Conductometric Titration of Sulfuric and Hydrochloric Acids and

Their Mixtures in Anhydrous Acetic Acid

TAKERU HlGUCHl and CARL R. REHM
School o f Pharmacy, University o f Wisconsin, Madison, Wis.

lowing neutralization of the first hydrogen can be ascribed to

the lower degree of dissociation of the alkali sulfate, which was
progressively formed in the system, as compared t o the alkali
bisulfate. Although straight-line approximations are used in
the plot of extrapolation purposes, theoretically the actual curves
are probably much more complex involving square root and
higher power terms of concentration. I n practice, however, a
linear plot seems to be a fair approximation in the concentration
range studied.
This explanation, based on the assumption that alkali sulfates
are very slightly dissociated in acetic acid, is certainly a rea-

Sulfuric and h j drochloric acids and their mixtures

have been titrated conductometrically in anhydrous
acetic acid with several alkali acetates. The results
represent the first time that the neutralization end
points of the two hydrogens of sulfuric acid have been
definitely differentiated in acetic acid. The conductometric plots for this acid exhibit two breaks corresponding to the neutralization end points of the first and
second hydrogens. Differences in the plots obtained
from titrations with different alkali acetates agree
with predictions based on conclusions of earlier investigators. Conductometric titration plots of mixtures of
sulfuric and hydrochloric acids in acetic acid with
lithium acetate were found to exhibit three breaks corresponding to the neutralization of one of the two
hydrogens of sulfuric acid, the hydrochloric acid, and
the second hydrogen of sulfuric acid, in t h a t order.
Quantitative estimations of sulfuric and hydrochloric
acids in such mixtures, based on the three breaks, are
in agreement with the amounts present.

X CONNECTIOS with other studies being carried out at

these laboratories, conductonietric titrations of sulfuric and
hydrochloric acids and their mixtures have been carried out in
acetic acid. The results are of particular interest because they
represent so far as known the first time that the neutralization
end points of the two hydrogens of sulfuric acid have been definitely differentiated in this solvent. These findings, together
with a rationalization of the ohserved facts, are presented a t
this time not so much tiecause of possible direct analytical application of the conductometric method to the particular acids
studied hut rather because they cast some light on the complex
behavior of acid-base reactions in acetic acid and other solvents
of lo^ dielectric constant which are enjoying wide usage in analytical fields.
Apparently very little work has been done on conductometric
titrations of acids in acetic acid. Perchloric and hydrobromic
acid have been titrated conductometrically in acetic acid with
sodium acetate by Kolthoff and Killman (4)and perchloric acid
has heen titrated conductonietrically with a number of organic
amines by Hall and Spengeman (3). -4lthough these investigators have shown the general feasi1)ilit.vof the method, there hap
been very little sustained interest in this field.

+
+

>\IHSO4 HAC
~ I I ~ S OHAC
~

First break corresponds to conversion of sulfuric acid t o sodium bi-1

sulfate: the second break corresponds to conversion of sodium bi311lfate t o sodium sulfate

t
1000-

900

-+

Figure 1. Conductometric titration of 100 ml. of

0.0176.1.1 sulfuric acid in acetic acid with 0.500M
sodium acetate a t 23" C.

The general type of conductometric titration plot yielded by

sulfuric acid solution in acetic acid when titrated by an alkali
acetate solution is shown in Figure 1. There are two significant
breaks in the curve which correspond very closely to the stoichiometric reactions:

+ HzSO,
+ RIHSO4

ML. SODIUM ACETATE

SULFURIC ACID

MAC
hIAc

M V.

(1)
(2)

It is evident that the plot is different from the usual acid-base

conductometric plots found in aqueous systems. The initial
increase in the conductivity in the figure can be attributed to
the higher degree of dissociation of the alkali bisulfate into current-carrying alkali ions and bisulfate ions as compared to the
original sulfuric acid molecules. The drop in conductivity fol-

700

ML. SODIUM ACETATE

Figure 2. Potentiometric titration of 2 ml. of

sulfuric acid (0.049M) with sodium acetate
(0.0507M) in glacial acetic acid

408

V O L U M E 2 7 , NO. 3, M A R C H 1 9 5 5

409

boilable one. Because of its high central charge, it seems logical

to expect, for example, the triple ion Sap+SOn-- to be less dissociated than the ion pair Na+HS04- The effective negative
charge tending to bind sodium ions would appear to be considerably greater in the case of I than in the case of I1 because of the
greater electrophilic nature of the proton as compared to the
sodium ion.
S04XaSOlH -

I1

Conductometric Determination of Sulfuric

Acid in ..icetic Acid

Titrant
NaAc
LiAe

Ii ..\c
(C5Hii)aNHAc

Potentiometric plots which are presently widely used in nonaqueous titrimetric determinations do not, in contrast to the conductometric plots, bring out this behavior. As shomm in Figure
2 the potentiometric titration curve of sulfuric acid in acetic
acid with sodium acetate exhibits only a single break corresponding to the titration of the first hydrogen. From potentiometric
response alone there is very little to indicate that the second
hydrogen can be titrated.
From a purely theoretical standpoint, the glass electrode, moreover, ip not necessarily the best indicator of the extent of these
acid-base reactions. It can be shown that the extent of such
reactions is roughly governed by the constant
(3)
11here

Table I.

K , = dissociation constant of the acid

Kb = dissociation constant of the base
K H A=~ autoprotolytic constant of acetic acid
Kob = dissociation constant of the resulting salt

Since the extent is not purely a function of the strengths of the

acid and of the base alone, an acidity indicator is thus not necessarily the best indicator of these reactions.
Further information as to the nature of this system can be
obtained b y comparing the types of conductometric titration
plots exhibited by different bases. The magnitude of the break
in going from the bisulfate to the sulfate would be expected to
be strongly influenced by the nature and size of the cations involved if the rationalization is valid.
Thus, if potassium acetate were used to titrate the acid, a
less pronounced break would be expected, since the larger pize
of the potassium ion (as compared to the sodium ion) nould re-

Millimoles
Millimoles 1st
Sdded
Hydrogen Found
1.72
1.74
0.889
0.904
0.587
0.586
0.586

0.580

0.586
0.580

0,580
0,580

0.492

0,497
0.583

0.58ij

Millimoles 2nd
Hydrogen Found
1.73
0.903
0.588
0.586
0.520
0.510
.

...

duce the coloumbic forces iiivolved in the ion-pair forination.

Similarly, the use of a base containing a very large orgaiiic
ration might result in a curve in which the break is almost conipletely suppressed. With a tiase containing a relatively small
cation, such as lithium acetate, one ~ o u l dexpect the break to be
even m w e pronounced than that produced by sodium acetate.
These predictions are based on the conclusions of Kolthoff and
Willman (4).
-111 of these expectations ivere boi~icout experimentally. In
Figure 3, conductometric titration plots of sulfuric acid titrated
(top t o bottom) with triamylaiiiiiioniuiii acetate, potassium acetate, sodium acetate, and lithium acetate are shown. Because
of the limited solubilities of lithium and potassium sulfates in
the system, it was found necessary to employ a lower concentration of the acid in obtaining these plots than that used in Figure
1. This resulted in somewhat poorer end-point breaks. It is
apparent, nevertheless, that the degree of the first break derreased progressively in the order lithium > sodium > potassium
> triamylamine. The point of break for the amine does not appear on the graph but consisted of a very slight positive break.
I n Table 1; analytical result.- shown in Figure 3 are given for
each end point. Although no seiious efforts were made to obtain
highly accurate data, because of the type of extrapolation used
as discussed previously, these results nevertheless indicate
for most cases good stoichiometric relationships.
3IIXTURE O F SULFURIC 4YD HYDROCHLORIC ACIDS

Although it is impossible to distinguish the alkalimetric titration end points of miutures of hydrochloric and sulfuric acids by
potentiometric means either in n ater or in acetic acid, acceptable
end points can be detected bv use of conductometric means in
the latter solvent. From the results of the present inveatigation,
it appears that one of the t u o hjdrogens of sulfuric acid is first
titi ated, then hydrochloiic acid, and finally the second hydrogen
of sulfuric acid.
The conductance curves obtained on titrating 0.11951 hydrochloric acid alone in acetic acid i\ith 0.200.V lithium acetate,
sodium acetate, potassium acetate, and triam~~latiiinoiiiuii~
acetate are shown in Figure 4. Significant breaks &ere obtained in the case of trianiylammonium acetate and lithium acetate. A slight break was obtained with sodium acetate. These
Iireakf correspond closely to the stoichiometric reaction

HCI
I

I.0
2.0
HOLES ALKALI ACETATE/HOLES

30
ACID

Figure 3. Conductometric titrations of 100 ml. of

0.00586.M sulfuric acid in acetic acid with 0.200.M alkali
acetates at 25" C.
9 Triamylammonium acetate

0 Potassium acetate
+0
Sodium acetate
Lithium acetate

The first break corresponds t o conversion of sulfuric acid t o the respective alkali bisulfates; the second break to the conversion of the alkali bisulfates t o t h e sulfates

+ SaAc

-+

SaCl

+ HAC

The iiiitial rise in conductance can be ascribed to the foiiii:ttion

of the chloride salts xhich appeal to be more highly conducting
than hydrochloric acid. The positive break obtained in the case
of triamylammonium acetate indicates that this base is mole
highly dissociated than the rhloride salt The absence of any
discontinuity in the plot obtained with potassium acetate indicates that potassium acetate and potassium chloride are effectively dissociated t o about the same degree The negative
breaks obtained in the case of sodium and lithium acetate indicate that these bases are probably less dissociated than their
respective chloride salts in thefe systems.

ANALYTICAL CHEMISTRY

410

Determinations of hydrochloric acid made with the previously

mentioned bases (except potassium acetate) are shown in Table
11. The slightly low results obtained were undoubtedly due to
the high volatility of hydrochloric acid in acetic acid.
Titration of several different molar ratios of mixtures of sulfuric acid and hydrochloric acid with lithium acetate are shown
in Figure 5. The initial rise in conductance was due to the formation of bisulfate. The first break corresponds to the stoichiometric end point of removal of one of the two hydrogens of
sulfuric acid. The subsequently greater rate of increase in
conductance upon further addition of base indicates that the
lithium chloride formed is somewhat more conducting (dissociated?) than lithium bisulfate. The second break in the conductance curve corresponds to the stoichiometric end point of
the neutralization of the hydrochloric acid in the system. The
decrease in conductance after the second break is explained in
the same manner as before, the results of marked tendency for
ion-pair formation between the sulfate ion and the lithium ions
The amounts of hydrochloric acid and sulfuric acid found,
calculated on this basis, agree reasonably n i t h the amounts
added as shown in Table 111.

Table 11. Conductometric Determination of Hydrochloric Acid in Acetic Acid

Titrant
NaAc

~IillimolesAdded"
1.19

Millimoles Found
1.11
1 19
1.12
1 19
1 20
LiAc
1,lQ
1.10
(CaH1i)sNHAc
1.19
1.19
1.16
1.16
a Because of the high volatility of hydrogen chloride in acetic acid, it was
difficult to maintain accurate concentration of the gas in solution.

Table 111. Conductometric Estimation of Mixtures of

Hydrochloric and Sulfuric Acids in Acetic Acid with
Lithium Acetate
Sample
1

Millimoles of
Acid Added
0.559
0.589
1.16
0.589
0.559
1.18

Acids
Added
HC1

HCl
HzSO4
HCl
HzSOd

Millimoles of
Acid Found
1st H
2nd H
0.594
0.580
0:526
1.16
0.540
0:560
0.626
...
1.12
1.20

GEKERAL DISCUSSIOS

These conductometric results are indicative of the vast difference between acid-base behavior in water and in nonaqueous
solvents, especially of low dielectric constant. From purely
theoretical considerations, titrimetric differentiation in water of
sulfuric acid, bisulfate, and hydrochloric acid is impossible either
potentiometrically or conductometrically, all three acids being
effectively of the same strength. Yet, as is evident from the
present study, relatively sharp end points can be detected for
mixtures of these acids in acetic acid.

It

conductometric plots it was tacitly assumed that the conducting

species were essentially simple ions, it must be recognized that,
especially a t higher concentrations, complex ionic agglomerates
play important roles in the over-all process of electrical conductc
ance ( 2 ) . Because of the complexity of these particular systems, hoi? ever, their full and complete analysis is unfeasible.
The simplified picture presented earlier appears to be sufficiently
valid to provide a working hypothesis for analytical studies in
these areas.
EXPERIMENTAL

Apparatus. B cylindrical jacketed borosilicate glass vessel,

5 em. in diameter and 12 cm. deep, was used as the conductance
cell. A fitted rubber plug was provided with holes for the electrodes, stirrer, and buret tip. The electrodes were brightly
polished platinum plates with a cross-sectional area of 2.25 sq.
em. Distance between the plates was less than 2 mm. The
cell constant n a s determined using 0.01M potassium chloride
and was found to be 0.06. I t was found necessary to thermostat
the conductance cell because of an appreciable temperature

12 0

61

3.75t-

E 2.75
g250

2
MOLES A L K A L I ACETATE/MOLES

nci

Figure 4. Conductometric titrations of 100 ml. of

0.0119M hydrochloric acid in acetic acid with 0.2001M
solutions of alkali acetates at 25' C.
3 Triamylanimonium acetate

+00

Potassium acetate
Sodium acetate
Lithium acetate

$225

"

200
175
1.80
1.25

IO0
I

It is of some interest t o note that potentiometric titrations of

these same acids in acetic acid actually give only little indications
of the reactions taking place, KO significant breaks are found
which can be correlated to the individual end points. This
behavior, as discussed before, is probably due to the fact that
the extent of the neutralization reaction is not dependent only
on the strength of the acid and the base, as in water, but also on
the relative dissociative tendency of the salt which is formed.
Although in the somewhat naive explanations of the observed

7
B
9
10
1
I
ML. LITHIUM ACETATE

12

1 3 1 4 1 5

16

17

Figure 5. Conductometric titrations of mixtures of

sulfuric and hydrochloric acids in acetic acid with
lithium acetate at 25" C.
Plots for titrations of mixtures of hydrochloric and sulfuric acids with
0 , 2 0 0 M lithium acetate are shown:
I. 1.16 millimoles of hydrochloric acid and 0.589 millimole of sulfuric
acid
11. 0.559 millimole of hydrochloric acid and 1.18 millimoles of sulfuric
acid
111. ,0.5B9 millimole of hydrochloric acid and 0.589 millimole of sulfuric acid

V O L U M E 27, NO. 3, M A R C H 1 9 5 5
coefficient of electrical conductance in acetic acid. FVater from
a constant temperature bath circulating through the cell jacket
permitted temperature control to Zt0.2" C. of the desired temperature. A Leeds & Northrup conductance bridge (catalog
No. 4866) was used to determine the conductance values. I n
order to increase the sensitivity of the bridge a t high resistances
a cathode ray oscilloscope (Type 304-H, Allen B. Dumont Laboratories) was connected in parallel with the null point galvanometer of the bridge. The null point of the bridge was determined from the resulting screen pattern of the oscilloscope.
Chemicals and Reagents. ANHYDROUS
ACETIC ACID. Reagent grade acetic acid was rendered anhydrous by refluxing over
boron acetate ( 4 ) for 4 hours and subsequently distilling the
anhydrous acid. The water content of acetic acid prepared by
this method vias less than 0.027, by the Karl Fischer method.
STASDARD
SULFURIC
ACID. A standard solution of sulfuric
acid in anhydrous acetic acid was prepared by diluting absolute
sulfuric acid (5)Tyith acetic acid. The molarity of the acid solution was determined by barium sulfate precipitation.
STAXDARD LITHIUM,SODIUM, 4 N D POT.-ISSIC.\r ACETATE. ACcurately weighed quantities of these reagent grade salts previously
dried overnight in a vacuum desiccator were dissolved in anhydrous acetic acid and diluted to volume.
STASD.4RD TRIAVYL OYICM ACET-ITE.Commercial triamylamine was purified by distilling several times under reduced
pressure, rejecting the first and last 20% of the distillates. Accurately Feighed quantities of the amine viere dissolved in anhydrous acetic acid and diluted to volume. The molarity of the
resulting solution &-as checked by titrating with standard perchloric acid in acetic acid, using quinaldine red as the indicator.
It was noted that acetic acid solutions of the triamylamine used
developed a deep red color upon standing for several days.
STASD-IRD HYDROCHLORIC
ACID. Anhydrous hydrochlorir
arid A as passed into cool anh>-drous acetic acid until fairly satu-

411
rated. The resulting solution was diluted with acetic acid and
the molarity was determined by silver chloride precipitation.
Frequent restandardization of this solution was found necessary
owing to the high volatility of hydrochloric acid in acetic acid.
Procedure. Accurately measured quantities of previously
standardized acids were pipetted into the conductance cell and
diluted to a volume of 100 ml. with anhydrous acetic acid. The
solution was stirred until it had attained the equilibrium temperature of the thermostated vessel. Small increments of
standardized base were added and the solution was stirred for
about 30 seconds. The conductance reading was taken nrhen it
became constant after stirring had stopped.
ACKNOWLEDGMENT

This study was supported in part by the research committee

of the Graduate School from funds supplied by the Wisconsin
Alumni Research Foundation.
REFERENCES

Eichelberger, W.C.. and La Mer, V. K., J . Am. Chem.

Soc., 55,

3633 (1933).

Fuoss, R. II.,and Kraus. C., Ibid., 55, 476, 1019, 2387 (1933).
Hall, N. F., and Spengeman, TV. F., Trans. Wisconsin Acad. Sci.,
30, 51-6 (1937).
Kolthoff, I. XI., and Willman, A , , J . A m . Cheni. Soc.. 56, 1007
(1934).

Kunzler, J. E., ASAL.CHEM.,25,93-7 (1953).

R E C E I V EJune
D 9, 1954. Accepted November 18, 1954. Presented before
the Division of Analytical Chemistry at the 126th Meeting of t h e . ~ M E R I C A X
C H E M I C ASOCIETY,
L
h'ew York, September 1954.

Purification, Purity, and Freezing Points of Sixty-four American

Petroleum Institute Standard and Research Hydrocarbons
A N T O N 1. STREIFF, A U R A R. H U L M E , P H Y L L I S A. C O W I E , N E D C. K R O U S K O P , and FREDERICK D. R O S S l N l
Carnegie lnstitute of Technology, Pittsburgh, f a .

The purification and determination of freezing point

and purity are described for 64 hydrocarbons of the
American Petroleum Institute Standard and Research
series, including 11 paraffins, 3 alkyl cyclopropanes, 1
alkyl cyclopentane, 4 alkyl cyclohexanes, 24 monoolefins, 12 alkyl benzenes, 3 dicycloparaffins,3 dinuclear
aromatics, 1 cycloparaffin-aromatic, and 2 olefin-cycloparaffins. Values of freezing points and cryoscopic
constants are reported.

HE investigation reported is a continuation of the work of

producing highly purified hydrocarbons of the API Standard
and Research series ( 2 , 5-9). This paper describes the purification and determination of purity and freezing points of 61
hydrocarbons, which include 11 paraffins, 3 alkylcyclopropanes,
1 alkyl cyclopentane, 4 alkyl cyclohexanes, 24 mono-olefins,
12 alkyl benzenes, 3 dicycloparaffins, 3 dinuclear aromatics,
1 cycloparaffin-aromatic, and 2 olefin-cycloparaffin hydrocarbons. The final lots of material labeled -4PI Standard are sealed
in vacuum in glass ampoules and made available as -4PI Standard
samples of hydrocarbons, by the Carnegie Institute of Technology.
(Twenty-seven of the Standard hydrocarbons are also available
from the National Bureau of Standards, Washington 25, D.C.)
T h e material labeled B P I Research is made available in appropriate small lots through the American Petroleum Institute
Research Project 44 for loan to qualified investigators for the
measurement of needed physical, thermodynamic, and spectral
properties.
Table I gives the names of the 64 compounds, the laboratories
providing the starting material, details concerning the first and

succeeding distillations or other methods of purification, the character of the plot of the freezing point of the hydrocarbon part of
the distillate as a function of its volume, and the volumes of
the final lots of API Standard and Research material.
The procedures followed in the process of purification and
determination of purity were the same as those described in
previous papers (3,5-9). Details of the distillation apparatus
and operations also have been described ( 4 , IO).
Figures 1, 2, and 3 show graphically the results of some typical
distillations. Figures 1, 2, and 3 represent the cases where the
purest material is, respectively, largely in the forepart of the
distillation, in the middle of the distillation, and in the after
part of the distillation. I n each figure plots are given for refractive index, boiling point, freezing point, and purity, as a
function of the volume of the hydrocarbon part of the distillate.
As emphasized in the previous reports, the blending of fractions
of distillate for the preparation of material of the highest purity
can be done safely only on the basis of the freezing points.
Table I1 gives the following information for the compounds
measured: the kind of time-temperature curves, whether freezing
or melting, used to determine the freezing point; the freezing
point of the actual sample; the calculated value of the freezing
point for zero impurity; the value of the cryoscopic eonstant,
determined from the lowering of the freezing point on the addition
of a known amount of a suitable impurity ( 3 , 4 ) ;and the resulting
calculated amount of impurity in the -4PI Standard and Research
materials.
ACKNOWLEDGMENT

Grateful acknowledgment is made to the organizations mentioned in Table I for their contributions of starting materials.