tween electrodes spaced one centimeter apart.
2 Equivalent Conductance at Infinite DilutiolL
Conduction of electricity through an electro-
lyte solution involves migration of positively
charged species toward the cathode and nega-
tively charged ones toward the anode. The
conductance, which is a measure ofthe current
that results from the application of a unit elec-
trical force, depends directly upon the number
of charged particles in the solution. All ions
contribute to the conduction process, but the
fraction of current carried by any given species
is determined by its relative concentration and
its inherent mobility in the medium.
The application of direct conductance mea-
surements to analysis is limited because of the
nonselective nature of this property. The
principal uses of direct meaSurements have
been confined to the analysis of binary water/
electrolyte mixtures and to the determination
of total electrolyte concentration. The latter
measurement is particularly useful as a crite-
rion of purity for distilled wa~er.
On the other hand, conductqnetric titrations,
in which conductance measurements are used
for end-point detection, can be applied to the
determination of numerous substances!
The principal advantage to the conduc-
tometric end point is its applicability to the
titration of very dilute solutions and to systems
in which the reaction between the titrant and
analyte is relatively incomplete. Thus, for
example, the conductometric titration of an
aqueous phenol (K.:::: to-10) solution is
feasible, even though the change in pH at the
equivalence point is insufficient for either a
potentiometric or an indicator end point.
Conductometric titrations become less accu-
rate and less satisfactory wit~ increasing total
;
1 For further discussion of conduetometric methods, see:
J. W. Loveland, in Treatlu 011 AlIGlytlc4l/ CMmIstry, eds.
I. M. Kolthoff and P. J. ElviJI&. New York: Intcncience,
1963, Part I, vol. 4, Chapter SI; and T. SbedIoVlky and
L. Sbedlovsky, in Physkal Methods ofClrem&try, eds. A.
Weissberger and B. W. ROIIitor. New York: Wiley-inter-
science, 1971, vol. I, Part llA, Chapter 3.
electrolyte concentration. Indeed, the change
in conductance due to the addition of titrant
can become largely masked in solutions with
high salt concentrations; under these circum-
stances, the method cannot be used.
Upon application of a potential, ions in a so-
lution are essentially instantly accelerated to-
ward the electrode of opposite charge. The rate
at which they migrate, however, is limited by
the frictional forces generated by their motion.
As in a metallic conductor, the velocity of the
particles is linearly related to the applied field;
Ohm's law is thus obeyed by electrolyte
solutions.
Some Important Relationships
Conductance G. The conductance of a so-
lution is the reciprocal of the electrical resist-
ance and has the units of ohm - t. That is,
G=.!..
R With I fixed by definition at one centimeter,
where R is the resistance in ohms.
Specific Conductance k. Conductance is di-
rectly proportional to the cross-sectional area
A and inversely proportional to the length I
of a uniform conductor; thus,
A C
G=k-
I
where k is a proportionality constant called
the specific conductance. Clearly, it is the con-
ductance when A and I are numerically equal.
If these parameters are based upon the centi-
meter, k is the conductance of a cube of liquid
one centimeter on a side. The dimensions of
specific conductance are then ohm - t em - 1.
Equivalent Conductance. The equivalent
conductance A is defined as the conductance
of one gram equivalent of solute contained be-
Neither the volume of the solution nor the area
of the electrodes is specified; these vary to
satisfy the conditions of the definition. For
example, a 1.0N solution (1.0 gram equivalent
per liter) would require electrod"es with indi-
vidual surface areas of 1000 em2; a O.lN solu-
tion would need 10,000-cm2 electrodes. The
direct measurement of equivalent conductance
is thus seldom, if ever, undertaken because of
the experimental inconvenience associated
with such relatively large electrodes. Instead,
this quantity is determined indirectly from
specific conductance data. By definition, A will
be equal to G when one gram equivalent of
solute is contained between electrodes spaced
one centimeter apart. The volume V of the
solution (em3) that will contain one gram
equivalent of solute is given by
V= 1000
C motion of the oppositely charged ions sur-
where C is the concentration in equivalents
per liter. This volume can also be expressed in
terms of the dimensions of the cell
V= IA
V= A = 1000
C behind the moving particle.
Substitution into Equation 22-2 thus gives
A = l000k
Equation 22-3 permits calculation of the equiv-
alent conductance from the experimental value
of k for a solution of known concentration.
2 In the context of electrolytic conductance, the equiva-
lent is defined in terms of the number of cbarses carried
by an ion and not upon its fate in a specific reaction.
Thus, the weight of one gram equivalent of Ba2 + is equal
to the atomic weight of barium divided by two.
The mobility of an ion in solution is governed
by four forces. An electrical force, equal to the
product of the potential of the electrode and
the charge of the ion, tends to move the par-
ticle toward one of the electrodes. This effect
is partially balanced by a frictional force that
is a characteristic property for each ion. These
are the only two effects that playa significant
role in determining the conductivity of a dilute
solution; under these circumstances the
equivalent conductance of a salt is inde~ndent
of its concentration.
At finite concentrations, two other factors,
the electrophoretic effect and the relaxation ef-
fect, become important and cause the equiv-
alent conductance of a substance to decrease
as its concentration increases. The behavior
of a sodium chloride solution is typical and is
shown in Table 22-1.
The electrophoretic effect stems from the
rounding the ion of interest. These ions carry
with them molecules of solvent; the motion of
the primary particle is thus retarded by the
flow of solvent in the opposite direction. The
relaxation effect also owes its genesis to move-
ment of the ionic atmosphere surrounding a
given particle. Here, however, the ion is slowed
by the charge of opposite sign that builds up
For strong electrolytes, a linear relation-
ship exists between equivalent conductance
TABLE 22-1 EFFECT OF
CONCENTRATION ON
EQUIVALENT CONDUCTANCE
Concentration of Nan eqfIiter A
0.1 106.7
0.01 118.5
0.001 123.7
Infinite dilution 126.4(Ao)
 The equivalent ionic conductance is a mea- conductance measurements are made at suf- power source S provides an alternating cur-
and square root of the concentration. Extrap-
sure of the mobility of an ion under the in- ficiently low frequencies so that the latter mech- rent in the frequency range of 60 to 1000 Hz
olation of this straight-line relationship to
fluence of an electric forCe field and is thus anisms are not important. Oscillometry, on the at a potential of 6 to 10 V. The resistances
zero concentration yields a value for the equiv-
a gauge of its capacity for transporting elec- other hand, makes use of radio frequencies; RAe and RBC can be calculated from the posi-
alent conductance at infinite dilution Ao. A
similar plot for a weak electrolyte is nonlinear, tricity. For example, the ionic conductance of here, the dielectric current becomes important. tion of C. The cell, of unknown resistance R",
a potassium ion is nearly the same as that of Oscillometric measurements are discussed at is placed in the upper left arm of the bridge
and direct evaluation ot Ao is difficult.
a chloride ion; therefore, electricity passing the end of this chapter. and a precision variable resistance R. is placed
At infinite dilution, interionic attractions
become nil; the overall conductance of the through a potassium chloride solution is car- in the right-hand side. A null detector N D is
solution then consists of the sum of the indi- ried nearly equaliy by the two species. The used to indicate the absence of current between
vidual equivalent ionic conductances situation is quite different with hydrochloric D and C. The detector may consist of a pair
acid; because of the greater mobility of the THE of ordinary headphones, since the ear is re-
Ao=.l.~ +.l.~ hydrogen ion, a larger fraction of the electric- MEASUREMENT sponsive to frequencies in the 1000 Hz range;
ity [3SO/(350 + 7~) = 0.82] is carried by that OF CONDUCTANCE alternatively, it may be a "magic eye" tube, a
where .l.~ and .l.~ are the equivalent ionic species in an electrolysis. cathode ray tube, or a microammeter.
conductances of the cation and the anion of Ionic conductance data permit comparison A conductance measurement requires a source Capacitance effects within R" cause an al-
the salt at infinite dilution. Individual ionic of the relative conductivity of various solutes. of electrical power, a cell to contain the solu- ternating-current device such as this to suffer
conductances can be determined from other Thus, we are juStified in saying that O.OIF tion, and a suitable bridge to measure the . a loss in sensitivity when very high resistances
electrolytic measurements; values for a number hydrochloric acid will have a greater conduc- resistance of the solution. are measured; in practice, a variable capaCi-
of common ions are given in Table 22-2. Note tivity than O.OIF sodium chloride because of tor across R. compensates for this effect.
that symbols such as tMgH, iFe3+, arid
the very large ionic conductance of the hy- Power Sources Conductance can also be determined by
tSOi - are used to emphasize that the con-
drogen ion. Such' conclusions are important means of a simple electronic circuit such as
centration units are in equivalents per liter. in predicting the pourse of a conductometric Use of an alternating current source elimi- that shown in Figure 3-21a (p. 62). Here, the
The differences that exist among the equiv- nates the effect of faradaic currents. There are,
titration. ' conductance is read directly from a dc meter
alent ionic conductances of various species however, both upper and lower limits to the fre- or a recorder.
(Table 22-2) arise primarily from differences quencies that can be employed; audio oscil-
in their size and the degree of their hydration. Alternating Currents in a Cell lators that produce signals of about 1000 Hz
are the most satisfactory. Cells
As was pointed out earlier (p. S05~ conduc-
tion of dc electricity across a solution/electrode For less refined work, an ordinary 6O-cycle Figure 22-1 depicts three common types of
interface is a faradaic process in which oxida- current, stepped down from 110 to perhaps cells for the measurement of conductivity. Each
tion and reduction must occur at the two 10 V, is also used. With such a source, how- contains a pair of electrodes firmly fixed in a
electrodes. An alternating current, on the other ever, faradaic processes often limit the accu- constant geometry with respect to one another.
TABLE 22-2 EQUIVALENT IONIC racy of the conductance measurements. On
hand, requires no electrochemical reaction at The electrodes are ordinarily platinized to
CONDUCTANCES AT 25°C
the electrodes (p. 506); here, electricity flows the other hand, the convenience and ready increase their effective surface and thus their
>..~ Anion >..!. availability of 6O-cycle power justify its use
Cation as a consequence of nonfaradaic processes. capacitances; faradaic currents are minimized
Because the changes associated with faradaic for many purposes. as a result.
H3O+ 349.8 ow 199.0
conduction can materially alter the electrical Power sources with frequencies much great- Determination of the Ceil Constant. Ac-
Li+ 38.7 Cl- 76.3
characteristics of a cell, conductometric mea- er than 1000 Hz create problems in conduc- cording to Equation 22-2, the specific conduc-
Na+ SO.1 Br- 78.1
surements are 8dvantageously based upon tance measurements with a bridge. Here, the tance k is related to the measured conductance
K+ 73.5 1- 76.8
nonfaradaic processes. cell capacitance and stray capacitances in other G by the ratio of the distance separating the
NHt 73.4 NO; 71.4
At low frequepcies, conduction of ac elec- parts of the circuit cause phase changes in the electrodes to their surface area. This ratio has
Ag+ 61.9 CIO; 67.3 tricity through ari electrolyte involves periodic current for which compensation is difficult. a fixed and constant value in any given cell
tMg2+ 53.1 C2H3Oi 40.9
motion of the ions toward and away from and is known as the cell constant. Its value is
teaH 59.5 -tSO~- 80.0 seldom determined directly. Instead, the <:on-
the electrodes, as noted earlier (p. 506);
tBaH 63.6 too~- 69.3
however, at radio frequencies, a significant
Resistance Bridges ductance of a solution whose specific conduc-
tPbH 69.5 te20~- 742 fraction of ac electricity is transported in the The Wheatstone bridge arrangement, shown tance is reliably known is measured; the cell
iFe3+ 68.0 iFe(CN):- 110.5
form of a dielectric current which results from in Figure 2-24 (p. 35), is typical of the appara- constant can then be calculated. Solutions of
iLa3+ 69.6 potassium chloride are commonly chosen for
induced and orientation polarization. Most tus used for conductance measurements. The

cell calibration.3 Typical data are shown in
Table 22-3.
Once the value of the cell constant has
been determined, conductivity data can be
easily converted to terms of specific conduct-
ance with the aid of Equation 22-2.
Temperature Control The temperature
coefficient for conductance measurements is
about 2"1oiC; as a consequence, some tem-
perature control is ordinarily required during
a conductometric measurement. Although a
constant temperature is necessary, control at
• G. Jones and B. C. Bradshaw, J. A"",r. C/oem. Soc,
1780 (1933).
TABLE 22-3 CONDUCTANCE OF SOLUTIONS
FOR CELL CALIBRATION
Grams KCI per
1000I or Solutionin Vaa.n
71.1352
7.41913
0.745263
some specific level is not required for a suc-
cessful conductometric titration. For many
purposes, it is sufficient to immerse the cell in
a reasonably large bath of water or oil, which
is at room temperature.
Conductometric measurements provide a con-
venient means for locating end points in titra-
tions. Sufficient measurements (three to four
before and after the equivalence point) are
needed to define the titration curve. After being
ss. corrected for volume change, the conductance
data are plotted as a function of titrant volume.
Specific CODlIactance at ZSOC,
oIun-1 em-I
0.111342
0.0128560
0.00140877
The two linear portions are then extrapolated,
the point of intersection being taken as the
equivalence point.
Because reactions fail to proceed to ab-
solute completion, conductonietric titration
curves invariably show departures from strict
linearity in the region of the equivalence point.
Curved regions become more pronounced as
the reaction in question becomes less favorable
and as the solution becomes more dilute. The
linear portions of the curve are best defined
by measurements sufficiently removed from
the equivalence point so that the common ion
effect forces the reaction more nearly to com-
pletion. It is in this respect thllt the conducto-
metric technique appears to 'best advantage;
in contrast to potentiometric or indicator
\.
\ them in solution.
\.
\ /
\ ~
\. \
\ 1\
H.O·' r--..
\ \V
' ,
\
-- .-
CI-
\
1\-
No' I--~1--
'\
-'
1/'';
1-"
FIGURE 22-2 Conductonietrictitration of
a strong acid with a strong base. The solid
line represents the titration curve, corrected
for volume change. Broken lines indicate the
contribution of the individual species, also
corrected for volume change, to the con-
ductance of the solution.
methods, which require observations under
conditions where reaction is least complete, a
conductometric analysis can be employed suc-
cessfully for titrations based upon relatively
unfavorable equilibria.
The conductometric end point is completely
nonspecific. Although it is potentially adapt-
able to all types of volumetric reactions, the
number of its useful applications to oxidation-
reduction systems is limited; the substantial
excess of hydrogen ions typically needed for
such reactions tends to mask conductivity
changes associated with the volumetric reac-
tion.
Acid-Ba.e Titration.
Neutralization titrations are particularly well
adapted to the conductometric end point be-
cause of the large ionic conductances of
hydrogen and hydroxide ions compared with
i the conductances of the species that replace
Titration of Strong Acids or Bases. The
solid line in Figure 22-2 represents a curve
/ (corrected for volume change) obtained when
/
hydrochloric- acid is titrated with sodium
hydroxide. Also plotted are the calculated
/ contributions of the individual ions to the
conductance of the solution. During neutral-
/ ,
OH-:/
ization, hydrogen ions are replaced by an
// equivalent number ofless mobile sodium ions;
the conductance changes to lower values as a
,
~7
/ -- .-~,-
result of this substitution. At the equivalence
point, the concentrations of hydrogen and
hydroxide ions are at a minimum and the
solution exhibits its lowest conductance. A
reversal of slope occurs past the end point as
the sodium ion and hydroxide ion concentra-
tions increase. With the exception of the im-
mediate equivalence-point region, an excellent
linearity exists between conductance and the
volume of base added; as a result, only three
or four observations on each side of the
equivalence point are needed for an analysis.
The percentage change in conductivity dur-
 (K. = 6 x 10- 10) with strong base. This reac-
tion is so incomplete that a potentiometric or
visual indicator end point is unsatisfactory. In
the early stages of the titration, a butTer is
rapidly established that imparts to the solu-
-C.10N " tion a relatively small and nearly constant hy-
VolumeNaOH drogen ion concentration. The added hydrox-
lb)
-ide ions are consumed by this buffer and thus
do not directly contribute to the conductivity.
species is so slight, however, that little or no
curvature occurs with the establishment of
the butTer region (see Figure 22-380 for exam-
ple). As the strength ofthe acid (or base) be-
comes greater, so also does the extent of the
curvature in the early portions of the titration
curve. For weak acids or bases with dissocia-
tion constants greater than about 10- 5, the
curvature becomes so pronounced that an
what less mobile nitrate ions of the reagent· a
slight decrease in conductance results. After the
reaction is complete a rapid increase occurs
owing to the addition of excess silver nitrate:
. ?<>~uctometric methods based upon pre-
CipItatIon or complex-formation reactions are
not so useful as those involving neutralization
processes. Conductance changes during these
titrations are seldom as large as those observed

tbd]
VolumeHel
Cd)
Volume AgN03
(fl
FIGURE 22-3 Typicalconductometricti-
tration curves. Titration of (a) a very weak
acid (K. ::::10-1°) with sodium hydroxide;
(b) a weak acid (K.:::: 10-5) with sodium
hydroxide (Note that for O.ot N solutions,
conductance'x 10 is plotted); (c) a weak acid
(K. ::::10-5) with aqueous ammonia; (d) the
salt of a weak acid; (e) a mixture of hydro-
chloric and acetic acids with sodium hy-
droxide; and (I) chloride ion with silver
nitrate.
ing the course of the titration of a strong acid
or base is the same regardless of the concen-
tration of the solution. Thus, very dilute solu-
tionS can be analyzed with an accuracy com-
parable to more concentrated ones.
Titration of Weak Adds or Bases. Figure
22-3a illustrates application of the conducto-
metric end point to the titration of boric acid
.A gradual increase in conductance does result,
:however, owing to the increase in concentra-
tion of sodium and of borate ions. With attain-
:ment of the equivalence point, no further
borate is produced; additions of base then
. cause a more rapid increase in conductance
: due to the highly mobile hydroxide ions.
Figure 22·3b illustrates the titration of a
moderately weak acid, such as acetic acid
(K. ~ 10-51 with sodium hydroxide. Non-
linearity in the early portions of the titration
curve creates problems in establishing the end
point; with concentrated solutions, however,
the titration is feasible. As before, we can
interpret this curve in light of the changes in
comJMiition that occur. Here, the solution
initially has a moderate concentration of hy-
drogen ions (-10 - 3 M). Addition of base re-
sults in the establishment of a buffer system
and a consequent diminution in the hydrogen
ion concentration. Concurrent with this de-
crease is an increase in the concentration of
sodium ions as well as the conjugate base
of the acid. These two factors act in opposi-
tion to one another. At first, the decrease in
hydrogen ion concentration predominates and
a decrease in conductance is observed. As the
titration progresses, however, the pH becomes
stabilized (in the buffer region); the increase
in salt content then becomes the more im-
portant factor, and a linear increase in con-
ductance finally' results. Beyond the equiv-
alence point, the curve steepens because of the
greater ionic conductance of hydroxide ion.
In principle, all titration curves for weak
acids or bases contain the general features of
Figure 22-3b. The ionization of very weak
end point cannot be distinguished .
Figure 22-3c illustrates the titration of the
same weak acid as in Figure 22-3b, but with
aqueous ammonia instead of sodium hydrox-
ide. Here, because the titrant is a weak elec-
trolyte, the curve is essentially horizontal past
the equivalence point. Use of ammonia as
titrant actually provides a curve that can be
extrapolated with less uncertainty than the
corresponding curve based upon titration
with sodium hydroxide.
Figure 22-3d represents the titration curve
for a weak base, such as acetate ion, with a
standard solution of hydrochloric acid. The
addition of strong acid results in formation of
sodium chloride and undissociated acetic acid.
The net effect is a slight rise in conductance
due to the greater mobility of the chloride ion
over that of the acetate ion it replaces. After
the end point has been passed, a sharp rise in
conductance attends' the addition of excess
hydrogen ions. The conductometric method is
convenient for the titration of salts whose
acidic or basic character is too weak to give
satisfactory end points with indicators.
Figure 22-3e is typical of the titration of a
mixture of two acids that ditTer in degree of
dissociation. The conductometric titration of
such mixtures frequently leads to more accu-
rate results than those obtained with a poten-
tiometric method.
Precipitation and Complex-Formation
TitratiolB. Figure 22-3fillustrates the con-
ductance changes that occur during the titra-
tion of sodium chloride with silver nitrate.
The iriitial additions of reagent in effect cause
a substitution of chloride ions by the some-
with acid-base reactions because no other ion
approaches the conductance of either the
hydrogen or the hydroxide ion. Such factors
as slowness of reaction and coprecipitation
represent further sources of difficulty with
precipitation reactions.
APPLICATIONS OF DIRECT
CONDUCTANCE MEASUREMENTS
Direct conductometric measurements sutTer
from a lack of selectivity, since any charged
species contributes to the total conductance
of a solution. On the other hand, the high
sensitivity of the procedure makes it an im-
portant analytical tool for certain applica-
tions. As we have noted, an important use of
the method has been for estimating the purity
of distilled or deionized water. The specific
conductance of pure water is only about
S x 10- 8 ohm -I em -I; traces of an ionic im-
purity will increase the conductance by an
order of magnitude or more.
Conductance measurements are also em-
ployed for determining the concentration of
solutions containing a single strong electrolyte,
such as solutions of the common alkalis or
acids. A nearly linear increase in conductance
with concentration is observed for solutions
containing as much as 20 % by weight of solute.
Analyses are based upon calibration curves.
Conductance measurements are also widely
used to measure the salinity of sea water in
oceanographic work.
Finally, conductance measurements yield
valuable information about association and
dissociation equilibria in aqueous solutions-
provided, of course, that one or more of the
reacting species is ionic.
As mentioned earlier (p. 506~ the conduction
of ac radio-frequency (10' to 107Hz) electricity
through a solution is a complex process that
involves not only ionic motion but also induced
and orientation polarization of the molecules
in the medium. As a result of these various
conduction mechanisms, the impedance of a
solution to the flow of current varies in an
intricate way with the dielectric constant, the
electrolyte concentration, and the frequency.
Interpretation ofthe relationships among these
variables is difficult, and the use of high-
frequency currents could hardly be justified
were it not for the fact that the experimental
measurement does not require direct contact
between the electrodes and the solution.
Instruments
As shown in Figure 22-4, a typical cell for
high-frequency measurements consists of a
glass container designed to fit snugly between
a pair of cylindrical metal electrodes. The elec-
trode and cell are then made part of the reso-
nant circuit of a sine-wave oscillator (p. 24);
the behavior of this resonant circuit can be
interpreted by assuming that the solution in
the cell acts like a parallel capacitor and resis-
tance. The capacitive reactance depends upon
frequency and the dielectric constant of the
solution; the resistive impedance is also fre-
quency-dependent and is related to the number
and kinds of ions in the solution as well. At
high frequencies, the resistive impedance is
generally lower than that measured with
currents in the l000-Hz range.
Instruments are available commercially that
are based upon either the change in frequency
or the change in oscillator circuit current (at
constant frequency) caused by the presence of
FIGURE 22-4 Sample cell and elec-
trodes for high. frequency measurements.
the sample and cell. In the former, one or more
variable capacitors are wired in parallel with
the cell and the circuit is tuned to its resonance
frequency in the absence of sample. The sample
is then introduced and the capacitance that
must be subtracted (by means of a calibrated
capacitor) to restore resonance is determined.
For instruments based on the resistive im-
pedance of the sample, the change in oscillator
current resulting from the introduction of
sample is measured.
Because of the limited scope of oscillometry,
we shall not dwell further on the somewhat
complicated instrumentation and complex in-
terrelations associated with this technique; the
reader is referred to the treatment of the subject
by Reilley4 and Pungor.'
4 C. N. Rci11ey, in New lrutnunental Methods in Electro-
cltntlsrry, ed. P. Delahay. New York: Intenciencc, 19S4,
Chapter IS.
• E. Punlor, Oscillometry and CondllCtometry. New York:
Pergamon Press, 1965.
Applications
are similar to those for conventional low-
Analysis of Binary Mixtures. Oscillometric frequency condu~o~etric titrations. The ap-
measurements have been employed for the ~rance of the titration curves is often quite
determination of binary mixtures of nonionic ~ifferent, however; both V-shaped curves and
species. Such analyses are b8sed upon the Inverted V-type end points are encountered.
dielectric behavior of the mixtures and re- Curvature is also frequently observed; data
quire that the dielectric constants for the two must, therefore, be collected in the immediate
co~ponents ~iffer significantly. For this appli- end-point region. For a given reaction the
cation, a~ Instrument based .on frequency titration curve depends upon the concentr~tion
changes IS employed. Empirical calibration of the substance titrated as well as upon the
curves permit conversion of inStrument read- parameter measured (that is, the change in
ings to concentration ratios. Examples of this frequency or the oscillator current).
type of application include the analysis of The high-frequency method does not ap-
mIXtures of ethanol and nitrobenzene, benzene pear to yield titration data of higher accuracy
and chlorobenzene, alcohol and water and 0- than the classical method, and suffers the draw-
and p-xylene. " backs of greater empiricism and of requiring
Titratio... Oscillometric measurements measurements near the end point. Thus, except
~ave ~ employed to locate the end point where the presence of electrodes interferes with
In vanous types of titrations. The methods a titration, oscillometry offers little advantage.
For each ~f the' following problems, derive an approximate titration
curve o~ specIfic conductance versus volume of reagent, employing the
assumptIon that
(a) 100.0 ml of 1.00 x 1O-3N 50lution is being titrated with
1.00 x 1O-2N reagent;
(b) the volume change occurring as the titration proceeds can be
neglected;
(c) t~e .equivalen~ ionic conductances of the various ions are not
slgmficantly different from their equivalent ionic conductances at
infinite dilution (Table 22-2).
~alcula~~ theoretical specific conductances of the mixtures after the follow-
Ing addItIons of reagent: 0.00, 2.00, 4.00, 6.00, 8.00, 10.0, 12.0, 14.0, 16.0 ml.
1. Ba(OHh with HCI
2. Phenpl with KOH (use K. = 1.0 X 10-10 and All. = 30 for C6H,O-)
3. Sodium acetate with HCl04 (assume K. for acetic acid = 1.8 x 10-')
4. P~oPllnoic acid (All. = 35.8 for CH3CH2COO- and K. = 1.3 x 10-')
WIth NaOH
5. Propanoic acid with NH3
6. Pb(N03h with Naa
7. Pb(N03h with LiCI