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McBride
S.
CONTENTS
Page
I.
Introductory Part
612
1.
612
2.
612
3.
613
614
616
4.
II.
(6)
End-point corrections
Rate of addition of the permanganate
(c)
Volume
(d)
(a)
III.
e)
616
617
618
619
-
of the solution
624
624
628
Review
(b)
(e)
632
632
by
(d)
63
of possible errors
(a)
(c)
volatilization
633
633
633
634
636
Loss of oxygen
Incomplete reduction of the permanganate
(k) Impurities in the oxalate
(/)
637
(g)
639
639
639
640
(*)
2.
3
4.
62
641
641
611
Bulletin of the
612
I.
1.
Bureau
of
Standards
ivoi.s
INTRODUCTORY PART
OBJECT OF THE RESEARCH
The standardization
if
of potassium
own
labora-
oxalate as a standard.
2.
is
of the laboratory.
McBride]
(c)
613
neither
in standardization
cates
is
satisfactory.
1
Zs. anal.
Bulletin of the
614
Bureau
of
Standards
[Voi.8
Along with such striking advantages we find certain disadvantages, but none of these appear serious.
The more important are
as follows:
The
largest sample
action of light.
The
(6)
detection of small
sodium oxalate
in the
is
amounts
The
(c)
initial
compounds
by comparison of
other samples of known purity.
of allied organic
II.
III.
Among
II.)
by Schillow 4 and by
From measurements of
those
Skrabal. 5
the former
II.
III.
The second
II,a.
II,b.
of these
Mn(OH) 3 .2H 2 C 2
Mn(OH) 4 .2H 2 C a
neous)
Zs. anorg.
Chem., 42,
p. 1; 1904.
McBride)
However,
615
this
following statements:
"This scheme
is
is
mean
in
concentration
Under other
which can be
2Mn(OH) 3 +H 2 C 2
IV.
=2Mn(OH) 2 + 2 C0 2 +2H 2
These
last reactions,
"
cit.)
advances the
Incubation period:
(1)
(2)
HC
HC
2
(3)
(less
(4)
Mn""+H
Induction period:
(5)
rapidly)
C2
,,
(6)
End
period:
i(7)
(8)
"i;[(10)
HC
2
instantaneous)
(practically instantaneous)
experimental work,
it
any one
of the systems
6i6
Bulletin of the
II.
Bureau
of
Standards
[Voi.8
EXPERIMENTAL PART
1.
REAGENTS EMPLOYED
the conditions of
its use.
same manner
as the
main
solution.
titration.
About 40 grams
of solution
McBride]
by Mr.
J.
was a sample
B. Tuttle.
It
is
617
For the
Table IV, b, another sample of sodium oxalate, made by
the Mallinckrodt Chemical Works especially for our use, was
This material was shown by test to be as pure as
employed.
that prepared in our own laboratory.
indicated a total impurity of not over 0.05 per cent.
tests of
2.
Since in
article
all of
618
Bulletin of the
Bureau
of
Standards
[Voi.s
sodium oxalate
gram
is
in the
as follows: Dis-
warm
to 70 ,
and
permanent pink.
It was desirable to determine the effect of the variation of the
following conditions upon the result obtained, viz, temperature,
acidity, volume of solution, rate of addition of the permanganate,
access of air, presence of added manganous sulphate and in connection with these, the corrections necessary upon the apparent
end points. In order to accomplish such determination, the
factors were varied one at a time, noting the difference, if any,
produced upon the apparent value of the permanganate. The
results of the titrations are reported as the ratios of the oxalate
These values
used to the permanganate used multiplied by 10-2
are proportional to, and, indeed, numerically almost equal to, the
iron value of the permanganate.
Therefore, for purposes of discussion the values are treated as if they were the iron value of the
permanganate, expressed in grams of iron per gram of solution.
It should be noted that an increase in the iron value represents a
decrease in the permanganate consumed, and vice versa. A
variation of 0.0 1 cc in the amount of permanganate used in a
titration is approximately equivalent to a change of one unit in
the last expressed figure of the iron value.
.
McBride]
619
END-POINT CORRECTIONS
is
under the various conditions of titration, we examined experimentally the following points:
(a) Does the equivalent in oxidizing power of the permanganate
excess remain in the solution long enough to allow the necessary
cooling before the titration with thiosulphate?
(b) Does the thiosulphate titration give the total permanganate
excess used to produce the end point, or does it indicate only the
permanganate which remains in the solution as such ?
(c) Does the depth of the pink color at the end of the titration
show how great an excess of permanganate has been added in
order to produce that end point ?
Before applying the method of correction proposed by Bray, it
is
room temperature.
Therefore,
as
is
desirable, the
determined valueless.
with varying acidities (2-10 per cent by volume H 2 S04 ) and with
the addition of various amounts of manganous sulphate (up to 1 g
MnS0 4 .4H 2 0). These experiments showed that no appreciable
loss occurred within a period of one-half hour, if only a small
8
J.
620
Bulletin of the
Bureau
of
Standards
[Vol.
to
tri-
or tetra-valent
(Mn*" or Mn""). The lapse of 5 to 10 minutes necessary for cooling the solution to room temperature, is
thus shown to be without influence and it is evident that the procedure described determines not only the permanganate remaining
manganese
salts
McBride]
621
may
be as much as
(b)
The
manganous
condition, easily
0.1 cc.
upon the
been shown
The
result obtained. 7
influ-
The
amount
permanganate added
was first
This factor has an influence only at low temperatures
tested.
(below 40-50 ), as at any higher temperature the reduction proceeds rapidly from the very start. Tests made at 30 in 5 per
cent sulphuric-acid solution gave results as follows
influence of varying the
of
Amount
of
KMn04
added
before
Results
KMn0
obtained
(strength
cc
10 cc
40 cc
25 cc
of
4)
o.
005936
o.
005936
37
35
34
37
o.
005932
o.
005929
33
1909.
1903.
1909.
A. N. Friend:
'
J.
Chem.
622
Bulletin of the
Bureau
TABLE
of
Standards
[Voi.8
volume
Acidity,
Experiment No.
H S04
per cent
Time
Temperature
for titration
(minutes)
005945
118
120
45
27
46
56
119
80
125
120
129
120
121
0.
56
0.
005942
123
[
122
42
37
44
30
124
120
44
230
0.5
231
0.5
92
206
92
93
223
30
207
0.
005592
91
94
225
60
226
60
95
232
0.5
233
0.5
208
98
5600
90
209
0.
005589
88
227
30
00
229
830
5598
After the
initial
of addition of the
Dropwise with
stirring.
main portion
of the
I.
tion of the
tion.
McBride]
The
at the end
623
permanganate just
but the
make
the only variable was the rate of the addition of the permanganate
TABLE
II
End
Point
of
permanganate
Acidity,
Temperature
volume
Color blank
per cent
Iodine blank
H2SO4
30
Uncorrected
0.01
0.03
.25
.34
.03
.09
.15
.39
.05
.085
.08
.19
.04
.08
Iodine
corrected
005584
0.005586
37
71
87
005929
.005933
.005942
5894
12
005030
.005034
17
26
005923
0.
0.
005589
30
30
30
30
10
60
60
83
.51
5871
.06
.11
.005636
.08
.14
.05
.05
005037
.005929
005935
005642
005648
43
50
005649
.005649
.03
.05
45
.05
07
.005638
005646
.05
.06
.06
.07
005650
.06
.06
.05
.04
-2
.15
37
33
.
005642
38
49
51
.
005649
005651
96
42
.
73764
Color
corrected
40
44
46
005642
45
52
52
005647
.005652
.005651
33
61
54
13-
Bulletin of the
624
(C)
The volume
Bureau
of
Standards
[Voi.s
of the solution in
which the
titration
is
made might
affect the rate of the reaction and, therefore, possibly the result
Tests were
of the titration.
volume
initial
containing 5
made
of this point
made
in a series of titrations
by varying the
at 90
of sulphuric acid.
in solutions
The
results
were as follows
Initial
volume
250 cc
50 cc
Values obtained
o.
005139
0.
005139
36
500 cc
0.
005136
005133
0.
32
34
39
1000 cc
700 cc
0.
005127
29
37
By
is
initial
indicated
less
as follows
Initial
volume
50 cc
Values obtained
o.
005943
45
1000 cc
250 cc
o.
005942
o.
005945
42
ACIDITY
AND TEMPERATURE
The
two
effects of acidity
and
of
McBride]
625
obtained in some cases show duplicates as discordant as experiments carried out under somewhat different conditions; nevertheless, the tendency in the two directions is rather convincing that
these factors have a real influence
upon the
The
results obtained.
TABLE
III
of
permanganate
Acidity,
Temperature
volume per
cent
30
45
60
H SO*
Color blank
Iodine blank
Uncorrected
Color
corrected
005135
Iodine
corrected
0.04
0.06
.04
.05
33
33
39
.04
.05
27
32
34
.03
.035
27
31
31
10
.05
.10
18
25
32
10
.02
.09
21
24
.02
.03
005134
.005136
0.
005129
0.
0.
005137
33
.
005138
40
.03
.04
34
38
.03
.04
30
34
.03
.025
30
37
10
.01
.03
35
36
10
.03
.03
31
35
35
10
.02
.035
37
40
42
.02
.02
.005129
.005132
.005132
.03
.03
36
40
40
.035
.035
33
37
37
.04
.05
35
41
42
35
-
36
39
.04
.06
26
32
46
.05
.05
32
39
39
10
.05
.05
33
40
40
10
.03
.05
33
37
40
10
.02
.04
34
38
40
626
Bulletin of the
TABLE
Bureau
of
Standards
[Vol.8
III Continued
Continued
Value
permanganate
of
Acidity,
Temperature
volume per
cent
75
SO*
86
92"
Color blank
Iodine blank
H2SO4
Uncorrected
Color
corrected
Iodine
corrected
0.03
0.02
005144
0.005143
.03
.03
37
41
41
.04
.025
37
42
40
.03
.03
39
43
43
10
.05
.06
29
36
37
10
.06
.04
34
43
40
.05
.045
.02
.03
36
39
40
.04
.05
36
42
43
.03
.05
38
42
44
.04
.04
39
44
44
10
.03
.03
34
38
38
10
.03
.03
36
40
40
.04
.03
005146
.005144
.02
.03
40
43
43
.03
.035
38
42
43
.02
.02
37
40
40
10
.02
.02
38
41
41
10
.03
.045
35
39
.02
.03
.02
.03
46
48
49
.035
.04
39
43
44
.05
.05
32
39
39
.05
.06
30
37
39
.06
.06
31
39
39
10
.05
.05
32
38
38
10
.06
.06
30
38
38
0.
005141
.005138
C05142
005143
0.
005145
005146
005144
41
.
Q05148
McBrid*}
TABLE
627
IV
SERIES
1,
is
the average
of
Acidity,
at least
III
two determinations]
Temperature
2
30
per cent
per cent
10 per cent
005138
0.005133
45
39
35
38
60
38
42
40
0.
0.
005132
75
42
42
38
80
42
44
39
86
44
42
41
92
48
40
38
(b)
30
0.
005646
60
SERIES
0.
005646
50
80
0.
48
005649
48
50
85
51
92
50
44
50
95
53
52
'
46
first
is without
be apparent when considered in connection with the results of the tests given in Table
appreciable effect.
VIII.
The
significance will
Bulletin of the
628
Bureau
of
Standards
[Vol.8
TABLE V
Time
at
oi 5
per cent
by volume
sulphuric acid]
Value
: (a) Initial, (b) during
part of titration, (c) at end
Temperature
main
Color
blank
point
Uncorrected
(a)
(6)
(e)
90
90
90
90
30
30
90
30
30
Color
corrected
Iodine
corrected
0.05
0.06
.06
.06
31
39
39
.03
.07
29
33
38
.03
.065
30
34
39
.03
.09
25
?9
37
.04
.12
19
24
.03
.05
005126
.005130
0.
005130
0.
005137
0.
005139
30
30
permanganate
{
r
90
of
Iodine
35
.
005133
.08
24
32
.04
.085
22
27
32
.05
.06
25
31
33
.07
.09
25
34
35
.05
.05
25
30
30
.04
.05
29
34
34
.03
.03
29
34
34
.03
.03
31
35
35
..05
36
30
90
30
30
90
90
{I
(e)
the following
10
See
this
is
not known; Schroder has tested this point recently (Zs. offentliche Chem.,
McBride)
The
629
of special
form
=^7
tests
made
in this
manner
are
summarized
in
Tables
TABLE
VI
Temperature
0.
11
See
The carbon
p. 616.
005041
0.
005037
in
beaker
open to air, as in ordi-
Titration
nary procedure
0.
005040
40
38
39
42
40
41
42
43
40
42
47
41
41
51
44
VI was found
methane.
Bulletin of the
630
Bureau
TABLE
oj
Standards
[Vol. 8
VII
Temperature
0.
30
005591
60
90
The data
of Tables
by volume
sulphuric acid]
0.
Titration
open to
in
baaker
as in ordi-
air,
nary procedure
005592
0.
005591
91
93
92
94
99
97
94
99
97
94
5600
98
95
01
5632
large error
comes
over,
when
McBride]
is
63
not an impor-
tant factor in the oxalate titration, the effect of the rate of titra-
initial rate of
two at 30
was
the reaction,
tested.
upon the
but the
manganous
its effect
of
One
cc
Table VIII.
It appears from these data that unless the MnS0 4 be added before
the beginning of the titration it has little effect upon the result
obtained. However, if even a small amount is added before starting the reaction at 30 the value obtained is the same as is ordinarily
obtained at 90 without the addition of manganous salt. Addition
before titration at 90 has no influence.
in
Bulletin of the
632
Bureau
TABLE
but
last
two
Amount MnSC>4
lution
tests at 30
last
two
Standards
at 90
so-
all
started in 250 cc of
Time
added
of
[Vol.8
VIII
Added Manganous
Effect of
[All
of
Sulphate
5
per cent
by volume
addition
sulphuric acid]
Value of KMnO*
found
0.
005576
77
None.
77
79
[
cc
005582
81
20 cc
83
.
Ice
[After decolorization of 10 cc of
005578
77
KMnO<
005578
20 cc
80
.
005579
005578
1 cc
[just before
20 cc
end
81
point
78
I
i
None
005582
|l
1
III.
5H C
2
is
The
may
tend
McBride]
may
633
acid
by
sulphuric acid;
(d)
air;
)
by contact
of
liberation of
compounds
of
(h)
presence of
(a)
The
danger of
loss
from
its
is
solution
Bulletin of the
634
Bureau
of
Standards
[Vd. 8
of titration.
12
Schroeder has shown that in the presence of manganous sulphate oxalic acid solutions are oxidized by the air at an appreciable
speed. This author presents a large amount of experimental data,
from which he draws very decided conclusions. Those which are
of importance in the present discussion are as follows (numbered
13
as in original)
(3)
KMn0
By
13
Zs. offentliche
Chem.,
McBride]
635
(Tables
tion.
Slow
(c)
3, 4, 5, 10,
and
11.)
permanganate than
(d)
(1
to 5 g) tends to
less
acid.
It
ineffective, since
was very
Bulletin of the
636
Bureau
0}
Standards
Vol.
<?
permanganate values
of
permanganate standardization
iodine standardization
is
presented to
standardization
is
is
systematically studied.
when
titrations are
made
in a
is
in a
Therefore
it
air
indicate
is
is
oxidized.
Mn-
(or
The
reaction:
MnOJ + H C
2
=Mn'"
+H
+ C0
McBride]
637
in the presence of
free oxalic acid
the reaction
Mn(OH) .xH C
3
HC
Since the
KMn0
formed by
= Mn(OH) +xH C
3
by the
The
end
of a titration contain
(f)
LOSS OF OXYGEN
14
amounts
by the
5H C
(a)
(b)
of
MnS0 + 2KMn0 + 2 H
4
2Mn0 + 2H S0 = 2MnS0 + 2H
(d)
3MnS0 + 2KMn0 + 2H
= 5lvin0 + K S0 + 2 H S0
(c)
= 5Mn0 + K S0 + 2H
2
is
SC>4
evolved from
Zs. anorg.
1892.
16
when
J.
ScL,
[3]
Bulletin of the
638
Bureau
of
Standards
[Voi.8
Incubation
period'.
MnVII->Mnn +
II.
(1)
Induction period:
Mn
III.
this author's
End
VII
f->Mn n +MnIV
(2)
|->Mnn +
(3)
+Mnn ->Mn m or
period:
MnIV->Mnn +
(4)
HMn0
or
Mn0
Mn
3)
in the
nous condition.
McBride)
would account
noted in
all
639
of the experiments
addition of
influence
upon
is
if
loss of
corrected
(h)
The question
of purity of the
acid,
As
has been eliminated even beyond the accuracy of the tests for
purity of the oxalate, since only comparative values were employed.
(i)
13
Bulletin of the
640
Bureau
of
Standards
[Vol. 8
latter could
The
e. g.,
2.
As
is
17
McBride)
641
Although
it
obtained slightly more precise and also to insure the use of those
conditions under which the difficulty of proper operation
minimum.
operation
For
is
this
is a
purpose the following detailed method of
recommended
4.
642
Bulletin of the
Bureau
of
Standards
[Vols
that
order to check
its
value.
probably no more conclusive than those now at hand. The difficulty is that of end points, for in each case mentioned the uncertainty in the blank correction required for an end point is about of
the same order as that of the uncertainty in the oxalate values,
namely, 0.1 per cent (usually equivalent to 0.05 cc of N/10 KMnOJ
We therefore, at the present time, would assume no greater absolute accuracy for the values obtainable than one-tenth of 1 per cent.
Washington June
,
912