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MEASUREMENT OF
TRANSFERENCE NUMBERS
OF THE BISULFATE ION
IN AQUEOUS SULFURIC ACID
*****
Howard W. Gardner
MEASUREMENT OF
TRANSFERENCE NUMBERS
OF THE B I SULFATE ION
IN AQUEOUS SULFURIC ACID
by Howard W. Gardner
Lieutenant, United States Navy
MASTER OF SCIENCE
19
T-Jbrnry
V. s. Naval Postgraduate School Monterey, California
MEASUREMENT OP
TRANSFERENCE NUMBERS
OF THE B I SULFATE ION
IN AQUEOUS SULFURIC ACID
by
Howard W. Gardner
MASTER OF SCIENCE
from the
United States Naval Postgraduate School
ABSTRACT
The unusually high mobility of the hydrogen ion and the hydroxide ion
in water has been ascribed to a proton transfer chain mechanism. In re-
In an
effort to determine the nature of the mechanism in the transition from chain
707.
acid by weight.
The trans-
migration only and not a proton jump chain transfer; hence these values may
be considered as a confirmation of the existence of a chain mechanism in
S.
Naval
ii
TABLE OP CONTENTS
Section
1.
Title
Page
1
Introduction
Experimental Procedure
Experimental Results
2.
3.
4 15
4.
Conclusions
22
Bibliography
23
25
Appendix
Appendix II
30
iii
LIST OP ILLUSTRATIONS
Figure
1.
Page
3 5 8
2.
3.
Electrolysis circuit
Bisulfate ion transference numbers
4.
17
II-l
II-2
39
44
iv
1.
Introduction
The abnormally high conductance of the hydrogen ion in water has been
known for many years and has been explained by a type of Grot thus chain
mechanism
p.,
2,
7J
numbers of barium and strontium ions in sulfuric acid and found that almost none of the current was being carried by the cation; they proposed a
similar mechanism of chain conductance in sulfuric acid.
More recent work,
6,
17}
the hydrogen
ion conducts by the excess proton mechanism, and the hydroxide ion conducts
ion
conducts by an excess proton mechanism, and the HSOa" ion conducts by a defect proton mechanism.
The autoproto lysis of water is given by:
(1)
H2
H3 +
OH"
(2)
H S0 4 2
H S04 + 3
HS0 "'
4
[^3}
(3)
H 2 S0
HSO4"
a good approximation,
greater than 0.5, the ionic species present will be the hydroniura ion and
the bisulfate ion.
the HSO," ion through the sulfuric acid molecules and for the excess pro-
Transference
number measurements were made on the sulfuric acid itself in the concentration range from 30 to 85 mole percent lUSO/ in the hope that information
could be obtained for comparison of the two conductance mechanisms.
The physical properties of aqueous sulfuric acid show remarkable var-
There
Similarly there is a conductivity minimum at a mole fraction of sulThe viscosity- conductivity product
These
The
mit much more than confirmation of the existence of the chain conductance
'
'
'
1
i
'
"^
1
I j
R M*
:#
.
.
.
'-
.,
*
t
y
\ Jo
1 fi
\
1
ft U
1 lJ
Via
rrio'i
v .product
/
/
..
.,
\ "V
v,
/
A >.T
.
"^-^
Sw
/
\
at) 3)
O 3 3
i
:
/
1
\
:
'a
Vij SCO sit y
,
i
2
d r.
.
>2j^
*
\
o e
H
y
0,
y
h
1
\
,
|:S
\
n
W
y
.
^
0. C
\
0. 8
\ \
\
0, [2
H >
0, 4
JU
'
Mo le FinACt ion
I
s0 '
I :
Fv
i
rc
H
*
2.
Experimental procedure.
Furthermore,
for the purpose of this study, it is impossible to say with the cell potential measurements whether the conductance is by a chain mechanism or by
migration.
ing the liquid junction, probably as the result of an air leak in the joint
or stopcock.
was adopted.
Vent
Vent
Figure 2
Transference Cell
Acid
attack on the rubber stoppers was reduced by wrapping the stoppers with
commercial saran film.
The cell was mounted on a removable "Flexofrarae"
[9 J reported the formation of ozone and other oxidizing agents at the anode
and the formation of sulfur dioxide and free sulfur at the cathode.
Exper-
were unsuccessful; gas evolution and the liberation of free sulfur were re-
Production of ozone and hydrogen peroxide would not affect the reTherefore, it was
nored, and only the anode and center compartments were analyzed.
3.
The record-
the usual silver or copper coulometer since other errors in the procedure
would probably negate any increased accuracy gained by use of the more accurate coulometers.
In conducting the electrolysis,
bridge assembly was then put In place, and the liquid Junctions were filled.
The entire assembly was then placed in the water bath, where the cells were
2.
Upon com-
pletion of the electrolysis, the liquid seals were broken, the anode compartment was removed and weighed, and samples were taken from the anode
and center compartments and were titrated with sodium hydroxide.
The acid solutions were made by diluting
ic acid to the desired strength.
967.
507.
reagent grade
99.97..
Three samples of about five grams of acid each were taken from each
to the nearest tenth milligram in covered sample bottles and then quant-
0.8 M sodium hydroxide was added by pipette; then titration to the end point
0)
CO
a U
w
E
-C
o
X
H
CO
V
u 3
fcO
X O
y cr
o
<N
H
*-
>> -H
o
C
"3
CD
00
WW
a*
indicator.
The 0.8 M sodium hydroxide was standardized against potassium acid
phthalate by titration of 100 ml of the base from the pipettes used in the
acid titrations with an approximately 0.33 M solution of potassium acid
with the above analytical procedure since the hydrogen ion produced per
faraday is the same as that produced in liberation of free oxygen.
The
cation of the procedure of Treadwell and Hall QoJ which utilized hydrolysis
of the peroxysulfates was used.
titration,
potassium persulfate mixtures and found to be quite satisfactory, the results checking to about one part in 10,000 for total acid after hydrolysis
of the persulfate.
presence of the persulfate rendered the first end point indefinite but that
the second was sharp.
In the actual runs there never was a detectable
change in the end point after boiling; this indicates that peroxysulfate
(4)
3 H
2
"
2 e"
it is necessary that any side reactions either must not affect the analy-
That
HS0 4
=
a.
H S
2 2
2 e"
HSO4"
9
II
2 H2
H 2 S0 5
6 H CT 3
+
+ +
H3CV 6 e"
2
2 e'
=
=
O3
+
2
4 H2
H2
H 3 CT
From equations (7) and (8) it can be seen that the production of ozone
or hydrogen peroxide results in the formation of one mole of hydrogen ion
per faraday, which is the same result as that obtained from reaction (4).
These reactions therefore will not interfere with the analysis of data on
the assumption of equation (4).
(9)
H 2 S 2 <>8
H2
s =
H 2 so 4
H 2 S0 5 H2 2
(10) (11)
H 2 S0 5
+
=
H2
H2
H 2 S04
h o2
H2
The sum of these equations with the appropriate electrode reaction leads
to an equation equivalent to equation (4).
10
base used will be the same as if all the acid had existed as H2SO4 and the
method of Weissberger
[l8J
(12) v '
(n ).. v
11
'final
)
.. . (iO. x Tr initial
(An v n) R'migr.
.
where:
(n
(il ).
=
1
(Ani X
ex. rn.
(An
).
enter into the effective electrode reaction, and because of the requirement
for electroneutrality,
'
(An
H 2 S04
"
el.rn.
is equal to zero, H
and:
(13)
(n
H S0 4 ) final
2
(n
H 2 S0 4 )initlal
(AnH
S0 4 )mi r -
(14)
H S0 2
HS0
"
p'
(15)
H
3
0"'
II
p"'
The protons represented in these equations are removed from the anode com-
partment by chain transfer; the net effect in the compartment is the for-
mation of bisulfate ions and water molecules from sulfuric acid molecules
and hydronium ions.
In order to find the relation between actual physical
migration of bisulfate ion and the analytical data, material balances were
c =
II
charge transfer.
d =
HO
(16)
(4)
3 H
0''
e"
HSO, A
H SO
2
HO
4
2
electrode reaction
ion migration
+1
-
3/2
+ a
chain transfer
total
1
- d
-
+b
a
-
-b
-
+ d -3/2 + d
c -d
1-c-d
(3)
HO'
'
HSO
"
HO
H S0
2
(17)
An
q
cA H J>U
2
= 4
q j~(a + b)
>-
b]
qa
where:
a;
this is by definition
[l8J
(18)
hso 4 -
r^
\
J
.
equivalents NaOH
'
"l^SO^
[Vno 8 *c id sample
final
no . equiv. NaOH a
no
.
g.
sample
initial
...
sample wt.
(g) v&/
^n
ference number, as shown above, results only from the physical migration
of the bisulfate ion and not from the effective migration resulting from
14
3.
Experimental results.
i
not used because proper precautions had not been taken against moisture,
and it was made with a Hg,Hg 2 SO, cathode which did not function properly
small and the end point was over-run on addition of the 100 ml. of 0.3 M
NaOH.
One run was spoiled by the addition of the 0.8 M NaOH solution be-
fore the base had been standardized; the base was then found to be approx-
The
numbers were such that an error in analysis of one part in 15,000 would result in an error of about one percent in the transference number.
eral,
In gen-
the precision of the analyses was such that the accuracy of the analy-
mated that the error in the result from analytical errors may be as high as
about 20%, assuming that the combination of errors from the two analyses is
positions of two solutions which had been exposed to essentially the same
atmospheric conditions.
partment were in a similar environment at all times and since the acid
15
1 1
6-S
J
-*
go
r^-t
St
cr>
co
CO
CO 00 <t
CO
00 <t
o
co 00
00
1-4
CM
r-4
cm
t-t
r-4
0C+
O vO
00 <t
00
tf
r^
00
co
co
a:
o on o
r^
co
f-i
v>
vO rH
CM
r-t
r-l
o.
o CM
r-l
co -*
r-4
CO <r
r-4
ON
I
f-l
> c r-l 3 O
O*
(0
m O O O o
co
-ci-
o o o o
in
o oo o o
00
CO
r-l
vO ON
i-4
o o o
o o o o
m 00 o o o o
r*
CM
&0
o o o
i-t
o o o o
<Ji-
CO <*
r-l
r-l 1-1
o o o
o o o
r-l
u
c
4J
s-\
-iJ
c
1
i
00 CO CM 00
vO CO
o r^
CM <t
CO
CM
r>
on
00
vO
MT
l>
o r^
r-*
CO
vS
ov
r-.
m ON
o m
r^ o m *t
o o on
r
3
CO
f)
i-i
o
(0
Ci
r-4
Rj
60
*%,
H
r-l
>
H
XI *J
C h s
1-4
w
li (0 i-i
rl <u
3 V 41 o 5 "< a
VO
on CM 00
r-l
o ON o r^ o
T-l
CM CO
1-1
t-l
m
i-i r i-4
00 CM
r-l
CM
vO
r-4
CO vO
<t
r-4
CO
r*
r
o> ft
m m vD
<r
r-4
r*
I-*
ON
t-l
r-i
r-l
1-4
o 00 rH o
r-4
a
X
tl
> vO
CM
vO
^5
r*.
m o r^
CM UO
si-
<f
(-4
*
i-*
CO vO ON
in <t
m
<fr
ON ON 00
t*
-h
CO <J
tj-4
>-*
r-.
O V o a O r-t
O.
CN
r-4
r-l
O CM
CO
CO 00
o
CO
ON
CO vO
m m
m CO m
o o m
1-4
00
CO
00
V ^S M a r-l M c 3 c3 CO o
r>-
ON ON
r-4
vO
O
CO
r-l
t^
o ft
-xt
O 00
CM
m *
CM
r-l
ft
CO
o CO o CO
o m
r* CM
00 CO CM
rH
CO CM
CN
r-l
vO
CM
3
04
CO
<-i
CM
<!
vo
co
on
16
" "- 1 !
,
r-
^.^_ iiijs
OIKby
tir^
te
.
'
Q 1
z;
f - i,
?
'
:
Ll
<D M 2 c
a
1
o
|
T
I
.'
T*
r,
C .1
>
1
';.
>
'
1
n
()
0, 2
0. 4
0. 6
0.8
1.
Mo le
_
',
Frcjtct
ton
ff
^
i
".
F] gu< r^c 4
.
.
ti i
-rj
ilum hers
'
'
1
|
.
1
-
3
....
-
H
.
-H
1 ?
i
. i
f-j
The
error from this source should then be small in comparison with the other
errors.
For oxygen evolution this loss would amount to about 0.2 gram or
half gram will occur by physical removal with the electrode assembly.
loss will introduce another error of the order of one percent.
Thermal diffusion errors may have existed but were probably negligible
in comparison with the other errors.
Free sulfur
formed in the catholyte and its diffusion through the liquid bridge could be
observed.
In no case was the free sulfur observed to move over one third of
with the operation of the thermostat on the water bath; the difference in
current caused by this effect was approximately one milliampere.
This var-
aged based on the high value then adjusted downward to correct for the lower
average value.
257..
dicated in Fig.
4.
Accord-
(17)
^j
X]
constant
ionic conductance of species
J
where:
=
=
7?
(18)
?o
X so H
fA* T^-~
"
where:
jc^=
X H j =
[15]
(?
y
j\
25
TjjgQ,- =
Ar
c^_
1000
= =
Concentrations of the ionic species present were determined from the Raman
spectra studies of Young and others [19, 20J.
The results of the appliIt
2.
is apparent that in
most cases the approximation from the experimental measurements is about half that predicted from the limiting ionic conductance.
However, the fact
that the values are of the same approximate magnitude indicates that the
20
Table
Comparison of
70J(
products
HSO
2
1000
4
c
f
[12]
T
4
At ^
.14 .14
.27
0.31
0.31
0.48
11.5
235 235
123 123 123 123
128
.096
11.5
12.3
.096
.195
.27
.14 .13
.11
.27
0.48
0.48
.195 .195
.195
0.48
0.57
.10 .12
.190
.183
0.61
0.82
9.6 4.1
3.8
131 110
.09
.12
.07
.30 .60
.37
.186
.191
0.84
104
^ AHS04
c+
0.47
21
4.
Conclusions.
transference number,
by migration,
impossible to distinguish by this method of measurement which chain mechanism may in fact be carrying the current.
it
The
mechanisms of chain conductance and physical migration may thus be considered competing mechanisms for ion which may conduct by either a proton
is presented in Appendix
22
'
BIBLIOGRAPHY
1.
D. Bernal and R. H. Fowler, "A Theory of Water and Ionic Solution with Particular Reference to Hydrogen and Hydroxyl Ions", J_^ Chem.
J.
Phys.
2.
1,
515 (1933).
M.
Eigen and L. de Maeyer, "Hydrogen Bond Structure, Proton Hydration and Proton Transfer in Aqueous Solution", The Structure of Electrolytic Solutions (V. J. Hamer, Ed.), pp. 65-88, John Wiley and Sons, Inc., New York (1959).
R.
3.
J. Gillespie and S. Wasif, "Solutions in Sulfuric Acid. Part IX. The Electrical Conductivity of the Water- Sulphur Trioxide System in the Region of the Composition of Sulphuric Acid, 1953 , J. Chem. Soc. 209-215, (1953).
;
5.
R. J. Gillespie and S. Wasif, Part XI. 'Solutions in Sulphuric Acid. Densities and Viscosities of Some Sulphuric Acid Solutions", J^ Chem. Soc 215-221 (1953).
,
6.
R. J. Gillespie and S. Wasif, "Solutions in Sulphuric Acid. Part XII. Electrical Conductivity Measurements", J^ Chem. Soc, 1953 , 221-231
(1953).
7.
S. Glasstone, K. J. Laidler, and H. Eyring, The Theory of Rate Processes Chapter X, pp. 552-575, McGraw-Hill Book Company, New York
,
(1941).
8.
J. Hamer, "Temperature Variation in Transference Numbers of Concentrated Sulfuric Acid as Determined by the Galvanic Cell Method' J. Am. Chem. Soc 57, 662-667 (1935). W.
,
9.
L.
P. Hammett and F. A. Lowenheim, "Electrolytic Conductance by Proton Jumps; The transference Number of Barium Bisulfate in the Solvent Sulfuric Acid", J. Am. Chem. Soc , 56, 2620-2625 (1934).
S. Karned and B. B. Owen, The Physical Chemistry of Electrolytic Solutions 3rd Ed., Reinhold Publishing Corporation, New York (1958).
,
10.
H.
11.
E. Kunzler and W. F. Giauque, "The Change in Electrical Conductivity of Aqueous Sulfuric Acid Near Absolute H 2 S0^ and H2SO^.H 2 0", J. Am. Chem. Soc , 74, 804-6 (1952).
J.
12. Landolt-Bornstein,
,
Zahlenwerte und Funktionen aus Physik Chemie Astronomie Geophysik Technik Vol. IV, Part 1, Springer-Verlag, Berlin (1955).
, ,
,
13.
W. M.
Latimer and J. H. Hildebrand, Reference Book of Inorganic Chemistry (revised Ed.), The Macmillan Company, New York (1940).
W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry (revised Ed.), The Macmillan Company, New York (1940).
14.
J.
23
15.
B.
B. Owen and R. W. Gurry, "The Electrolytic Conductivity of Zinc Sulfate and Copper Sulfate in water at 25", J^ Am^ Chem. Soc. 60 3074 (1938).
,
16.
F.
P.
Treadwell and W.
Vol.
II,
Ed.,
17.
pp.
T. Hall, Analytical Chemistry Ninth English 522-3, John Wiley and Sons, Inc., New York (1945).
,
S. Wasif, "Properties of Sulfuric Acid Solutions. Part I. Transport Number Measurements in Sulfuric Acid and Oleum Solutions", J_^ Chem.
Soc
18.
1955
372,
(1955).
, ,
A. Weissberger
(editor), Techniques of Organic Chemistry Vol I. Physical Methods of Organic Chemistry Part IV, Chapter 46, pp. 3049-3111, Interscience Publishers, Inc. New York (1960).
,
19.
F. Young, L. F. Maranville, and H. M. Smith, "Raman Spectral Investigations of Ionic Equilibria in Solutions of Strong Electrolytes", The Structure of Electrolytic Solutions (W. J. Hamer, Ed.), PP. 48-63, John Wiley and Sons, Inc., New York (1959). T.
,
20.
T.
F. Young and G. E. Walrafen, "Raman Spectra of Concentrated Aqueous Solutions of Sulphuric Acid", Trans Faraday Soc. 57, 34-39 (1961).
. ,
24
APPENDIX
[18J
and were plotted and smoothed with the values for the
dilute solutions.
furic acid solutions a "relative abundance" was used (Appendix II); this
is defined by:
c
(I-D
Z
k
= =
where:
Y.
c.
i
and subscripts
and k indicate any of the molecular or ionic species present in the sol-
ution.
25
cj 0)
oCM
Os
OS
en
m
so"
CM
m
en
sO
CM
CO
r-t
CO
iI
00
vl-
en
o CO
CO CM
H 8
i-i
<r
to CM
O
0)
m
* t-t
sO CO
CO
o o
CO
r-\ cj
f CO
in
<t CM
CO
cn
en
OS
<*
r
o
so
CO
sO
CO
cn
cn
CO
DC
m CM
tS)
u
CO
co
^
co
h iH
o CO
X
m m
CM
1 1 1 1
sO
1
1
1 1
1
1
1
** .o
c4
O o H CJ M o
4)
I I
Os
00
r-
<t
in OS
CM
6*
CO
6*
CO
h
r-t
*
co
Os
sO*
00
m o
OS
-
rH
o
CO
r^
<t
00 OS
sO
sO*
en
r4
A U
H
St
4J <X
O CM
CO
OS r*
OS
<r
CM
i-< r-
>ct
m
St CO
m m
<t
CO
OS CO
3 o co
<*
r>
*
St
St <*
Os
<t
CM
in f*
r-l
00 Os CM
r-l
CO OS
sO Os
Os oo
CO r^
sO
CM
CO CM
o CM
m
r-l
O
r-l
JC
H
4J
o O
O CO
<t
CM
CO EC
o o o o o
00
r-l
m
r-*
i-i
vO
CM
Os st
o Os
sO
CM
CO SO
00
St
f-4
so
st
r-
l-l
r-4
sO
CM
m
CO
5
<*
s*
CM
sO
00
co CO
CO CO sO
CM CM
m
o m
m
in lO
sO
r^
J3
*-S
OJ -
O O
r-l
<t O CO
CM
o
r-4
m
r-t
o CM
26
m CM
co
m CO
aj
in <t
sO
"V
o
r
"4
9 u V
r-4
O CM
:.
H
id
9 O V
O CO
CM
<r
vO
r^
rH
CM
CO
o m
r^
vO
vO
CO
3
I
m sm
o>
4-
~\
CJ
o en w
<o <r
CO
co
CO rH
r>.
CM
o CO
CO
m CM
(S;
uX
m m
CO
cj
M
t>
-J-
m m o CO m re
o
2 o M H
CO
4J
i-l
co
*^
rH
CO
CO
<~i
CO
'
rH
rH
V X w
O
I
rC
co
opa
I
1
I
o o
2 O
CJ S3
c
iH
i
K
i
CM
to CM
01
CJ
M 4J d V
<*
cj CM
w
rfl
s
x o
n
o
H
O 4J a
u H
(A
c_>
cj
1
cj*
CO
r-t
I I
<fr
CO
CM
CO cj
oCM oCO o
8CM
S3
O
4)
3
r
iH
c o
oCM
vO CO
o
o
CM rH CM
CM CO
CO
o o
cj*
cj
CJ
09 EC
<t
CO
CM
U3
co 4J CM CO EC
O o
<*
U">
\0 00
CO
o
00
o CO
ii
NO
r^
r^
CO
CO
CO
.fl
-?
4) "-<
H
4J
O O
to
2 K
O to
st
m
r
o CO
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27
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28
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29
(II-l)
Yi
k
where:
Y. 1
i i.
and subscript
ic species,
For
bisulfate ions,
H,SO
'"
[_20j
I.
Y* "
+
3
4-
v* "
V
H o S0,
HSO.
Y* H S0
5
5
+ -
Y 1^0
Y*
SO.
--
Y
HSO, 4
Y
H SO,
2
Eigen and
deMaeyer
f_2 J
of the hydronium ion as evidence for a short lifetime of the hydronium ion
in dilute water solutions.
that is,
(ii-*)
Xj.
Aj
A
'
*j
=
f'O-Y^
ionic conductance by migration only.
where:
i^f
ex-
cept in the case of the hydroxide ion and the hydronium ion where the chain
assumed that the conductivity due to the chain mechanism is some function of the total concentration; it was found empirically that the best approximation with the other assumptions was that the conductivity by the chain
32
(II-3)
Yj
cK "
1?
(% c"7V/3
where:
^' &ha,n
proportionality constant.
(H-4)
-'
Vj cKoln
\j
/i<?
r.
or
obviously could not be used since they include both effects of chain conductance and migration.
No information was available for the H_ SOion.
The values used for the computations with this model were:
ion
A
"
HSO
4
4
50
p2,
rioj
15)
h so
"
80
80 40
H
3
H,
(assumed)
(assumed)
.so/
33
These val-
ues were then subtracted from the known experimental values of the viscos-
ity-conductivity product.
compared to the values for
^_ Y.Y*.
furic acid,
The values of k
were then averaged and the average value of k was used to calculate an esti-
mated curve.
mated by the model are plotted together with the experimental values for
V-
'j
XjO-Y/")
=? Ye*r
(II-6)
T<j
fj
rr\>qr.
where
f"<<^r
Test
For chain conductance:
(II-7)
chair\
=
where
Ij
chain
is shown in Fig.
II-2;
these
the general concept of competing mechanisms is believed to be sound The most serious apparent
discrepancy in the fit of the model to the observed values is in the concentration range more dilute than the monohydrate.
The difference between
the form of the experimental curve and the curve derived from the model
used.
over the concentration range the variation of the total number of charge carriers in a given volume is not significant.
Then the proportionality to
It is thus possible
conductivity data for sulfuric acid alone; by a trial and error adjustment
of a number of variables it should be possible to achieve a good fit to the
35
known conductivity data without any assurance that the model represents
the actual process.
36
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