 to reach an end point with bromocresol green indicator. Calculate
the molar concentration of the HCl.
Solution
In the titration, 1 mmol of Ba(OH)2 reacts with 2 mmol of HCl:
Ba(OH)2 1 2HCl S BaCl2 1 2H2O
Thus, the stoichiometric ratio is
2 mmol HCl
stoichiometric ratio 5
1 mmol Ba(OH)2
The number of millimoles of the standard is calculated

ed by
b substituting
sub into Equation 13-4:
m
mmol Ba OH)2
Ba(OH)
amount Ba(OH)2 5 29.71 mL Ba(OH)2 3 00.01963
01
Şź
mL Ba(OH)
m (OH 2
Ƹɧ Ɖ
To find the number of millimoles of HCl, we multiply
p this
hiis result
resul by the stoichiometric
ratio determined from the titration reaction:
2 mmol HCl
amount HCl 5 (29.71
71 3 0.01963) OH)2 3
963) mmol Ba(OH)
Ԯ 1 mmol Ba(OH)2
To obtain the number of millimoles off H

Therefore,
HCl per mL, we divide by the volume of the acid.
❮ Insignificant
determining the number of
fican
ca figures to retain in
volumetric
umetric
et ccalculations, the
.71 3 0.01963 3 2) mmol HCl
(29.71 stoichiometric
io ratio is assumed
cHCl 5 to be
be known
kn w exactly
kno
k exac without
50.0 mL HCl uncertainty.
u
uncertain
ncertai
rtaain
ainty.
m
mmol HCl
ɧƈ Ĺ
5 0.023328 5 0.02333 M
ź
mL HCl
ΎΑ ϥ΍έΗϳΗ ϝϭϠΣϣ ϥΩέ̯ έ΍ΩϧΎΗγ΍
ƸŻ ֌ Ϫϳϟϭ΍ Ωέ΍ΩϧΎΗγ΍
źƼࣰ
Ĺ ͇Г
EXAMPLE
EX
XAMPL
PLE 113-5
PLE
Titration
ra i of 0.2121 g of pure Na 2C 2O 4 (134.00 g/mol) required 43.31 mL
of KMnO
K 4 . What is the molar concentration of the KMnO 4 solution? Th
The
h
chemical reaction is
2MnO42 1 5C2O422 1 16H1 S 2Mn21 1 10CO2 1 8H2O
Solution
From this equation we see that
2 mmol KMnO4
stoichiometric ratio 5
5 mmol Na2C2O4
The amount of primary-standard Na2C2O4 is given by Equation 13-2
1 mmol Na2C2O4
amount Na2C2O4 5 0.2121 g Na2C2O4 3
0.13400 g Na2C2O4
(continued)
To obtain the number of millimoles of KMnO4, we multiply this result by the stoi-
chiometric ratio:
0.2121 2 mmol KMnO4

amount KMnO4 5 mmol Na2C2O4 3
0.1340 5 mmol Na2C2O4
The concentration
n of
o KMnO
KM 4 is then obtained by dividing by the volume consumed.
K
Thus,
0.2121
212
12 2
a 3 b mmol
m KMnO4
0.13400
133 5
cKMnO4 5 5 0.01462 M
43.31 mL KMnO4
Ƹɧķ
͕Ԯ
Note
N
Not
ote th
that units are carried
car through all calculations as a check on the correctness of
the
hee relationships
rel
re
rela
l used in Examples 13-4 and 13-5.
‫ڢ‬
Calculating
Cal
Calc
Caal the Quantity of Analyte from Titration Data ta
ɧƈ Ĺ Ҏ
As ssh
A shown by the examples that follow, the systematic approach
roach
ch
h just
ju
ust
stt described
de
desc is
i also
sed to ccompute analyte concentrations from titration data.
used a.
ź
EXAMPLE 13-6 εϫΎ̯-εϳΎγ̯΍ ϥϭϳγ΍έΗϳΗ ί΍ ϩΩΎϔΗγ΍ ΎΑ ϥΩόϣ ̲ϧγ έΩ ϥϫ΁ ϥϳϳόΗ
A 0.8040-g sample of an iron ore is dissolved
solv in acid. The iron iss then
hen reduced
֌
źƼࣰ
to Fe21 and titrated with 47.22 mL of 0.02242 M KMnO4 solution. io

on. Calculate
C
the results of this analysis in terms of (a) % Fe (5
(55.847 g/mol)
mol)
ol) andd (b)
(b
b % Fe3O4
Г
(231.54 g/mol).
Solution
The reaction of the analyte with the reagent is described
sc byy the
th equation
MnO42 1 5Fe21 1 8H1 S M

Mn21 1 5F
Fee31 1 4H2O
5Fe
iɰȧ
5 mmol FFe21
(a) stoichiometric ratio 5
1 mmol
mol KMnO
K 4
0.02242 mmol KMnO4

amount KMnO4 5 47.22 mL KMnO4 3
mL KMnO4
5 mmol Fe21
amount Fe21 5 (47.22 3 0.02242) mmol KMnO4 3
1 mmol KMnO4
The mass of Fe21 is then given by
g Fe21
mass Fe21 5 (47.22 3 0.02242 3 5) mmol Fe21 3 0.055847
mmol Fe21
The percent Fe21 is
(47.22 3 0.02242 3 5 3 0.055847) g Fe 21

% Fe21 5 3 100% 5 36.77%
0.8040 g sample
(b) To determine the correct stoichiometric ratio, we note that
5 Fe21 ; 1 MnO42
Therefore,
5 Fe3O4 ; 15 Fe21 ; 3 M O42

MnO
and
ol Fe3O4
5 mmol
rat 5
stoichiometricc ratio
3 mmol KMnO4
As in part (a),
47.22 m KMnO4 3 0.02242 mmol KMnO4

77.22 mL
oun KMnO4 5
amount
mL KMnO4
Ĺ
ź
5 mmol Fe3O4
Fe3O4 5 (4
amountt F (47.222 3 0.02242)
0.022 mmol KMnO4 3
3 mmol KMnO4
5 g Fe3O4
mass Fe3O4 5 aa47.2
a47.22
4 3 0.02242 3 b mmol Fe3O4 3 0.23154
ƸŻ ֌
3 mmol
ol F
Fe3O4
5
a47.22 3 0.02242 3 b 3 0.23154 g Fe3O4
3
Ĺ ͇҅Г
% Fe3O4 5 3 100% 5 50.81%%
0.8040 g sample
ź
FEATURE 13-1
Another Approach to Example 13-6(a)
that
Some people find it easier to write out the solution to a problem in such a way that
the units in the denominator of each succeeding term eliminate the units in the nu-
merator of the preceding one until the units of the answer are obtained.2 For example,
the solution to part (a) of Example 13-6 can be written
0.02242 mmol KMnO4 5 mmol Fe 0.055847 g Fe

47.22 mL KMnO4 3 3 3
mL KMnO4 1 mmol KMnO4 mmol Fe
1
3 3 100% 5 36.77% Fe
0.8040 g sample
2
This process is often referred to as the factor-label method. It is sometimes erroneously called
dimensional analysis. For an explanation of dimensional analysis, perform a search at the Wikipedia
website. In earlier texts, the factor-label method was sometimes called the “picket fence” method.
EXAMPLE 13-7
A 100.0-mL sample of brackish water was made ammoniacal, and the sulfide
it contained was titrated with 16.47 mL of 0.02310 M AgNO3. The analytical
reaction is
2Ag1 1 S22 S Ag2S(s)
Calculate the concentration

cen
centr
n noof H2S iin the water
w in parts per million, cppm.
Solution
At the end point,
1 mmol H2S
stoichiometric
stoicchio
sto ratio 5
2 mmol AgNO3
mmol AgNO3
NO3 5 16.47 mL AgNO3 3 0.02310
amount AgNO
mL AgNO3
‫ڢ‬ ͕
1 mmol
mo H2S
amount H2S 5 (16.47 3 0.02310) mmol AgNO3 3
2 mmol
ol AgNO3
ɧƈ Ĺ Ҏ
1 g H2S
mass H2S 5 a16.47 3 0.02310 3 b mmol H2S 3 0.034081
m 4081
811
2 mmol
m oll H2S
ź
5 6.483 3 1023 g H2S
6.483 3 100233 g H2S
cppm 5 3 1006 p
ppm
100.0 mL sample 3 1.00 g sam
sample/mL sample
ƸŻ ֌
5 64.8 ppm
źƼࣰ
Ĺ ͇҅Г
.Ωϳϧ̯ ϪΟϭΗ ppm ϑϳέόΗ ϪΑ
FEATURE 13-2
Rounding the Answer to Example 13-7
Note that the input data for Example 13-7 all contained
ontained four or more significant fig-
ures, but the answer was rounded to three. Why?
We can make the rounding decision by doing a couple of rough calculations
in our heads. Assume that the input data are uncertain to 1 part in the last sig-
nificant figure. The largest relative error will then be associated with the sample
size. In Example 13-7, the relative uncertainty is 0.1/100.0. Thus, the uncertainty
is about 1 part in 1000 (compared with about 1 part in 1647 for the volume of
AgNO3 and 1 part in 2300 for the reagent concentration). We then assume that
the calculated result is uncertain to about the same amount as the least precise
measurement, or 1 part in 1000. The absolute uncertainty of the final result is
then 64.8 ppm 3 1/1000 5 0.065, or about 0.1 ppm, and we round to the first
figure to the right of the decimal point. Thus, we report 64.8 ppm.
Practice making this rough type of rounding decision whenever you make a
computation.
EXAMPLE 13-8 αϭ̰όϣ ϥϭϳγ΍έΗϳΗ ί΍ ϩΩΎϔΗγ΍ ΎΑ ̶ϫΎϳ̳ ̵΍ΫϏ ̮ϳ έΩ έϔγϓ ̵έϳ̳ ϩί΍Ωϧ΍
The phosphorus in a 4.258-g sample of a plant food was converted to PO432
and precipitated as Ag g3PO4 by y adding 50.00 mL of 0.0820 M AgNO3. The
excess AgNO3 was back-titrated with 4.06 mL of 0.0625 M KSCN. Express
the results of this analysis in terms of % P2O5.
Solution
The chemical reactions are
P2O5 1 9H2O S 2PO432 1 6H3O1

2PO432 1 6 Ag1 S 2Agg3P
PO s
O4(s)
excess
N2 S AgSCN(s)
Ag1 1 SCN
The stoichiometric ratios are

re
1 mmol P2O5 1 mmol KSCN

and
6 mmo
mmol AgNO
NO3 1 mmol AgNO3
mmol AgNO3
total amount AgNO3 5 50.00
0 mL 3 0.0820 5 4.100 mmol
mL
mmol KSCN
Ĺ
amount AgNO3 consumed KSCN 5 4.06 mL 3 0.0625
med by KSC
ź
mL
1 mmol AgNO3
3
mmol KSCN
5 0.2538 mmol
ƸŻ ֌ 1 mmol P2O5
Ĺ ͇Г
moou P2O5 5 (4.100 2 0.254) mmol AgNO3 3
amount
am
6 mmol AgNO3
5 0.6410 mmol P2O5
ź
0.1419 g P2O5
0.6410 mmol 3
mmol
% P2O5 5 3 100% 5 2.14%
4.258 g sample
EXAMPLE 13-9 ̵έΗϣϭΩϳ εϭέ

The CO in a 20.3-L sample of gas was converted to CO2 by passing the sample
over iodine pentoxide heated to 150°C:
I2O5(s) 1 5CO(g) S 5CO2(g) 1 I2(g)
The iodine was distilled at this temperature and was collected in an absorber
containing 8.25 mL of 0.01101 M Na2S2O3.
I2(g) 1 2S2O322(aq) S 2I2(aq) 1 S4O622(aq)
The excess Na2S2O3 was back-titrated with

w 2.16 mL of 0.00947 M I2 solution.
Calculate the concentration of CO (28.01 g/mol) in mg per liter of sample.
(continued )
Solution
Based on the two reactions, the stoichiometric ratios are
5 mmol CO 2 mmol Na2S2O3

and
1 mmol
mm I2 1 mmol I2
We divide the firstt ratio by the

he second
on too get a third useful ratio
5 mmol
mm COC
2 mmol
ol Na2S2O3
This relationship reveals

veals that
ha 5 mmol of CO are responsible for the consumption of
2 mmol
mol oof Na2S2O3. Thehe total
tota amount of Na2S2O3 is
mmol Na2S2O3
amount Na2S2O3 5 8.25 mL Na2S2O3 3 0.01101
mL Na2S2O3
͕
5 0.09083 mmol Na2S2O3
‫ڢ‬
The
Th
T h amount of Na2S2O3 consumed in the back-titration is
ɧƈ Ĺ Ҏ
mmol I2 mo Na2S2O3
2 mmol
amount Na2S2O3 5 2.16 mL I2 3 0.00947
am 3
mL I2 mmol I2
m
ź
5 0.04091 mmol Na2S2O3
The number of millimoles of CO can then

the be calculated by using
si tthe third
sing
stoichiometric ratio:
ƸŻ ֌
źƼࣰ
5 mmol
mmol CO
C
amount CO 5 (0.09083 2 0.04091) mmol Na
N 2S2O3 3
Ĺ ͇Г
2 mm
mmoll Na2S2O3
5 0.1248 mmol CO
28.01
001 mg CO
mass CO 5 0.1248 mmol CO 3 5 3.4956 mg
mmol CO
O
mass CO 3.4956 mg COO mg CO
5 5 0.172
0.17
vol sample 20.3 L sample L sample
13D GRAVIMETRIC TITRATIONS

Mass (weight) or gravimetric titrations differ from their volumetric counterparts
in that the mass of titrant is measured rather than the volume. Therefore, in a mass
titration, a balance and a weighable solution dispenser are substituted for a buret
and its markings. Gravimetric titrations actually predate volumetric titrations by
more than 50 years. With the advent of reliable burets, however, mass titrations
were largely supplanted by volumetric methods because the former required rela-
Remember that for historical
reasons we often refer to weight ❯ tively elaborate equipment and were tedious and time consuming. The availability
of sensitive, low-cost, top-loading digital analytical balances and convenient plastic
or weighing, but we really mean
mass, although most of us cannot solution dispensers has changed this situation completely, and mass titrations can
bring ourselves to say massing. now be performed as easily and rapidly as volumetric titrations.
13E Titration Curves315
13D-1 Calculations Associated with Mass Titrations

The most common way to express concentration for mass titrations is the weight
concentration, cw, in weight molar concentration units, Mw, which is the number of
moles of a reagent in one kilogram of solution or the number of millimoles in one
gram of solution. Thus, aqueous 0.1 Mw NaCl contains
ntaains
ns 0.1
0 mol of the salt in 1 kg of
solution or 0.1 mmol in 1 g of the solution.
The weight molar concentration cw(A) off a solution
ution ofo a solute
so
solute A iss computed
compu
comp us-
ing either one of two equations that are analogous
ogous too Equation
E
Equa
Eq tion on 4-2:
ion 4-2:
Ƹɧķ Ɖ Ю
Şź
no.
o. mol
ol A no.
n mmol
no m lA
weight molar concentration 5 5 (13-5)
no. kg solution
olu on
olu n no g ssolution
no.
n
nA
A) 5
cw(A)
mso
soln
͕Ԯ
where nA is the number of moles species A and msoln
les off spec
speci soln iis the mass of the solution.
Gravimetric titration data
ata ccan then
heen
henn be
b treated by using the methods illustrated in
Sections 13C-2 and 13C-3 after
3C-3 afte substitution
err subs
substi
b
bs of weight concentration for molar con-
‫ڢ‬
centration and grams and kilograms
kilogram ams for milliliters and liters.
ram
am
ɧƈ Ĺ Ҏ
13D-2 Advantages
Advantag
vanta s off Gravimetric
Gravime
Gravim
G Titrations
ź
In addition
ion too greater speed
sp
speed
d and convenience,
conven
conv mass titrations offer certain otherr
advantages over
er their
tth volumetric
volume ric counterparts:
olu tric count
1. Calibration
libration
ration off gglassw
glassware
glasswa
gla
la and tedious cleaning to ensure proper per drainage
raina are a
ƸŻ ֌
completelytely elimin
eliminated.
źƼࣰ
2. Temperature
mp atu co corrections are unnecessary because the mass (weight) ht) molar la
concentration
concen
oncen
cen
cent
entratio
rat does not change with temperature, in contrast to the volume um
m
Ĺ ͇҅Г
concentration.
molar ccon
molar on This advantage is particularly important in nonaqueous
queo
ueous
eo
eou
titrations
titratiio because of the high coefficients of expansion of most organic liquids
tr tio liqquid
quids
qu
(about
(abo
b 10 times that of water).
3. Mass measurements can be made with considerably greater precision and accuracyy
than can volume measurements. For example, 50 g or 100 g of an aqueous ueous
ou solu-
tion can be readily measured to 61 mg, which corresponds to 60.001 mL. This
greater sensitivity makes it possible to choose sample sizes that lead to significantly
ficantly
icantly
smaller consumption of standard reagents.
4. Gravimetric titrations are more easily automated than are volumetric titrations.
13E TITRATION CURVES

As noted in Section 13A-1, an end point is signaled by an observable physical
change near the equivalence point of a titration. The two most widely used signals
involve (1) changes in color due to the reagent (titrant), the analyte, or an indicator
and (2) a change in potential of an electrode that responds to the titrant concentra-
tion or the analyte concentration.
To understand the theoretical basis of end point determinations and the sources of
titration errors, we calculate the data points necessary to construct titration curves Titration curves are plots of a
for the systems under consideration. A titration curve is a plot of some function of concentration-related variable versus
the analyte or titrant concentration on the y axis versus titrant volume on the x axis. titrant volume.
13E-1 Types of Titration Curves

The vertical axis in a sigmoidal
titration curve is either the ❯ Two general types of titration curves (and thus two general types of end points)
occur in titrimetric methods. In the first type, called a sigmoidal curve, important
p-function of the analyte or
titrant or the potential of an observations are confined to a small region (typically 60.1 to 60.5 mL) surround-
analyte- or titrant-sensitive ing the equivalencee point.
p oin A sigmoidal curve in which the p-function of analyte
poin
electrode. (or sometimes thee titrant)ran is
titra
trant)
tra
ra i plotted as a function of titrant volume is shown in
Figure 13-2a. a.
The vertical axis of a linear-
❯ In the secondond type
ype
pee of ccurv
curve,
urve,
urve
ve ccalled
alled
led a linear
line segment curve, measurements are
Ƹɧķ Ɖ Ю
Şź
segment titration curve
is an instrument signal
made on both sides ides
des of,
f, but
b well
wel
w l away
a y from,
from
fro m,, the
th equivalence point. Measurements
that is proportional to the near equivalence nce are
re avoided.
av ded d. In
I this type
t of curve, the vertical axis represents
concentration of the analyte an instrument reading adin g that
adin t hat is
i directly
direc
d proportional to the concentration of the
or titrant. analytee oro the titrant.t. A typical
nt. ypi linear
typic line segment curve is found in Figure 13-2b.
Thee sigm
sigmoidal
sig type
pe offers
pe offe
off
offfers
fers the
t advantages of speed and convenience. The linear
segment
seegment nt type
ty is advantageous
vantageo
antageeous forf reactions that are complete only in the presence of
͕Ԯ
a considerable
con
considerab
sider excess of the
th reagent or analyte.
p-function
In this chapter and several that follow, we deal exclusively with sigmoidal titration
n tth
thi
curves.
veees We explore linear segment curves in Chapters 23 and 26.
curve
ves
‫ڢ‬
Equivalence
ɧƈ Ĺ Ҏ
point 13E-2 Concentration
113E-
13
13E
3E Changes During Titrations
rations
ions
ons
Reagent volume
me The
he equ
equivalence point in a titration is characterized
equiv d by majorr changes
chan t e rela-
ha ges in the
th rrel
re
ela--
(a) Sigmoidal curvee tive concentrations
con
concen 3-1 illustrates
of reagent and analyte. Table 13-1 ustrates
ess this
t phen
phenomenon.
hen
enom
no enon.
non
ź
The dat
data in the second column of the tablele show the changess in the
th hydronium
on ion
on
concentration
once as a 50.00-mL aliquot of a 0.10
0.1000 M solution
ion of hydrochloric
ydrrochlor acacid is
Instrument reading
titrated with 0.1000 M sodium hydroxide. de. The

roxide. Th neutralization
n on reaction
io is described
tion
ion de
describ
by the equation
ƸŻ ֌
źƼࣰ
H3O1 1 OH2 S 2H
H2O (13-6)
Ĺ ͇҅Г
Equivalence
E
point
To emphasize the changes in relative concentration
ntration
at
atio that
th occurr in i the equivalence
Reagent
eage volume
Rea point region, the volume increments computed ted
d are
aare those
t r
required to cause tenfold
(b) Linear segment curve decreases in the concentration of H3O1 (or tenfold
nfol
fold
fo d in
increases
crease in hydroxide ion con-
Figure 13-2Two types of titration centration). Thus, we see in the third columnolumn
umn that aan addition of 40.91 mL of
n aad
1
curves. base is needed to decrease the concentrationtion
n of H3O by one order of magnitude
from 0.100 M to 0.0100 M. An addition of only 8.11 m mL is required to lower the
concentration by another factor of 10 to 0.00100 00 MM; 0.89 mL causes yet another
tenfold decrease. Corresponding increases in OH2 concentration occur at the same
time. End-point detection then depends on this large change in the relative con-
centration of the analyte (or titrant) that occurs at the equivalence point for every
type of titration. Feature 13-3 describes how the volumes in the first column of
Table 13-1 are calculated.
The large changes in relative concentration that occur in the region of chemical
equivalence are shown by plotting the negative logarithm of the analyte or the titrant
concentration (the p-function) against reagent volume, as seen in Figure 13-3. The
data for these plots are found in the fourth and fifth columns of Table 13-1. Titration
curves for reactions involving complex formation, precipitation, and oxidation/reduction
all exhibit the same sharp increase or decrease in p-function in the equivalence-point
region as those shown in Figure 13-3. Titration curves define the properties required
of an indicator or instrument and allow us to estimate the error associated with titra-
tion methods.
Unless otherwise noted, all content on this page is © Cengage Learning.
13E Titration Curves317
TABLE 13-1
Concentration Changes During a Titration of 50.00 mL of 0.1000 M HCl
Volume of 0.1000 M [H3O1], Volume of 0.1000 M NaOH to Cause
NaOH, mL mol/L a Tenfold Decrease in [H3O1], mL pH pOH
0.00 0.1000 1.00 13.00
40.91 0.0100 40.91
91 2.00 12.00
49.01 1.000 3 1023 8.111 3.00 11.00
49.90 1.000 3 1024 0.89
899 4.00 10.00
49.99 1.000 3 1025 00.09
009 5.00
00 9.00
Ƹɧķ Ɖ Ю
Şź
49.999 1.000 3 1026 0.009
009 6.000 8.00
50.00 1.000 3 1027 0.001
001 7.00 7.00
50.001 1.000 3 1028 0.00101
01 8.00 6.00
50.01 1.000 3 1029 0.009
0.0 09 9.00 5.00
50.10 1.000 3 10210 0.09
099 10.00 4.00
51.10 1.000 3 10211 0.91
.9 11.00 3.00
61.11 1.000 3 10212 10.10
0.10 12.00 2.00
‫ڢ‬ ͕Ԯ
14
pH
12
ɧƈ Ĺ Ҏ
1
10
H or ppOH
H
ź
6
pH
4
pOH
2
ƸŻ ֌
źƼࣰ
3 TiTitra
Figuree 13-3Titration
13-3
3-3
3 curves of pH
0
andd pOHOH versus
rs volume
rsus v of base for
Ĺ ͇҅Г
0 10 20 30 40 50 60 70 thee titration
itratio
ioon of
ion o 0.1000 M HCl with
Volume NaOH, mL 0.10000 M NaOH.
N
FEATURE 13-3
Calculating the NaOH Volumes Shown in the First Column of Table 13-1
3
Prior to the equivalence point, [H3O1] equals the concentration of unreacted HCl
(cHCl). The concentration of HCl is equal to the original number of millimoles of
HCl (50.00 mL 3 0.1000 M) minus the number of millimoles of NaOH added
(VNaOH 3 0.1000 M) divided by the total volume of the solution:
50.00 3 0.1000 2 VNaOH 3 0.1000

cHCl 5 3 H3O14 5
50.00 1 VNaOH
where VNaOH is the volume of 0.1000 M NaOH added. This equation reduces to
50.00 3 H3O14 1 VNaOH 3 H3O14 5 5.000 2 0.1000VNaOH
Collecting the terms containing VNaOH gives
VNaOH(0.1000 1 3 H3O14 ) 5 5.000 2 50.00 3 H3O14

(continued )
or
5.000 2 50.00 3 H3O14

VNaOH 5
0.1000 1 3 H3O14
H3O1] 5 0.0100 M, we find

Thus to obtain [H
5.000 2 550.00
5.0 00 3 0.0100
OH 5
VNaOH 5 40.91 mL
0.10000 1 0.0100
01
Challenge: Use the same

me reasoning
eas to show that beyond the equivalence point,
50.000 3 OH24 1 5.000

NaOH 5
VNaO
0.1000 2 3 OH24
͕Ԯ
Ƹ Spreadsheet Summary Chapter 7 of Applications ns of Microsoft ®
‫ڢ‬
Excel in Analytical Chemistry, 2nd ed., deals with plotting ti titration curves.
ɧƈ Ĺ Ҏ
Several types of titrations are presented and ordinary titration
n curves
cu are plot-
ted aalong with derivative plots and Gran plots. The stoichiometricc appro
approach
proa developed
ppr
pr lo
in this
his chapter is used and a master equation approach is explored.
ź
WE
WEB Look up titration in Wikipedia, the online encyclopedia.
loped Give the definition of o titration
tit
ƸŻ ֌
WO
WORKS found there. Is a chemical reaction necessary for a quantitative procedure to be cacal
called
lled
d a titra-
źƼࣰ
tion? From what Latin word does titration derive? Who developed
dev the first buret
buret and in
what year? List five different methods to determine the end d point
p of a titration.
ation. Define
itratio D the
Ĺ ͇҅Г
term acid number, also called the acid value. How are titrations
atio
ti applied too biodiesel
bioddi fuels?
QUESTIONS AND PROBLEMS

13-1. Define REQUIRED)ED)) to express this ratio for calculation of the
*(a) millimole. percentage of
(b) titration. *(a) hydrazine in rocket fuel by titration with standard
*(c) stoichiometric ratio. iodine. Reaction:
(d) titration error.
13-2. Write two equations that—along with the stoichiometric H2NNH2 1 2I2 S N2( g) 1 4I2 1 4H1
factor—form the basis for the calculations of volumetric
titrations. (b) hydrogen peroxide in a cosmetic preparation by
13-3. Distinguish between titration with standard permanganate. Reaction:
*(a) the equivalence point and the end point of a titration.
(b) a primary standard and a secondary standard. 5H2O2 1 2MnO42 1 6H1 S
13-4. Briefly explain why the concentration units of milli-
2Mn21 1 5O2( g) 1 8H2O
grams of solute per liter and parts per million can be
used interchangeably for a dilute aqueous solution.
*(c) boron in a sample of borax, Na2B4O7 # 10H2O, by
13-5. Calculations of volumetric analysis ordinarily consist
titration with standard acid. Reaction:
of transforming the quantity of titrant used (in chemi-
cal units) to a chemically equivalent quantity of analyte
B4O722 1 2H1 1 5H2O S 4H3BO3
(also in chemical units) through use of a stoichiometric
factor. Use chemical formulas (NO CALCULATIONS
Questions and Problems319
(d) sulfur in an agricultural spray that was converted *13-13. Describe the preparation of
to thiocyanate with an unmeasured excess of (a) 1.00 L of 0.150 M KMnO4 from the solid reagent.
cyanide. Reaction: (b) 2.50 L of 0.500 M HClO4, starting with a 9.00 M
solution of the reagent.
S(s) 1 CN2 S SCN2 (c) 400 mL of a solution that is 0.0500 M in I2, start-
ing with MgI2.
After removal of the excess cyanide, thee thiocyanate
thiocy
thiocya
ocya
cyanate
yyan (d) 200 mL of 1.00% (w/v) aqueous CuSO4 from a
was titrated with a standard potassium
m iodate
ate solution
solutio
soluution
ution 0.218 M CuSO4 solution.
in strong HCl. Reaction: (e) 1.
1.50 L of 0.215 M NaOH from the concentrated
Ƹɧķ Ɖ Ю
Şź
ccommercial reagent [50% NaOH (w/w), sp gr
2SCN2 1 3IO32 1 2H1 1 6Cl2 S 1.525].
(f) 1.50 L of a solution that is 12.0 ppm in K1, start-
2SO422 1 2CN2 1 3ICl
Cll22 1 H2O
ing with solid K4Fe(CN)6.
13-14. A solution of HClO4 was standardized by dissolving
1
13-6. How many millimoles of solute lutete are ccontained
d in
n
0.4008 g of primary-standard-grade HgO in a solu-
(a) 2.00 L of 2.766 3 10 1 233 M KMnOKM 4?
͕Ԯ
tion of KBr:
(b) 250.0 mL of 0.0423 .0423
042233 M KSCN?
KSCN
(c) 500.0 mL of a solution ion
n co
cont
containing
ontaini
nta
nt 2.97 ppm CuS
C
CuSO
S 4?
HgO(s) 1 4Br2 1 H2O S HgBr422 1 2OH2
(d) 2.50 L of 0.352 .35 M KCl?
KC
KCl
Cl?l??
‫ڢ‬
*13-7. How many millimoles
millimo of solute are contained in
o solu
(a) 2.95 mL of 0.0789 M KH The liberated OH2 consumed
onsumed
um 443.75 mL of the acid.
K 2PO4?
ɧƈ Ĺ Ҏ
Calculate the molar
ar concentration
nccentr
entr
en of
o the HClO4.
(b) 0.201120 L of 0.0564 644 M H HgCl2?
*13-15. A 0.4723-g sample plee off primary-standard-grade
primary-sta
prima
p r st dard-
ard
(c) 2.56 L of a 47.5 5 ppm
p soluti
solut
solution of Mg(NO3)2?
Na2CO3 required
quired
ed 34.78
78 mL
mL of an H2SO O4 solutio
solution
olutio to
(d) 79.8 mL m oof 0.1379
379 M NH4VO3 (116.98 g/mol)?
reach the end point
oint in the
he reaction
tion
ion
on
ź
13-8. What att mass of solu
solute
sol te in milligrams
milligram is i contained in
(a) 26.0 mL off 0.250 0 0 M sucrose
sucros (342 g/mol)?
H 1 S H2 O 1 C
CO322 1 2H ( g)
CO2(g)
(b)b)) 2.92 5.2 3 102
92 L of 5.23
2..92 244
M H2O2?
(c) 67673 m mL
L of a solution that contains 5.76 ppm
What is tthe molar concentration
Wha ncentration
tion of
tio o the H2SO4?
P
Pb(NO 3)2 (331.20
( g/mol)?
ƸŻ ֌ 13-16. A 0.5002-g sample that hat

at assayed
ass
a ss
ssay 96.4% Na 2SO 4
źƼࣰ
(d)) 6.75 mL of 0.0426 M KNO3?

required
equired 48.63 mL
d 448.6 ar um chloride solution.
L off a barium
arium
9. W
*13-9.
3-9.
-9. What hat mamass of solute in grams is contained in
Ĺ ͇҅Г
Reaction:
ction:
n
n:
((aa)) 450.0
(a) 45
4 mL of 0.0986 M H2O2?
(b) 26.4 mL of 9.36 3 1024 M benzoic acid (122.1
(b)
Ba21 1 SO422 S BaSO4(s)
B
g/mol)?
(c) 2.50 L of a solution that contains 23.4 ppm
SnCl2? Calculate
alculate
ulat
laaate the
th analyti
analy
analytical molar concentration of BaCl2
in
n the solution
solution.
on.
n.
(d) 21.7 mL of 0.0214 M KBrO3?
*13-17. A 0.4126-g sa sample of primary-standard Na2CO3 was
sampl
13-10. Calculate the molar concentration of a solution that is
treated
ated
ted with 40.440.00 mL of dilute perchloric acid. The
50.0% NaOH (w/w) and has a specific gravity of 1.52.
*13-11. Calculate the molar concentration of a 20.0% solu-
ϪϠ΋γϣ solutionon was boiled to remove CO2, following which
tion (w/w) of KCl that has a specific gravity of 1.13. 13-13 the excess HClO4 was back-titrated with 9.20 mL of
13-12. Describe the preparation of εϳ΍έϳϭ dilute NaOH. In a separate experiment, it was estab-
lished that 26.93 mL of the HClO4 neutralized the
(a) 500 mL of 0.0750 M AgNO 3 from the solid έΗ ̶ϣϳΩϗ NaOH in a 25.00-mL portion. Calculate the molari-
reagent.
ties of the HClO4 and NaOH.
(b) 2.00 L of 0.325 M HCl, starting with a 6.00 M
solution of the reagent. 13-18. Titration of 50.00 mL of 0.04715 M Na 2 C 2 O 4
(c) 750 mL of a solution that is 0.0900 M in K1, required 39.25 mL of a potassium permanganate
solution.
starting with solid K4Fe(CN)6.
(d) 600 mL of 2.00% (w/v) aqueous BaCl 2 from a
2MnO42 1 5H2C2O4 1 6H1 S
0.500 M BaCl2 solution.
(e) 2.00 L of 0.120 M HClO4 from the commercial 2Mn21 1 10CO2( g) 1 8H2O
reagent [60% HClO4 (w/w), sp gr 1.60].
(f ) 9.00 L of a solution that is 60.0 ppm in Na 1, Calculate the molar concentration of the KMnO 4
starting with solid Na2SO4. solution.
*13-19. Titration of the I 2 produced from 0.1142 g of C6H5COOH (122.12 g/mol). An end point was ob-
primary-standard KIO3 required 27.95 mL of sodium served after addition of 43.25 mL of base.
thiosulfate. (a) Calculate the molar concentration of the base.
(b) Calculate the standard deviation of the molar
IO32 1 5I2 1 6H1 S 3I2 1 3H2O concentration if the standard deviation for the
mass measurement was 60.3 mg and that for the
I2 1 2S2O322 S 2I2 1 S4O622
volume measurement was 60.02 mL.
c) Assuming
(c) sumin an error of 20.3 mg in the mass mea-
Assumin
Calculate the concentration of the Na2S2O3.
surement,
su
sur ement ccalculate the absolute and relative sys-
urement,
13-20. A 4.912-g sample of a petroleum product was burned
urned
ed
Ƹɧķ Ɖ Ю
Şź
tematic
tem
tematatic error
err
e in the molar concentration.
in a tube furnace, and the SO2 produced was col-ol-
25 T
* -25
*13-25.
25. The ethyl
thyl
hy acetate concentration in an alcoholic solu-
lected in 3% H2O2. Reaction:
tion was determined by diluting a 10.00-mL sample to
ti
100.00 mL. A 20.00-mL portion of the diluted solu-
100
SO2(g) 1 H2O2 S H2SO
O4
tion was refluxed with 40.00 mL of 0.04672 M KOH:
tio
A 25.00-mL portion of 0.00873
0873
873 M NaOH OH was
w intro-o-
CH3COOC2H5 1 OH2 S
͕Ԯ
duced into the solution of H2SO SO4, followin
following
ollowi which
the excess base was back-titrateded with
withth 15.17
15 mL of CH3COO2 1 C2H5OH
0.01102 M HCl. Calculate ate the
late th sulfur
ulfuu concentration
ulfur
lfu
fu
ur c
After cooling, the excess OH 2 wa
‫ڢ‬
in the sample in parts per million.
million
m on.
n. was bback-titrated
*13-21. A 100.0-mL sample of spring water wa
wat
w was treated with 3.41 mL of 0.05042 M H2SO O4. Cal
Calculate the
ɧƈ Ĺ Ҏ
to convert any iron

i sent too Fe 221. Addition of
present amount of ethyl acetate (88.11 mol) in the ooriginal
88.111 g/mol)
g/m
g/mmo
m
25.00-mL off 0.002517
0.0
0.002 M K2Cr2O7 re resulted in the sample in grams.
reaction 13-26. A 0.1475-M solution on of Ba(OH)
B H)2 w was u
wa used
used
d to titrate
titrat
titra
titrate
ź
the acetic acid (60.05
05 g/mol)
ol) in a dilute
d aque
aqueous
aqueo
que
ueou
ue
e solu-
olu-
Fe221 1 Cr2O7222 1 14H1 S
6Fe tion. The
he following
f results
ults werere obtained.
oob
Fe331 1 2Cr
6Fe
66F 2C 31 1 7H2O
Sample
amplee Sample
Samp Volume, mL Ba(OH)
H)2 Volum
Volume,
Vol
V ume, mL
ƸŻ ֌
The
he excess K2Cr2O7 w was back-titrated with 8.53 mL 1 50.00
50.0 43.17
33.
źƼࣰ
2 49.50
9. 42.68
42
42.6
of 0.00949
.00949
00
009 M Fe21 solution. Calculate the concentra- 3 25.00
5.0 21.47
2
21.4
21
21.
tion
ion
on of iron
iroon in the
th sample in parts per million.
Ĺ ͇҅Г
4 50.00
500. 43.33
4
13-22. Thee aarsenic
arsen nic
ic in a 1.203-g sample of a pesticide
was converted
con
co nve
v to H 3AsO 4 by suitable treatment. (a) Calculatee the
tth
he
h mean
me
m w/v
w percentage of acetic acid
13-18 The
he acid
a
ac was then neutralized, and 40.00 mL of in the sample.
mple
ple.
lee
0.05871 M AgNO3 was added to precipitate the ar- (b) Calculate
ate the
he standard
h stan dard deviation
andard
an
and de
d for the results.
senic quantitatively as Ag3AsO4. The excess Ag1 in (c) Calculate
ulate
ate the 90% % confidence
cco interval for the
the filtrate and in the washings from the precipitate mean.
was titrated with 9.63 mL of 0.1000 M KSCN, and (d) At the 90%
0%% confidence
confiden level, could any of the re-
confide
the reaction was sults be discarded?
carded
arded
*13-27. (a) A 0.3147-g sample of primary-standard-grade
Ag1 1 SCN2 S AgSCN(s) Na2C2O4 was dissolved in H2SO4 and titrated
with 31.67 mL of dilute KMnO4:
Find the percentage of As2O3 in the sample.
*13-23. The thiourea in a 1.455-g sample of organic mate- 2MnO42 1 5C2O422 1 16H1 S
rial was extracted into a dilute H2SO4 solution and
titrated with 37.31 mL of 0.009372 M Hg21 via the 2Mn21 1 10CO2( g) 1 8H2O
reaction
Calculate the molar concentration of the KMnO 4
4(NH2)2CS 1 Hg21 S [(NH2)2CS]4Hg21 solution.
(b) The iron in a 0.6656-g ore sample was reduced
Find the percentage of (NH2)2CS (76.12 g/mol) in quantitatively to the 12 state and then titrated with
the sample. 26.75 mL of the KMnO4 solution from part (a).
13-24. A solution of Ba(OH)) 2 was standardized against Calculate the percent Fe2O3 in the sample.
0.1215 g of primary-standard-grade benzoic acid, 13-28. (a) A 0.1527-g sample of primary-standard AgNO3
was dissolved in 502.3 g of distilled water.
13-21
Questions and Problems321
Calculate the weight molar concentration of Ag1 13-30. A solution was prepared by dissolving 367 mg of
in this solution. K3Fe(CN)6 (329.2 g/mol) in sufficient water to give
(b) The standard solution described in part (a) was 750.0 mL. Calculate
used to titrate a 25.171-g sample of a KSCN (a) the molar analytical concentration of K3Fe(CN)6.
solution. An end point was obtained after add- (b) the molar concentration of K1.
ing 24.615 g of the AgNO3 solution. C Calculate
alcu (c) the molar concentration of Fe(CN)632.
the weight molar concentration of the K KSC
KSCN
KS (d) the weight/volume percentage of K3Fe(CN)6.
solution. (e) the number of millimoles of K1 in 50.0 mL of
(c) The solutions described in parts arts (a)) and
aannd (b)
n ( b)) th
this solution.
Ƹɧķ Ɖ Ю
were used to determine the BaCll 2 # 2H
Şź
H 2O in (f the concentration of Fe(CN)632 in ppm.
( ) th
a 0.7120-g sample. A 20.102-g sample ple of thee 13-31.
13 Challenge
C Problem: For each of the following acid/
AgNO3 was added to a solution of the hee sample,
sam
ample,
mple, base titrations, calculate the H3O1 and OH2 concen-
and the excess AgNO 3 was back-titrated ra ted
rateded with th trations at equivalence and at titrant volumes corre-
7.543 g of the KSCN solution. ution Calculate the hee pe
p
per- sponding to 620.00 mL, 610.00 mL, and 61.00 mL
cent BaCl2 # 2H H2O in the sample.
samp of equivalence. Construct a titration curve from the
͕Ԯ
*13-29. A solution was prepared
prepar
rep are
red by dissolving
dissol
dis 7.48
.48 g of of data, plotting the p-function versus titrant volume.
KCl # MgCl 2 # 6H 2O (27 (277.85
(277.
77.85
.85 g/mol)
gg/ in sufficient
ffici
fficie (a) 25.00 mL of 0.05000 M HCl with 0.02500 M
water to give 2.000
000 L. Calculate
Calculat
lcu
cula
ula
ullat
late NaOH.
(a) the molarr analytical
analy al concentration
analytica conce
concen
nce
cen
ce of KCl # MgCl2 (b) 20.00 mL of 0.06000 000 M HCl with 0.03000 M
‫ڢ‬
in this solution.
olution.
utio NaOH.
(b) the molar concentrationat
atio of Mg21. (c) 30.00 mL of 0.07500 500 M H2SO4 with 0.1000 M
ɧƈ Ĺ Ҏ
(c) the
he molar
m concentration
centr
ntration
ntrati
attion ofo Cl2. NaOH.
(d)) the weigh
weight/volume
wei olume percentage of KCl # MgCl2 #
ume percen
percentag (d) 40.00 mL off 0.02500
25000MN NaOH with 0.05000
aOH with .0500 M
0.0500
6HH2O. HCl.
ź
(e)
e) the
th number of o millimoles of Cl2 in 25.0 mL of (e) 35.00 mL of 0.200.2000
.20000 M Na2COO3 with th
h 0.20
0.2000
0.2
0 200
00 M
this so
this solution.
s on. HCl.
(f ) th concentration
the conce
concentratio
con
oncentr
once of K1 in ppm.
ƸŻ ֌
źƼࣰ
Ĺ ͇҅Г
17B Titrations with Inorganic Complexing Agents 407
FEATURE 17-2
Determination of Hydrogen Cyanide in Acrylonitrile Plant Streams
Acrylonitrile, CH2CH}C {N, is an important chemical in the production of poly-

acrylonitrile. This thermoplastic was drawn into fine threads and woven into synthetic
fabrics such as Orlon, Acrilan, and Creslan. Although
g acrylic
acry fibers are no longer pro-
duced in the US, they are still made in many countries. s. Hydrogen
untries. d cyanide
c is an im-
purity in the plant streams that carry aqueous acrylonitrile.
itrrri The
onitril he cyanide
nid iss commonly
com
determined by titration with AgNO3. The titration reaction
ctio is
Ag1 1 2CN2 S Ag(CN)
N)22
In order to determine the end point of the titration, on the
th
he aqueous
aqu sample is mixed
with a basic solution of potassium iodide before the titration.
titra
ratioon
ra
rat on. Before the equivalence
point, cyanide is in excess, and all thee Ag1 is complexed.
ed. As
A soon
s as all the cyanide
1
has been reacted, the first excess
xce of Ag ca causes a permanent
manent turbidity
tur to appear in the
solution because of the formation of the A AgI precipitate
te according
ac to
Ag1 1 I2 S AgI(s)
‫ڢ‬
ɧƈ Ĺ Ҏ
108. Curve C involves a unidentate ntate
taate ligand,
l A, that forms MA4 in four steps with suc-
cessive formation
tion constants off 10
ion co 08, 106, 104, and 102. These curves demonstrate that a
much sharper
rper end point
po iss obtainedbtained with a reaction
r that takes place in a single step. For
or
ź
this reason,
n, multidentate
mu tidentate ligands nds are usually
lliggands usu preferred for complexometric titrations.
The mostt widely
wide used
widel d complexometric
comp lexometr titration with a unidentate ligand
c plexometri nd is the titra-
tion of cyanide
yanide wwith
th silver
ssilve nitrate,
ni a method introduced by Liebig in thee 1850s.
1850s This
methodod involves
nvolve thee formation
form
forma
ffo of soluble Ag(CN)22, as discussed in Feature
ature 17-2. Other
Oth
common
mmon inorganic
org com
complexing agents and their applications are listed in Table able
ƸŻ ֌
17-1..
l 17-1
źƼࣰ
Ĺ ͇҅Г
Spreadsheet
S
Sp
pr SummaryThe complexometric titration of Cd(II) with
th
h
Cl2 is considered in Chapter 9 of Applications of Microsoft ® Excel in Analytical
C ica
Chemistry, 2nd ed. A master equation approach is used.
17B-2 Precipitation Titrations

Precipitation titrations are based on reactions that yield ionic compounds nds of lim-
ited solubility. Precipitation titrimetry is one of the oldest analytical techniques,
es, dat-
ing back to the mid-1800s. The slow rate at which most precipitates form, however, ever,
limits the number of precipitating agents that can be used in titrations to a hand-
ful. We limit our discussion here to the most widely used and important precipitat-
ing reagent, silver nitrate, which is used for the determination of the halogens, the
TABLE 17-1
ϩΩϧϫΩ Ώϭγέέ̴ηϧ̯΍ϭ ϥϳέΗϣϬϣ
Typical Inorganic Complex-Forming Titrations
Titrant Analyte Remarks
Hg(NO3)2 Br2, Cl2, SCN2, CN2, thiourea Products are neutral Hg(II) complexes;
various indicators used
AgNO3 CN2 Product is Ag(CN)22; indicator is I2;
titrate to first turbidity of AgI
NiSO4 CN2 Product is Ni(CN)422; indicator is Agl;
titrate to first turbidity of AgI
KCN Cu21, Hg21, Ni21 Products are Cu(CN)422, Hg(CN)2, and
Ni(CN)422; various indicators used
408CHAPTER 17 Complexation and Precipitation Reactions and Titrations
halogenlike anions, mercaptans, fatty acids, and several divalent inorganic anions.
Titrations with silver nitrate are sometimes called argentometric titrations.
The Shapes of Titration Curves̵ϭϗ ίΎΑ/̵ϭϗ Ωϳγ΍ ϥϭϳγ΍έΗϳΗ ̶ϧΣϧϣ ϪΑΎηϣ ̶ϧΣϧϣ ϝ̰η
Titration curves for precipitation reactions are calculated in a completely analogous
way to the methods ds described
d
desc
descri in Section 14B for titrations involving strong acids
and strong bases.es. The only
onll difference
on dif is tha
that the solubility product of the precipitate
is substitutedd for thee ion-product
ion-
ion
ion-pro
n prod
product
du t constant
const
onstant nt for water.
w Most indicators for argentomet-
ric titrations respond
espond
ond d to changesge in
change
change
nges in the concentrations
cco
concentr
en of silver ions. Because of this
Ƹɧķ Ɖ Ю
Şź
response, titration
ionn curves
curves forr precipitation
precip
p
pr ation
ion reactions
rea
e usually consist of a plot of pAg
versus volumee of the silverlvver rea
reagen
reagent
gen (usuallyy AgNO3). Example 17-1 illustrates how
p-functions are obtained
btaained
btained
btaine d for the preequivalence-point region, the postequivalence-
tth pree
point regio
region, and thee equivalence
regi eqquivalence point
equiv
equ
quivalen
qu po for a typical precipitation titration.
͕Ԯ
Ε΍έΗϳϧ ϩέϘϧ ΎΑ ΩϳέϠ̯ ϡϳΩγ ϥϭϳγ΍έΗϳΗ ̶ρ >Ag+@ϪΑγΎΣϣ
EXAMPLE
EX
XA
XAM 17-1 N1V1=N2V2 .Ωϭη ϪΑγΎΣϣ ̵ίέ΍ ϡϫ ϪρϘϧ ϡΟΣ ̶ΗγϳΎΑ ΍ΩΗΑ΍
‫ڢ‬
Ca
Calculate
C the silver ion concentration in terms of pAg duringng the titration
off 50.00 mL of 0.05000 M NaCl with 0.1000 M AgNO3 after the
o th addition of
ɧƈ Ĺ Ҏ
tthe ffollowing g volumes of reagent: (a) in the preequivalence

nce point
po
p oi region
o at
10.00 mL, (b) at the equivalence point (25.00 mL), (c) c) after th equivalence
ter the ui enc
nt aat 26.00 mL. For AgCl, Ksp 5 1.82 3 10210.
point
ź
Soluti
Solution :̵ίέ΍ ϡϫ εϳ̡ ρΎϘϧ
(a) Preequivalence-Point Data ̶ϓΎο΍ Cl- ϭ AgCl Ώϭγέ
At 10.00 mL, [Ag1] is very small and cannotnot be computed from stoichiometric
hi
hiome
hiom con-
֌
siderations, but the molar concentration of chloride,
h cNaCl can be obtained
ned readily.
re The
źƼࣰ
equal to cNaCl
equilibrium concentration of chloride is essentially eq Cl.
original no. mmol Cl2 2 no. mol AgNO

gNO
O3 ad
added
[ Cl2 ] < cNaCl 5
total volume
m of solution
(50.00 3 0.05000 2 10.00 3 0.1000)
0..
0.10
5 5 0.02500
0 M
50.00 1 10.00
Ksp 1.82 3 100210
[ Ag1 ] 5 5 .28 3 1029 M
5 7.28
[ Cl2 ] 0.025000
pAg 5 2log (7.28 3 1029) 5 8.14
Additional points in the preequivalence-point region can be obtained in the same
way. Results of calculations of this kind are shown in the second column of Table 17-2.
TABLE 17-2
Changes in pAg in Titration of Cl2 with Standard AgNO3
pAg
50.00 mL of 0.0500 M NaCl 50.00 mL of 0.005 M NaCl
Volume of AgNO3 with 0.1000 M AgNO3 with 0.0100 M AgNO3
10.00 8.14 7.14
20.00 7.59 6.59
24.00 6.87 5.87
25.00 4.87 4.87
26.00 2.88 3.88
30.00 2.20 3.20
40.00 1.78 2.78
:̵ίέ΍ ϡϫ ϪρϘϧ
.Εγϳϧ ̶ϓΎο΍ ̭έΗηϣ ϥϭϳ ̵ϭΎΣ ϭ Εγ΍ ϩΩηέϳγ Ώϭγέ ί΍ ϝϭϠΣϣ
(b) Equivalence Point pAg
At the equivalence point,, [Ag1] 5 [Cl2], and [Ag1][Cl2] 5 Ksp 5 1.82 3 10210 5 [Ag1]2
[ Ag1 ] 5 "Ksp 5 "1.82 3 10210 5 1.35 3 1025
pAg 5 2log (1.35 3 1025) 5 4.87
(c) Postequivalence-Point Region :̵ίέ΍ ϡϫ α̡ ρΎϘϧ
At 26.00 mL of AgNO3, Ag1 is in excess so Εγ΍ ̵ΩΎϳί Ag+ϭ Ώϭγέ ̵ϭΎΣ ϝϭϠΣϣ
(26.00 3 0.1000 2 50.00 3 0.05000)
0.
0.05 )
[ Ag1 ] 5 cAgNO3 5 32 3 1023 M
5 1.32
76.00
ΏϳέϘΗ ί΍ Ύϳ΁ Ύϣη έυϧ ϪΑ
pAg 5 2log (1.32 3 1023) 5 2.88
2
ˮΕγ΍ ϩΩη ϩΩΎϔΗγ΍
Additional results in the postequivalence-point reg
region
ion are obtained in the same
on ar
way and are shown in Table 17-2. Thehe titration
t curve
ve can
ca also
als be derived from the
charge-balance equation as shown for an acid/base
ac titrationn in
tratioon i Feature
F 14-1.
͕Ԯ
Ƹ
The Effect of Concentration
ntratio
trat on
n Titration
Tit
T i Curves
‫ڢ‬
The effect of reagentt and analyte lyte
yte
te ccon
concentration on titration curves can be seen in
the data in Table 17-2 and the two t curves shown in Figure 17-2. With 0.1000 M
tw
ɧƈ Ĺ Ҏ
AgNO3 (Curve ve A), the change

ange
nge
ge in
n pAg in the equivalence-point region is large, about
2 pAg units.
ts. With the
th 0.01000
01000
000 M reagent,
reagen the change is about 1 pAg unit, but still
reag
pronounced.
ced. An n indicato
indicator that
hat produces
produce a signal in the 4.0 to 6.0 pAg region should d
ź
give a minimal
malal error
er
e forr the
t stronger
tronger solution.
sol
so For the more dilute chloride
ide solution
(Curve B),), thee change
chan e in pAg in
cha n the
h equivalence-point
q region wouldd be drawn
draw out
over a fairly
irly large
lar e volume
volum of reagent (,3
vol
vo ,3 mL as shown by the dashed
(, shed lines in the
ƸŻ ֌
źƼࣰ
10
Ĺ ͇҅Г
A
8
ϭ ϥ΍έΗϳΗ B έΩ
6 έΑ΍έΑ 10 ϩΩϧϭηέΗϳΗ
.Ωϧ΍ ϩΩη ϕϳϗέ Potential
pAg
end-point Equivalence
region point
4
έ̳ΎγΎϧη ΏΎΧΗϧ΍έΩ Ωϳϔϣ
2 Figure 17-2Titration curve for (A),

50.00 mL of 0.05000 M NaCl titrated
with 0.1000 M AgNO3, and (B),
50.00 mL of 0.00500 M NaCl titrated
with 0.01000 M AgNO3. Note the
0 increased sharpness of the break at the
0.00 10.00 20.00 30.00 40.00 end point with the more concentrated
Volume AgNO3, mL solution.
figure) so that to determine the end point accurately would be impossible.. The effect
here is analogous to that illustrated for acid/base titrations in Figure 14-4.
The Effect of Reaction Completeness on Titration Curves εϧ̯΍ϭ ϥΩϭΑ ϝϣΎ̯ έΛ΍
A useful relationship can be
derived by taking the negative ❯ Figure 17-3 illustrates the effect of solubility product on the sharpness of the end
point for titrations
ns w with
ith 00.1 M silver nitrate. Note that the change in pAg at the
logarithm of both sides of a
solubility-product expression. equivalence point becomes
ointt becomomes gr
om greater as the he ssolubility products become smaller, that
Thus, for silver chloride, is, as the reaction
ction between
betwe
twe
tw
ween
w n the
t analyt
aanalyte
alyte and sissilver nitrate becomes more complete.
By choosing an n indicator
ndicator
dicator
i ato that changes
thatt cch nges co r in the pAg region of 4 to 6, titration
ges color
Ƹɧķ Ɖ Ю
Şź
2log Ksp 5 2log ([Ag1][Cl2])
5 2log [Ag1] 2 log [Cl2] of chloride ions should
ns sho
hould possible
ld be pos
possibl
os with
th a mminimal titration error. Note that ions
forming precipitates
ipitatess with solubility
wiith solubi
solub
sol ubi products much larger than about 10210 do
pKsp 5 pAg 1 pCl not yield satisfactory
tory
orry eend
ory ndd poi
points.
p
poin
po
This expression is similar to the :̶ϫϭέ̳ ϑϳϠ̰Η
acid-base expression for pKw Titration
ation
tion Curves
C for
or Mixtures
M
Miixtures
Mixxtur of Anions Ύϫ ϥϭϳϧ΁ ρϭϠΧϣ ϥϭϳγ΍έΑϳϟΎ̯ ̶ϧΣϧϣ
T metho
The methods developed
eloped
oped inn Example
E 17-1 for constructing precipitation titration
͕Ԯ
pKw 5 pH 1 pOH
curves
urvess can be extended
cu
curve ed to mixtures that form precipitates of different solubilities.
ded
illustrate,
To iillu
illus
lllus
llu consider 50.00 mL of a solution that is 0.0500 M in iodide ion and
0.08080000 M in chloride ion titrated with 0.1000 M silver nitrate. The curve
0.0800 ur for the initial
‫ڢ‬
stages
ag of this titration is identical to the curve shown for iodide in Figure
stag
tages
tag gu 17-3
17 because
ɧƈ Ĺ Ҏ
silver
silv
sil ve chloride, with its much larger solubility product, does
silve es not
ot beginegin to precipitate
bbeeg prec
until w
un well into the titration.
It iss interesting
inte
i to determine how much iodide iss precipitated
cipitatedd before
ed re appreciable
bbefore appr
apppreciabl
ciabble
ź
ounts of silver chloride form. With the appearancee of thee smallest
amounts lle amount
llest nt of
unt o solid
olid
silver ch chloride, the solubility-product expressions
xpre for both precipitates
recipitates
cip apply,
ap and
ndd
division
visi of one by the other provides the useful relationship
Ksp(AgI) [ Ag1 ][ I2 ] 8.3 3 10217
ƸŻ ֌
27
5 5 210 5 4.56 3 10
7
[ Ag1 ][ Cl2 ] 1.82 3 102
źƼࣰ
Ksp(AgCl)
[I–] 5 (4.56 3 10
1 –7)[
)[Cl–]
Ĺ ͇҅Г
From this relationship, we see that the iodide concentration
concentra
onn
nce decreases
crea to a tiny frac-
crea
tion of the chloride ion concentration beforee silv
silver
ilv chlori
ilve chloride begins to precipitate.
16.0
Ksp = 8.3 × 10 –17
I–
14.0
12.0 :3-17 ϝ̰η

Ksp = 5.2 × 10 –13
Br – ̵ίϳΗ ̵ϭέ Ksp έΛ΍
10.0 ϥϭϳγ΍έΑϳϟΎ̯ ̶ϧΣϧϣ
Ksp = 1.8 × 10 –10
Cl –
pAg
8.0
ΏΎΧΗϧ΍ ϡϭίϟ
Ksp = 3.0 × 10 – 8
6.0
IO–3 ΏγΎϧϣ έ̳ΎγΎϧη
ϪρϘϧ ϥϳϳόΗ ̵΍έΑ
Figure 17-3Effect
17-3 of reaction com-
4.0
Ksp = 5.7 × 10 –5
ϥϻ΍ϭ ̶̯΍
pleteness on precipitation titration BrO 3–
curves. For each curve, 50.00 mL of 2.0
a 0.0500 M solution of the anion was
titrated with 0.1000 M AgNO3. Note 0.0
that smaller values of Ksp give much 0.00 10.00 20.00 30.00
sharper breaks at the end point. Volume 0.1000 M AgNO3, mL
So, for all practical purposes, silver chloride forms only after 25.00 mL of titrant have been
added in this titration. At this point, the chloride ion concentration is approximately
50.00 3 0.0800
cCl 2 < [ Cl2 ] 5 5 0.0533 M
50.00 1 25.00
Substituting into the previous equation yields
[I–] 5 4.56 3 10–7[Cl–] 5 4.56 3 10–77 3 0.0533

0.05533 5 2.433 3 100–8 M
0.053
The percentage of iodide unprecipitated at this
is point
nt can
oint ca be
be calculated
ca ated as
calculated a follows:
follow
oll
Ƹɧķ Ɖ Ю
Şź
amount I2 unprecipitated 5 (75.00 mL)(2.43 31028
2
mm I2/m
mmol /mL)) 51.82
/mL 3 26 mmol
822 310
original amount I2 5 (50.00 mL)(0.0500
00 mm ol/mL) 5 2.50
0 mmol/mL)
mmol/mL
ol/mL 2.5 mmol
1.8 3 1026
1.82
percentage I2 unprecipitated
ipit 5 3 100%
1000%
100
0 5 7.3 3 1025%
2.50
2.5
͕Ԯ
Thus, to within about 7.3 3 10 10–55 perc
percent of the equivalence
pe qui
quiv point for iodide, no
silver chloride forms. Up p tto tthiss point,
pooin
point
poi
o the titration curve is indistinguishable from
‫ڢ‬
that for iodide alone,
e, as shown
sh n in Fi Figure 17-4. The data points for the first part of
Fig
the titration curve, shown
own by thee solid o line, were computed on this basis.
sso
sol
ɧƈ Ĺ Ҏ
As chloride ion
io beginsns to precipitate,
preci
prec
reecip however, the rapid decrease in pAg ends
abruptly at a level that
th can n be
b calculated
ccalculat from the solubility product for silver chlo-
ride and the computed
omput chloride ride concentration
chloride concentrat
concen (0.0533 M):
ź
Ksp
s (A
(AgCl)
gCl) 1.82
1
1. 3 10210
[ Ag1 ] 5 5 5 3.41 3 1029 M
[ Cl2 ] 0.0533
pAg 5 2log(3.41 3 10–9) 5 8.47
ƸŻ ֌
źƼࣰ
su n eend to the sharp decrease in [Ag1] can be clearly seen in Figure

Thee sudd
sudden gure 17-4
7-4
Ĺ ͇҅Г
pAg 5 8.47.
at pAg 8.4 Further additions of silver nitrate decrease the chloride ion
88.47 n con-
con
on
centration,
centra
centrat
ration,
on and
a the curve then becomes that for the titration of chloride byy itself.
tse
16.0
I – + Cl –
14.0 A
12.0
Br– + Cl –
B
10.0
pAg
8.0
6.0
I – + Cl –
and
Br– + Cl –
4.0
2.0
0.0 Figure 17-4Titration curves for

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 50.00 mL of a solution 0.0800 M in
Volume 0.1000 M AgNO3, mL Cl2 and 0.0500 M in I2 or Br2.
For example, after 30.00 mL of titrant have been added,

50.00 3 0.0800 1 50.00 3 0.0500 2 30.00 3 0.100
cCl 2 5 [ Cl2 ] 5 5 0.0438 M
50.00 1 30.00
In this expression, the first two terms in the numerator give the number of
orid
millimoles of chloride dee anand iodide, respectively, and the third term is the number
of millimoles off titrant.
trant.
t.. Therefore,
T
There
82 3 10
11.82
1.8 102210
10
A 1] 5
[ Ag 5 4.16 3 1029 M
Ƹɧķ Ɖ Ю
Şź
0.0438
04438
pAg 5 8.38
The remainder of the he da
data
dataa po
points
poi
p for this curve can be computed in the same way as
for a curve
urve of chloridee byy iitself
itself.
it
Curverve A in Figure
uree 17-4,
17-444, which
17- whi is the titration curve for the chloride/iodide mix-
wh
͕Ԯ
ture
tuure just
tur ust considered,
con
co d, is a composite
ccom of the individual curves for the two anionic spe-
cies.
ies.. Two
cies Tw equivalence poi points are evident. Curve B is the titration curve for a mixture
off bro
bromide
brom
ro
rom and chloride ions. Note that the change associated with h the
t first equiva-
‫ڢ‬
lence
leence point
p becomes less distinct as the solubilities of the two precipitates
precipitat
ip approach
onen another. In the bromide/chloride titration, the initial pAg
ne Ag valuesue are lower
ues low than
ɧƈ Ĺ Ҏ
they
hey are
the
thh a in the iodide/chloride titration because the solubility tyy off silver
bility ill bromide
sil
si
iilve bromid
b ex-
ceeds
eeds that
tha of silver iodide. Beyond the first equivalence
th ce point,
oint, however,
however
howev
weverver, where
w eree chlo-
wh chl
ch
hlo-
o-
ride ionon is being
b titrated, the two titration curves aree identical.
identica
tical.
ź
Titration
Titra
Titratio curves similar to those in Figure 17-4 can an be obtainedn experimentally
experime
rim
im ally lly
by
by measuring
mea the potential of a silver electrode
ctro immersed in the analyte
ectrode naly solution
olu (see
Section 21C). These curves can then n be use to determine
d the
he concentration
centration
entr
ntr
ntratio oof each
eac
of the ions in mixtures of two halide ions. ion
ons. ΎΑ Ύϫ ϥϭϳϧ΁ ρϭϠΧϣ ϥϳϳόΗ έΩ ̶Ϡϣϋ ϩΩΎϔΗγ΍
ƸŻ ֌
źƼࣰ
End Points for Argentometric Titrations ns ̶ϧΣϧϣ έΩ ϥϻ΍ϭ ̶̯΍ ρΎϘϧ ϥΩέϭ΁ ΕγΩ ϪΑ
poin ̵έΗϣϭϳγϧΎΗ̡ ϥϭϳγ΍έΗϳΗ with
εϭέ ΎΑ
Ĺ ͇҅Г
Chemical, potentiometric, and amperometric end ndd points
p are
re used d in
in titrations
ttit
silver nitrate. In this section, we describe onee off tthe chemical all indicator
ind
in methods.
In potentiometric titrations, the potential difference
fference
feere
renc
rence between
betw a silver electrode and
a reference electrode is measured as a function onn of
of ttitrantt vo
volume. Titration curves
similar to those shown in Figures 17-2, 17-3, 3, and 17-4
-3, 7 4 are obtained.
17-
7-4 o Potentiomet-
ric titrations are discussed in Section 21C. C. In amperometric
amperomet
amperom met titrations, the current
me
generated between a pair of silver electrodes iss measured and an plotted as a function of
titrant volume. Amperometric methods are considered sidered in
nsidered i Section 23B-4.
Ϫϧϣ΍ΩέΩ ̶ΗγϳΎΑ έ̳ΎγΎϧη Chemical indicators produce
p a color change or occasionally
cca the appearance or disap-
ϪϳΣΎϧέΩ pAg ί΍ ̵ΩϭΩΣϣ pearance of turbidity in the solution being titrated. The requirements for an indicator for
a precipitation titration are that (1) the color change should occur over a limited range in
.ΩϫΩ ̲ϧέ έϳϳϐΗ ̶ϧΣϧϣ ίϳΗ
p-function of the titrant or the analyte and (2) the color change should take place within
the steep portion of the titration curve for the analyte. For example, in Figure 17-3, we see
that the titration of iodide with any indicator providing a signal in the pAg range of about
4.0 to 12.0 should give a satisfactory end point. Note that, in contrast, the end-point signal
for the titration of chloride would be limited to a pAg of about 4.0 to 6.0.
Method.The Volhard method is one of the most common argen-
The Volhard Method.
tometric methods. In this method, silver ions are titrated with a standard solution of
thiocyanate ion:
ϥ΍έΗϳΗ
Ag1 1 SCN2 8 AgSCN(s)
Iron(III) serves as the indicator. The
T solution turns red with the first slight excess of
thiocyanate ion due to the formation of Fe(SCN)21.
17C Organic Complexing Agents413
The most important application of the Volhard method is the indirect determi-
nation of halide ions. A measured excess of standard silver nitrate solution is added
to the sample, and the excess silver is determined by back-titration with a standard
thiocyanate solution. The strongly acidic environment of the Volhard titration is a
distinct advantage over other titrations of halide ions because such ions as carbon-
ate, oxalate, and arsenate do not interfere. The silver
verr salts
ssalt of these ions are soluble in
acidic media but only slightly soluble in neutral
ral media. a
Silver chloride is more soluble than silverr thiocyanate.
yanat
anate
ana at Ass a result,
ult, in
reesult, i chloride
chlori
chlo de-
Ƹɧķ Ɖ Ю
terminations using the Volhard method, the reaction
eaction
tion
Şź
AgCl(s) 1 SCN2 8 AgSCN( s 1 Cl–
AgSCN(s)
N(s)
occurs to a significant extent near the end of the back-titration.
baack-titrati
back- itratio This reaction causes
itrat
itration
the end point to fade and results in overconsumption
verc
verco n of
o thiocyanate
thiocyanat
thioc
th ion. The result-
ing low results for chloride can be overcom
dee ca overcome
verco by filterin
filtering
ngg the ssilver chloride before
lterin
ing
͕Ԯ
undertaking the back-titration. n. Filtration
ation.
tion F ration is not required
quire for f other halides because
fo
they form silver salts that are less
ss soluble
uble than
ssolu
oluble t silver thiocyanate.
hioc
hiocy Εγ΍ Ag+ ϥ΍έΗϳΗ
Other Argentometric icc M
Meth
Methods.In s I the Mohr method, sodium chromate serves
ods.
s.
‫ڢ‬
as the indicator for the he argentometric
argentom
arg tometri
tom
omet titration of chloride, bromide, and cyanide
ions. Silver ions react with chromate matt to form the brick-red silver chromate (Ag2CrO4)
mat
ɧƈ Ĺ Ҏ
precipitate in the eequivalence-point

nce-p
e-poin
ooint re
oi region. The Mohr method is now rarely used be-
cause Cr(VI) carcinogen.
VI) is a car
carci gen.
n.
The Fajans method
meth use uses orp ion indicator, an organic compound that
sess aan adsorptio
adsorption at
❮ Adsorption
sorpt
orp n inindicators
indica
ndicators
ators
tors were
we
were first
firs
fi
ź
described
cri by K. Fa
Fajans,
ans,
ns, a Po
Polish
P
Polis
oli
adsorbs onto too or desorbs
d from
fr m the surface
surfac of the solid in a precipitation titration. Ide- chemist
hemist
mi in 1926. 926 TiTitrations
ions
on
ally, the adsorption
dsorp desorption
ption or desorp
ption de occurs near the equivalence point and
on occ results not
nd resu involving
lving
vingg adsorption
adsorptio
adso indicators
ind
only in a color ch change
hange
ange
an b also in the transfer of color from the solution
nge but n to the ssolid
ution are rapid,id, accurate,
d, aacc urate, and
u
ura an reliable,
or vice
ce versa.
sa. Εγ΍ Ag+ ϥ΍έΗϳΗ butt their
eir application
ir appl
applicatio
pp is limited
ƸŻ ֌
źƼࣰ
to the
he few w precipitation
ew pre
p
precip titrations
att form
that
hat ffo m colloidal
col
oll precipitates
Ĺ ͇҅Г
rapidly.
rapidly
apidly
dly
dly.y
Spreadsheet
S
Spp Summary In Chapter 9 of Applications of Microsoft ft®
oft
Excel in Analytical Chemistry, 2nd ed., we plot a curve for the titration
n of
NaCl with AgNO3. A stoichiometric approach is first used and then a master
ster
tee
equation approach is explored. Finally, the problem is inverted, and the volume needed
ded
de
to achieve a given pAg value is computed.
17C ORGANIC COMPLEXING AGENTS

Several different organic complexing agents have become important in analytical
chemistry because of their inherent sensitivity and potential selectivity in reacting
with metal ions. Organic reagents are particularly useful in precipitating metals, in
binding metals so as to prevent interferences, in extracting metals from one solvent
to another, and in forming complexes that absorb light for spectrophotometric deter-
minations. The most useful organic reagents form chelate complexes with metal ions.
Many organic reagents are useful in converting metal ions into forms that can be read-
ily extracted from water into an immiscible organic phase. Extractions are widely used to
separate metals of interest from potential interfering ions and for achieving a concentrat-
ing effect by transfer of the metal into a phase of smaller volume. Extractions are appli-
cable to much smaller amounts of metals than precipitations, and they avoid problems
associated with coprecipitation. Separations by extraction are considered in Section 31C.
Several of the most widely used organic complexing agents for extractions are
listed in Table 17-3. Some of these same reagents normally form insoluble species

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meyer flask. In some titrations, known as coulometric titrations, the quantity

13A SOME TERMS USED IN VOLUMETRIC TITRATIONS1

The amountunt of silve nitrate

indicator changes include the appearance or disappearance of a color, a change in

3. Absence off hydhydrate water

Veryy feww ccompou

Few reagents completely meet these ideals.

13C-1 Some Useful Relationships

Any combination of grams,

13C-2 Calculating the Molar Concentration Ωέ΍ΩϧΎΗγ΍ ϝϭϠΣϣ ϪϳϬΗ

Describe the preparation of 2.000 L of 0.0500 M AgNO

To obtain the mass of AgNO3, we rearrange

0.0100 mmol Na1 1 mmol Na2CO3

From the definition of millimole, we write

Recall that the number ooff mil

Vconcd 3 cconcd 5 Vdil 3 cdil

refo to produce 50.0 mL of 0.00500 M Na1, 25.0 mL of the concentrated

Calculating Molar Concentrations from Standardization Data

A 50.00-mL portion of an HCl solution required 29.71 mL of 0.01963 M

Ba(OH)2 1 2HCl S BaCl2 1 2H2O

Thus, the stoichiometric ratio is

The number of millimoles of the standard is calculated

To obtain the number of millimoles off H

ΎΑ ϥ΍έΗϳΗ ϝϭϠΣϣ ϥΩέ̯ έ΍ΩϧΎΗγ΍

2MnO42 1 5C2O422 1 16H1 S 2Mn21 1 10CO2 1 8H2O

The amount of primary-standard Na2C2O4 is given by Equation 13-2

0.2121 2 mmol KMnO4

to Fe21 and titrated with 47.22 mL of 0.02242 M KMnO4 solution. io

MnO42 1 5Fe21 1 8H1 S M

0.02242 mmol KMnO4

The mass of Fe21 is then given by

The percent Fe21 is

(47.22 3 0.02242 3 5 3 0.055847) g Fe 21

(b) To determine the correct stoichiometric ratio, we note that

5 Fe3O4 ; 15 Fe21 ; 3 M O42

47.22 m KMnO4 3 0.02242 mmol KMnO4

0.02242 mmol KMnO4 5 mmol Fe 0.055847 g Fe

2Ag1 1 S22 S Ag2S(s)

Calculate the concentration

P2O5 1 9H2O S 2PO432 1 6H3O1

The stoichiometric ratios are

1 mmol P2O5 1 mmol KSCN

EXAMPLE 13-9 ̵έΗϣϭΩϳ εϭέ

I2O5(s) 1 5CO(g) S 5CO2(g) 1 I2(g)

I2(g) 1 2S2O322(aq) S 2I2(aq) 1 S4O622(aq)

The excess Na2S2O3 was back-titrated with

5 mmol CO 2 mmol Na2S2O3

We divide the firstt ratio by the

This relationship reveals

The number of millimoles of CO can then

13D GRAVIMETRIC TITRATIONS

13D-1 Calculations Associated with Mass Titrations

13E TITRATION CURVES

13E-1 Types of Titration Curves

titrated with 0.1000 M sodium hydroxide. de. The

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50.00 3 0.1000 2 VNaOH 3 0.1000

50.00 3 H3O14 1 VNaOH 3 H3O14 5 5.000 2 0.1000VNaOH

Collecting the terms containing VNaOH gives

VNaOH(0.1000 1 3 H3O14 ) 5 5.000 2 50.00 3 H3O14

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5.000 2 50.00 3 H3O14

2 Figure 17-2Titration curve for (A),

0.0 Figure 17-4Titration curves for