Académique Documents
Professionnel Documents
Culture Documents
By Lorrayne LeMar
LIBRARY
RESEARCH AND DEVELOPMENT LABORATORIES
PORTLAND CEMENT ASSOCIATION
********
June, 1947
TABLE OF CONTEMS 1
Page
ABSTRA.CT •••••••••••••••••••••••••••••• " • ., •.••••••". f ,"• • • • • • • • ' . 1
LABORATORY PROCEDUBES:
1. Standardization of the Oxidimetric Solutions ••••••••••• ,••••• 2
2. Determination of the Ferric Oxide Content of Portland Cement. 3
DISCUSSION:
1. Standardization of the Potassium Dichromate Solution••••••••• 3
(a) With Ferrous Ammonium Sulfate ••••••••••••••••••••••••• 3
(b) With Iron Ore '...••..••• ' . 4
(c) Wi th Iron Wire ••••.••..••.••.••·••.•..••••• i •••••••• 6
(d) Sl1IIIl'l1ary of Beaul ts .••.••.••.•••.•...•. 'f • • • • • • • • • ' , • • • • •
7
(e) Methods of Determining the Endpoints of the Titrations. 8
2. Standardiza.tion of the Ceric Sulfate Solution . 9
(a) With Ferrous Ammonium Sulfate •••••••••••.•••••••••••• 9
(b) With Iron Ore , ••••..•••••••• 9
(9) With Iron Wire ••••••••••••••.••••.•••••••••••••• ·... It • • •
9
(d) With Sodium Oxalate .••..•••••••••••.•••••••••••.•• '• •• 10
(1) Potentiometric Method Using Iodine Monochloride. 10
(2) Indicator Method Using Ferrous Ammonium Sulfate-. 10
(e) Summa.ry of Beaults •.•.•••.••••..•.•.••.• , .••.•..•.••• 11
(f) Methods of Determining the Endpoints of the Titrations 11
3. Determination of the Ferric Oxide Content of Portland Cement. 12
(a) With Potassium Dichromate .••••.•••••••••••••••.•••••• 12
(b) With Ceric Sulfate •••.••••••••••••••••••••••••••••••• 14
4. Comparison of the Two Oxidimetric Solutions •.••••••• ~ •••.••• 14
(a ) Preparation " to • • • • 14
(b) .Stabili ty . 14
(c) Use with Hydrochloric Acid ••.••••••••••••••••••.••••• 15
(d) Standardization . 15
(e ) Indicators 0............."..... _ ....... ... 16
( f ) SlllDlD.ary ....................................."................ 17
5. Results in Tables 1 to 6 ......•... '. .•................•...•.. 18
SUMMARY: Advantages and Disadvantages of:
1'. Ceric 'Sulfate •••••••••••••••••.••••••••.•••••••••••••••••••• 20-21
2. Potassium DichrolJUlte it
21 .
REAGENTS:
1. Standard Oxidimetric Solutions ••.•.•••••••••.•••••••••••••••• 1
(a) Potassium Dichromate ••••..•••••.••...•••••.•••••••••••• 1
(b) Cerie Sulfate , II' • 'I' •••••••••••••• 1
2 • Primary Stan.dards -. . . . . . . . . . . . . ". . . . . II 1
(a) Sodium Oxa.late ., . 1
(b) Potassium Dichromate .... ........ .- . 1
( c) Iron Wire ' ~ , 1
(d) Iron Ore ,', '. 1
(e) Ferrous Ammonium Sulfate Solution •••.••..••.••••••••••• 2
;. Indicators ,' .. I •••••••••••••••••• 2
(a) Ferroin ~ II • " ••••••• 2
(b) Diphenylamine Barium Sulfonate ••..•.•..••••..•••••••.•. 2
(c) N-methyldiphenylamine Barium Sulfonate .•••.•••••.•••••• 2
4. MiscellaneouB Reagents '" ' ,. , . 3
(.a) Normal Sulfuric Acid It .
3
(b) Normal Hydrochlorio Acid .•••••.•..•••••.••••......••..• 3
(c) Phosphoric Acid Solution ••••••••.••..•..•••.•••..•..••• 3
(d) Stannous Chloride Solution ••••.•.•.•••..••••.•••..•.... 4
(e) Iodine Monochloride Solution ••••.•.•••••••••••.•..•..•• 4
APPARATUS:
1. Potentiometer ". It . 4
2.. Electrodes " " It . 4
3. Silver Reductor e II ••••
5
METHODS:
1. Standardization of the Ferrous Ammonium Sulfate Solution 5
2. Standardization of the Potassium Dichromate Solution •••••••• 6
(a) With Ferrous Ammonium Sulfate •••••••.••••.•••••••••••• 6
(b) With Iron Ore ., I • • • • • • • • • • 7
(0) With Iron Wire "e.• ,-. e" e.... It , lit 8
3. Standardization of the Ceric Sulfate Solution ••••••••••••••• 9
(a) Wi~h Ferrous Ammonium Sulfate •••••••••••••••••••••.••• 9
(b) With Iron Ore eo.......... 10
(e) With Iron Wire It • • '.......... •••••••••••••••••••••• 10
(d) With Sodium Oxalate Plus Iodine Monochloride •••••••••• 10
(e) With Sodium Oxalate Plus Ferrous Ammonium S.ulfate ••••• 10
4. Determination of the Ferric Oxide Content of Portland Cement. 11
(a) Titration of Cements with Potassium Dichromate ••••••• , 11
(b) Titration of Cements with Ceric Sulfa~e •••••••••••• ~.. 12
Research laboratories of the
Portland Cement Association
33 West Grand Ave., Chicago
By Lorrayne LeMar*
-000-
ABSTRACT
Determinations were made on the ferric oxide content of port-
land cements with potassium dichromate and the indicators diphenylamine
barium sulfonate and N-methyldiphenylamine barium sulfonate as com-
pared with similar determinations made with ceric sulfate.and the
indicator ferroin. Results obtained with the indicators were checked
against potentiometric titrations • A s ilver reductor and the stannous
chloride method were used for reduc ing the iron. Also various primary
standards for determining the Fe20 s factor of the OXidizing solution
were compared. .
It was c9ncluded that aolution of potaseium dichromate is the
most suitable oxidizing agent for routine analYsis of the Fe20s con-
tent of portland cement because of' its stability, low equivalent
weight and low cost of' the salt, and ease of preparation of the
solution. Moreover, it can be used in a hydrochloric acid medium
without adverse side reactions.
. .
Iron wire was found to be the most suitable primary standard
for determining the Fe2 0 s factor of the oxidizing solution. Iron ore,
because of its slow solubility, its lack of homogeneity, and the
difficulty in handling the weighed sample of ore quantitatively, was
found to be less desirable than iron wire as a primary standard for
routine analyses.
A more reliable factor for the standard solution was obtained
by averaging the results of four or five determinations of the factor
(against 0.030 to 0.035g. Fe) than by using various factors determined
by One or two titrations whose volume approximated the volume required
by the cement. The reason is that individ\1al determinations of the
factor of the standard solution may vary considerably even thOUgh
titrated against the same weight of Fe, and theref'ore, single or even
duplicate determinations of the factor may not be accurate.
Certain changes are recommend,ed in the current A.S.T.M.
procedure (C 114-46) for determining the ferric oxide content of
portland cement.
* Associate Chemist, Research Laboratories, Portland Cement Assn., Chicago.
INTRODUCTION
IA:BORATORY PROCEDURES
1. Standardization of the Oxid1metric Solutions. In this
investigation two oxidtmetric solutions, potassium dichromate and
eerie sUlfate were used for determining the ferric oxide content of
portland cement. Potassium permanganate was not included in the study
inasmuch as it is a well-established fact that permangenate no~ly
gives high values in iron determinations tl ).
*2*
iron wire was reduced by passing the solution through a silver reductor
column. The endpoint of the ceric sulfate titrations wa.s determined
with the indicator ferroin and electrometrically with the potentiometer.
The reagents, apparatus, and details of the preparation and"standardiza-
tion of the oxidimetric solutions used in the investigation are des-
cribed in the appendix of this report.
2. Determination of the Ferric Oxide Content of.Portland
C·ement.. The standard solutions of potassium dichromate and ceric
sulfate were used for determining the ferric oxide content of eight
cements ,ranging from 0.4% to 5.4% Fe2 0 3 • The same afore"mentioned
indicators and the potentiometer were used for determining the endpoint
of the titrations. In the potentiometric titration, the cements were
reduced with stannous chloride and by passing the solution through a
silver reductor. In the indicator method the cements were reduced by
the stannous chloride procedure only. Details of the procedures
followed are given in the appendix of this report.
DISCUSSION
1. Standardization of the Potassium Dichromate Solution.
(Results reported in Table 2). A change of primary standard for
determining the Fe2 0 3 factor for the dichromate solution is being
contemplated by Committee C-l of the A.S.T.M. For this reason, the
results obtained using the various primary standards are of particular
interest. The following three primary standards for the dichromate
solution were studied:
(a) Ferrous annnonium sulfate (MOhr's salt) which
is frequently employed in research work in this
country and as a comon primary standard in
Europe (particularly in Germany) for the
standardization of oxidimetric solutions;
(b) Sibley iron ore, standard sample No. 270 of the
National Bureau of Standards, which is the new
standard proposed by Committee C-l of the
A.S.T.M., and
(c) Iron wire which is the present standard specified
by the A.S.T .M.
. (a) Standardization.of Potassium Dichromate with Ferrous
Ammonium Sulfate. Mohr's salt is subject to variations in percent
of Fe due to changes in water content and to oxidation of the salt by
the air. ConsequentlY, a solution of the salt was prepared with a high
percentage of sulfuric acid and stored in a tightly stoppered brown
bottle to mitigate OXidation of the ferrous iron. Details of the pre-
paration and standardization of the ferrous ammonium sulfate solution
are given in the appendix; results are reported in Table 1.
* 3*
Very sharp, clear-cut titrations were obtained with
either of the indicators. The diphenylamine barium. sulfonate changed
to a brilliant purple color and the N-methyldiphenylamine barium. su!..
fonate gave a rose-red color at the endpoint. The unusual brilliance
of the indicator color changes was a,ttribu..ted to the fact that no pre-
cipitate was present in this titration*.
Results using the potentiometer were also satisfactory
and checked the ~esults obtained by t~e indicator method. Here again
the absence of a precipitate in the solution was an advantage in that
practically no "poisoning" of the platinum. electrodes was noted.
However, the ferrous ammonium. sulfate solution was found
to have one decided disadvantage which limits its value as a practical
primary standard. Repeated standardization of the solution showed that
the ferrous salt was oxidized during storage in spite of the afore-
mentioned precautions taken to prevent such oxidation. The follOWing
data give the magnitude of the deterioration of the solution: The
initial normality found (potentiometrically) for the ferrous ammonium
sulfate solution was 0.05047. Two months later when the solution was
again standardized by the same procedure, the average normality was
found to be 0.04605. However, this deterioration of the solution in
no way affected the results reported in Tables 2 and 3 inasmuch as
little time elapsed between the initial standardization of the solution
and final use of it as a primary standard**.
(b) Standardization of Potassium. Dichromate with Iron Ore.
The potassium dichromate solution was also standardized against the
National Bureau of Standards' Sibley iron ore, No. 27b. The details
of the procedure are given in the appendix of this report.
Several difficulties were encountered in using iron ore
as a primary standard. When the sample was weighed in an ordinary
aluminum weighing pan,it was found to be extremely difficult to com-
pletely transfer the sample ·of ore to a beaker. Even after prolonged
brushing of the sample from the pan, some of the ore remained as evidenced
by the discoloration of a white towel used to Wipe the pan. For this
reason a glass weighing dish counterpoised by a similar glass dish was
used for weighing the samples of iron ore. Even using the glass dish,
great care had to be exercised in brushing the sample into the beaker to
prevent the ore from clinging to the edge of the weighing dish. The
following data illustrate that small differences in weight of the primary
standard or of the volume of the solution used to titrate the standard
greatly affect the numerical value for the Fe::ps factor of the solution:
*4 *
Primary Standard Vol. of Oxidizing Calculated
as g. Fe Solution Fe20s Factor
0.0100 ;.62 0.003962
0.0100 ;.57 0.004017
0.0393 13·90 0.004037
0.0392 13.90 0.004027
0.0400 14.15 0.004040
0.0400 14.10 0.004054
For this reason, two alterations in the current A.S.T.M. method (C 114-46)
of reducing the iron with stannous chloride were made. First, a 5~
instead of a lCf/o solution of stannous chloride was used, thus limiting
the amount of excess stannous chloride that would be added to the iron
solution. Second, the amount of saturated solution of mercuric chloride
added was changed from 10 to 5 ml. The mercuric chloride was added
after cooling the solution" of the sample and before diluting the sample
to the reqUired volume. Under these conditions,· the results obtained
after the stannous chloride reduction compared very favorably with those
obtained with the silver reductor. (Table 2). This eliminates the
necessity of setting up and maintaining a silver reductor column which
is less convenient to use than the stannous chloride method of reduction.
(d) Summary of Resu!ts • Iron wire proved to be the most
practical primary standard for the dichromate solution. One reason why
results with the iron wire were less erratic than those" obtained with
the ore may be the fact that the dissolved wire is largely in the ferrous
state whereas the ore is largely in the ferric state as indicated by
the following equations:
Iron wire: Fe + 2HCl --'liio- FeCl2 + H:2
Iron ore: .o3 + 6XCJ
Fee ->£- ~eCls + ;H20
*7*
However, the ready and complete sol.ubility of the wire
is its outstanding advantage since the most common cause of poor re-
sults with the ore was believed to be the failure to get the ore com-
pletely into solution. The use of stannous chloride to aid the solution
of the ore alleviated one trouble only to cause others of more serious
consequences.
The objection to ferrous ammonium sulfate as a practical
pril)18.ry standard is its instability. .
One other point, not preViously discussed but indicated
by the tables, is that with any of the three pril)18.ry standards the size
of the sample taken had an effect on the calculated FeaOs factor of the
dichrol)18.te solution. This was evident regardless of how the titration
was conducted. The smaller the weight or volume of the primary standard,
the lower the value for the FeaOs factor. However, with weights of
0.04 to 0.05 g. Fe, the factors became nearly constant. It will be
shown later that the difference in factor made no significant difference
in the values for the percent of FeaOs in the cements whether the
highest, lowest or average factor was used in the calculations.
(e) Methods of Determinipg the Endpoints of the Titrations.
It has been mentioned that the endpoints of the previously discussed
titrations were determined by three agents: .
(1) A Beckman Model G potentiometer,
(2) Diphenylamine barium SUlfonate,
(3) N-methyldiphenylamine barium sulfonate.
* 10 *
(e) SHDJ1I!B!l of Results. The most satisfactory method of
standardizing the eerie sulfate solution was with sodium oXalate. The
potentiometric method using iodii'le monochloride as catalyst was more
satisfactory than the indicator method. With sodium oxalate the size
of the sample had no effect on the factor of the solution. With iron ore,
iron wire or the ferrous ammonium sulfate solution, the size of the sample
had a demonstrable effect on the calculated factor of th~ solution.
In comparing the results of these various methods of
standardizing the eerie sulfate solution, the following significant
observation was made. Good agreement between average values obtained
with the various primary standards and between the indicator and po·
tentiometric methods were obtained when these determinations were made
during the same day or week (Tabie 3). However, the results clearly
indicate that the eerie sulfate solution deteriorated on standing.
This point is illustrated by the following data which show the average
factor obtained for the eerie sulfate solution and the date at which
it was standardized together with the method of standardization:
* 11 *
In the potentiometric titrations, the endpoint with oerie
sulfate was exceedingly sharp. One drop (0.04 to 0.05 rol.) of this
solution was sufficient to cause a break in potential averaging 300
to 400 millivolts. With potassium dichromate, the break in potential
averaged only 75 to 125 millivolts per drop of solution.
(3) Determination of the Ferric Oxide Content of Portland
Cement. The standardized solutions of potassium dichromate and ceric sul-
fate were used for determining the ferric oxide content of eight cements
ranging from 0.4% to 5.4% Fe 20 3 • The same methods previously described
were used to determine the endpoints of the titrations. 'In the indicator
methods the cement samples were reduced with stannous chloride. In the
potentiometric titrations, the cement samples were reduced by passing
the solutions through a silver reductor or by treatment with stannous
chloride. When the cement solutions were to be reduced in the s ilver
reductor, filtration of the sample was necessary to remove the undis-
solved silica which might otherwise clog the pores of the reductor.
The exact details of the procedures followed in the titration of the
cements are given in the appendix of this report., The use of the two
oxidimetric solutions with the various indicators and the potentiometer
for determining the ferric oxide content of the cements is discussed
below.
. (a) Titration of the Cements with Potassium Dichromate. As
pointed out in the discussion concerning the standardization of the
dichromate solution, the size of the sample of the primary standard
affected the calculated Fe203 factor for the solution. It is therefore
logical to assume that this same phenomenon would be present when
titrating cementa of varying Fe203 content. For this reason the
A.S.T.M. directs that in calculating the percent of ferric oxide in
cements, a solution factor should be used which has been determined
against a weight of primary standard that yielded a titration approxi-
mately equal to that reqUired by the cement sample in question(12) •
This procedure necessitates the individual standardization of the
oxidizing solution for each different Fe203 content of celllents. While
this procedure is sound in theory, the results reported in this study
show that the use of a specific factor rather than an average factor
for the oxidant is of no practical significance. The volumes of
dichromate solution usedwitli ea.ch indicator and the potentiometer
in titrating the cements were converted to percent of Fe203 by the
, following two methods (Table 4):
(A) The dichromate factor used to calculate the percent
of ferric oxide was determined with a weight of
primary standard that yielded a titration
apprOXimately equal to that reqUired by'the
cement sample. Separate factors for each
indicator,potentiometer and for the iron wire
and iron ore were used and are tabulated in
separate columns.
(B) An average dichromate factor was used to calculate
the percent of ferric oxide in the cements. The
average factor (from Table 2) for each indicator,
potentiometer, etc. was used.
* 12 *
A comparison b&tween the A columns with the corresponding
B columns in Table 4 shows that in the majority of cases the results
were identical whether an average factor or a specific factor for the
dichromate solution was used. The maximum difference between any value
shown in oolumn A and the corresponding value shown in column B was 0.0;
percentage points (one case only).
However, when the values obtained with the indicators
are compared with those obtained with the potentiometer, a difference
(still insignificant) in values is noted. A comparison on this basis
(Table 5) shows that somewhat higher values were obtained with the
indicators than with the potentiometer. :Results with diphenylamine
barium sulfonate are slightly higher than those with N-methyldiphenylamine
barium sulfonate but neither gave results as high as the diphenylamine
indicator specified inA.S.T.M. C 114-46.
Whether the dichromate factor was determined with iron
ore or with iron wire also made a slight difference in the calculated
Fe20 S contents of the cements •. The reason for this is that iron
ore as a primar,y standard gave a higher factor for the dichromate
solution than iron wire. The higher factor with the ore as the primary
standard might be explained on the bas'!s that the ore may not have been
transferred entirely quantitatively .from the weighing dish to the
beaker. A loss of a portion of the ore would result in less of the
OXidizing solution being required to titrate the ore which would give
a falsely high value for the OXidizing power of the solution. Likewise,
failure to obtain complete solution of the ore would produce the same
effect. A high factor for the solution would give a correspondinglY high
value for the Fe20Scontent of the cements.
The method of reducing the cement samples had the most
noticeable effect on the calculated values of Fe20 S content. The
results obtained when reduction was accomplished with the silver
reductor averaged 0.02 percentage points lower than results obtained
after the stannous chloride method of reduction (Table 4). The low
results with the silver reductor may be due in part to the fact that
the silver reductor column reduces iron only, wbile other common inter-
fering elements remain in the oxidized state\l;). Another explanation
may be that because of the presence of undissolved silica, which
would clog the passages through the silver particles in the reductor
. column, the cemeItt samples had to be filtered prior to reduction. Care
was taken to wash the filter papers and residues thoroughly but it
is well-known that it is exceedingly difficult to wash the last traces
of iron from silica, Low results would be obtained if part of the iron
remained in the filter paper.
SummariZing the foregoing statements, it is evident that'
the primary standard used to determine the solution factor, the method
of determining the endpoint of the titrations, and the method of
reducing the samples have a greater effect on the percent of Fe20s
found than does the use of an average factor or a specific factor in
the calculations.
* 1; *
(b) Titration of the Cements with Ceric SUlfate. As with
dichromate, both an average factor end a speoifio factor for oalou-
latins the peroel;'lt of Fe203 in the oew-ents were used. Again the
results were remarkably oonsistent regardless of the faotor used in
the oaloulations (Table 4).
On the other hand, there were slisht differenoes between
results obtained withtheindioator and those obtained with the poten-
tiometer. The greatest difference was noted when the cements were
reduoed. in the silver reduotor column. As previously observed with
the diohromate solution, res~ts after the cements were reduced in
the silver reduotor oolumn averaged 0.02 percentage points lower than
results obtained after stannous ohloride reduotion. Practicall1no
differenoe between the use of faotors determined with iron ore and with
iron wire could be seen in the calculated percentages of Fe20 S '
The foregoing discussion may be summarized as follows:
The ceric sulfate titrationa further supported the conclusion that
the use of a specif10factor for each cement rather than an average
faotor is of no practical signifio~oe. The method of determining
the endpoint of the titrations and the method of reducing the samples
had some effect on the oalculated peroentages of ferric oxide, but the
maximum difference between results obtained by any method using cerio
sulfate was only 0.05 percentage points. The maximum difference with
potassium. dichromate was 0.07 percentage-points (Table 4).
* 14 *
Such is not the ease with eerie sulfate. Solutions of this
oxidant are regarded as b@ing reasonably stable when compared with
permanganate solutions. Nevertheless, the fact that definite and eon·
tinuous deterioration does take place is evident not only from this
study but has also been shown by Smith and Getz(15) who investigated
the stability of eerie oxidim@tricsolutions of various normalities
and containing various acids. All the ceric solutions used in their
studies showed deterioration during storage. According to their .
results, some of the 0.05 N solutions changed as much as 4.72% in
six months. Their O.lB solution changed 2.04% in· 7~ mon'tjhs. This
Was a perchloric acid solution of the ceric salt which waS shown to
be the most stable of all. The authors stated that this perchloric
acid solution "was SUfficiently stable in ordinary light not to
require restandardization for a period of 20 days".
(0) Us~w.•tth H,ydrochloricAcid. Solution of portland cement
is largely dependellt upon the use of hydrochloric acid and in selecting
an OXidant for titrating such a solution, it is well to keep in mind the
possibility of side reactions between the oxidant and the acid. This
is another reason for selecting potassium dichromate for routine ferric
oxide determinations. Ceric sulfate may be used with hydrochloric
acid, but because of its greater oxidative power (resembling per-
manganate) it will react with hydrochloric acid under certain conditions.
On the other hand, potassium dichromate because of its lower oxidation
potential can safely be used in a hydrochloric acid medium.
(d) Standard.ization. However, in comparing the two oxidi-
metric solutions, the advantages of cerie sulfate should not be over·
looked. From an analytical standpoint, none of the methods of standariz-
ing the dichr0IM-te are entirely satisfactory. It was shown.in an
earlier report\2J that numerous variables such as acidity, temperature,
dilution, rate at which solution is added particularly as the endpOint
is approached, grams of Fe being titrated, and the presence of extraneous
salts markedly affect the reaction between the ferrous iron and the
oxidant. Thus erratic factors may be obtained with any ferrous
standard available for use with potassium dichromate. Moreover, there
exists a peculiar anomaly in the standardization of dichromate in that
with low weights of iron (below 0.04 to 0.05 grams of Fe) there is
a noticeable variation in the solution factor. The above points also
apply to ceric sulfate when standardized against ferrous iron. However,
because of the greater oxidative power of cericsulfate, it can be
standardized against sodium oxalate. With this primary standard .
results are much more reproducible and the size of the sample has no
effect on the factor of the solution. Thus in the comparison of the
standardization of the two solutions, the advantage lies withceric
sulfate. However, it has been shoVlIl that the anomalous variation in
factor produced practically no difference in the calculated percent
of ferric oxide in the cementa analyzedjconseguently, this advantage
is ofno gree.t significance.
Ceric sulfate as a volumetric reagent has one advantage which
cannot be refuted. Ceric sulfate can be used for a wide variety of
oxidimetric titrations whereas potassium dichromate because of its
lower oxidative power is of limited application. From the standpoint
of cement analyses, the most important constituent besides ferric oxide
which can be determined with eerie sulfate is calcium oxide.
* 15 *
(e) Indicators. Those who ardently advocate the U$e of eerie
sulfate will bring up another point, namely; the availability of suitable
indicators for use with each oxidant. They will have in mind that no
indicator can match the numerous advantages of ferroin; and it is true
that regardless of its other advantages, any oXidant would be of limited
value to an analytical laboratory unless suitable indicators for use·
''lith that oXidant were available. Consequently, this subject vli11 be'
discussed somewhat in detail.
It has been shown by this work and by previous workers that
indicators of the diphenylamine series are not very satisfactory for
use with eerie sulfate. Likewise rerroin is not satisfactory for use
with diohromate because the color change is exceedingly slow to appear
with this oxidant. Thus, at the present time, the analyst has ceric
sulfate with ferroin on the one hand, and potassium dichromate with
diphenylamine indicators on the other from which to choose.
It is admitted that ever since Knop's initial introductton
of diphenylamine, numerous investigators have been seeking a less
capricious indicator for use with dichromate. Most of the new compounds
suggested have been di];lheny1amine derivatives. Di];lhenylaminesu1fonic
acid (or the barium salt) has been generally accepted as the best of
these and has been ado];lted in numerous industrial laboratortes(2) and
in the Federal S];lecification for cement. The principal advantages of
this indicator are threefold:
(1) It is soluble in water,
(2) 'Fhe color change is very sharp, being recognizable
eveil when the solutions themselves have
considerable color,
(3) The indicator is not affected by tungsten or
various other salts which interfere with
diphenylamine.
However, diphenylamine barium sulfonate is not perfect. It
has a high indicator correction. Moreover, this correction is not
constl]nji but varies with different conditions. Thlje Whitehead and
Wil1s\lo) in their review article concerning redox indicators report
that all indicators for dichromate-iron titrations have one or more
disadvantages. These authors, however, were not aware of the attri-
butes of the indicator N-methyldipheny1amine barium sulfonate. As a
matter of fact, the only mention they make of this indicator is at
the end of their paper in a list of compounds reported as being
unsatisfactorl for use as redox indicators. The authors state that
this compound is reported as giving a long range of intermediate
colors as the endpoint is approached which renders it unsatisfactory
as an indicator.
This objection originates from the work of straka and Oesper(17)
vTho made the only previous investigation in this country of the indi-
cator properties of methyldiphenylamine and its sulfonic acid derivatives.
They state that these compounds are not suitable as indicators "since
a long range of intermediate colors precedes the development of the
full red, and the establishment of the exact endpoint is consequently
* 16 *'
obscured"*.
In the present study no long range of intermediate colors
but a sharp and clear-cut endpoint was observed with the N-methyldiphenyl-
amine barium sulf9~te indicator. This supports the work of Knop and
Kubelkova-Knopova\5J who found that this compound is not only satisfactory'
as an indicator but actually excels all others for dichromate-iron
titrations. It has all the advantages of diphenylamine barium sulfonate
without the disadvantage of a high indicator correction. Knop and his
co~worker report that the indicator correction for N-methyldiphenylamine
barium sulfonate is practically nil and can be ignored except in special
micro-titration. The results of this investigation support that con-
clusion since titrations with this indicator closely agreed with poten-
tiometric titrations.
Moreover, according to Knop and his co-worker, N-methyldiphenyl-
amine barium sulfonate is the most sensitive of all indicators. It
requires only 0.002 to 0.003 ml. of a 0.1 N solution of potassium di-
chromate to produce a color change. Diphenylamine barium sulfonate
requires 0.005 ml. of a O.lN solution, and ferro in requires 0.01 ml
of 0.1 N ceric sulfate to produce a color change(ll). Consequently,
because of its low indicator correction, sensitivity, and other quali-
ties of solubility and stability, N-methyldiphenylamine barium sulfonate
is as good, if not better than,ferroin as an indicator for iron titra-
tions. This advancement places dichromate in a new strategic position
as a volumetric reagent.
The use of N-methyldiphenylamine barium sulfonate is handi-
capped by the fact that this indicator is not yet manufactured com-
mercially. Consequently, in order to take advantage of the many de-
sirable properties of a dichromate exidimetric solution, the analyst
must synthesize the indicator at present or be content with the use
of diphenylamine barium sulfonate in spite of its larger indicator
correction. It should be pointed out, however, that a comparison be-
tween results obtaineq with any of the three indicators, ferroin and
the above two diphenylamine derivatives, agreed within 0.02 percentage
points (Table 5). It is believed that such results are entirely sat-
isfactory from a practical standpoint.
(f) Summar;y of the Comparison of the Two OXidimetric Solutions.
Potassium dichromate is considered the most practical OXidant for de-
termining the Fe2 0 S content. of cements because of the low cost and
low equivalent weight of the salt, ease of preparing the solution,
unquestionable stability of the solution,a;vailability 'of· sili table
f.i.~d.ioaJt;~i.<f04'c:uee W14/lti d;~,ll6.'l'b.tiOO, a!I'l1i i ts n~.•'!'eactivity "With .
hcrdJ:"'ochloric ac:id. Cerle sadfats ha13the, adv.ante:ge cx:f'C)bB1hg'e-a.a:lier
ito atanda.rn.ize and can be used for determining other cement oxides
such as CaO.
* Straka and Oesper used a different method of synthesizing their com-
pound from that of Knop and Kubelkova-Knopova (German investigators who
were apparently una'Ware of the preVious work in the U.S. done by Straka
and Oesper). It may be that the method of synthesis used by straka and
Oesper resulted in a mixture of compounds which would account for a mix-
ture of colors at the endpoint.
* 17 *
' .. Discussion of R.esult§ in T&:bles 1 to 6. At ve.r1ou~ times
references to th€ tables have been' made end points exemplified ha'ifeb~e1~
discussed. To aVoid repetition, these points will no:t again be :fully
discussed in this section. Emphasis will bEf placed on the data not
already mentioned and the points illustrated by these.
Table 1 - Standardization of Ferrous Ammonium Sulfate
Solution with National Bureau of Standards' Potassium Dichromate.
As previously mentioned for reasons of convenience a solution of
ferrous ammonium sulfate was prepared for use as a primary standard.
Table 1 gives the results of standardizing that solution with a
sample of potassium dichromate (N.B.S. NO. 1,6) using diphenylamine
barium sulfonate, N-methyldiphenylamine barium sulfonate and a Beckman
MOdel G potentiometer for the endpoint determinations. The size of
the sample of dichromate taken appears to have no effect on the normality
factor of the solution. However, the values obtained with diphenylatlline
barium sulfonate as the indicator are erratic and much higher than
those obtained with the N-methyldiphenylamine barium sulfonate or the
potentiometer. This is a striking example of what Knop and hie co-
worker(5) refer to as the "greater resistance to oxidative cleavage
and correspondingly much smaller indicator correction of N-methyldiphenyl-
amine barium sulfonate". Each of the indica.tors referred to in the
table was added at the beginning of the titration, but the diphenylamine
barium sulfonate indicator being highly susceptible to OXidation began
to use up the oxidizing power of the dichromate. This resulted in less
ferrous· ammonium sulfate solution being reqUired for the reduction.
The longer the time the titration required, the more the indicator
exerted its influence on the dichromate. Consequently, values for
the normality of the ferrous ammonium sulfate solution with the indi-
cator wer~ high and erratic. This agrees with results reported by
Brennecke{ll) who also noted the strikingly greater indicator correc-
tion for diphenylamine barium sulfonate when dichromate was back
titrated with ferrous sulfate.
With N-methyldiphenylamine barium sulfonate, no difficulty
was experienced in obtaining reproducible results. The normality
factor determined with this indicator agreed closely with both the
theoretical and the potentiometric factQr,.
In Table 1, the dates of standardizing the solution are
given since subsequent standardization showed that the ferrous solution
had deteriorated. Inasmuch as the indicator titrations were performed
on the same day, the differences in results with each of the indicators
cannot be attributed to deterioration of the solution.
* 18 *
Reasonably good agreement between all methods of standardizing
the dichromate is shown in Table 2. Results with the iron ore were
slightly higher than those obtained with iron wire. Using the oondi-
tions previously outlined, the two methods of reduoing the iron wire
gave results in remarkably olose agreement. These points have been
disoussed previously and their signifioanoe will not be reiterated.
* 19 *
Table 5 - Compari8on of the FeaO/i Content of Portland Cements
bl Different Methods. In this table the average results for each of the
indicators and the potentiometer with 'PotFl.ssium dichromate and for the
indicator and potentiometer with ceric mu1fate are shown. Also results
previously reported using the A.S.T.M. method for determining the FeaOs
content of the cements are given. The indicator diphenylamine gave the
highest results, and diphenylamine barium sulfonate the next highest.
N-methyldiphenylamine barium sulfonate and ferro in each gave about the
same values which were somewhat lower than results obtained with the other
indicators. Potentiometric results with eerie sulfate were about 0.02
percentage points higher than potentiometric results with potassium
dichromate. Also, results with samples reduced by the modified stannous
chloride procedure were about 0.02 percentage points higher than those
reduced in the silver reductor column. The significance of these points
has been discussed previously.
SUMMARY
Determinations were made of the ferric oxide content of
portland cements with potassium dichromate, and the indicators
diphenylamine barium sulfonate and N-methyldiphenylamine barium sul-
fonate, as compared with similar determinat:J.ons made with eerie sulfate
and the indicator ferroin. Results obtained with the various indicators
were checked against potentiometric titrations. A silver reductor and
the stannous chloride method were used for reducing the iron. Also
various primary standards for determining the Fetps factor of the
standard soluti"ons were compared. Potassium dichromate solution
standardized against iron wire using the indicator diphenylamine barium
sulfonate is recommended as the most sui table method until N-methyldiphenyl-
amine barium sulfonate becomes commercially available.
All the points previously discussed will not be included in
this summary; but for purposes of comparison, the advantages and dis-
advantages of' the two OXidants, of the primary standards iron ore and
iron Wire, and of' the indicators diphenylamine barium sulfonate and
N-methyldiphenylamine barium sulfonate will be summarized.
* 20 *
1. Cerie Sulfate:
Advantages:
(1) It has a high oxidation potential~ being almost as
strong in oxidative power as potassium permanganate.
(2) It can be used for determining a number of· elements
besides iron, the most important of which, from the
standpoint of cement analysis, is calcium.
(3) In potentiometric titrations, the break in potential
is much greater than with potassium dichromate.
(4) It can be standardized against sodium oxalate which
gives a constant factor regardless of the weight of
the sample taken.
Disadvantages:
(1) The solution is much lesa stable than a potassium
dichromate solution.
(2) Because of the high oxidative power of eerie sulfate,
under certain conditions, it Will react with hydro-
chloric acid thus showing a $imilarity to potassium
permanganate. Therefore the concentration of the
hydrochloric acid must be more carefully controlled
than with potassium dichromate.
(3) Preparation of the eerie sulfate solution is a more
involved process in comparison with the preparation
of a potassium dichromate solution.
(4) Ammonium. nitrato-cerate from which the eerie sulfate
solution is prepared is more expensive than potassium
dichromate, and 10 times more of the cerate salt must
be used than to prepare the corresponding quantity of
dichromate solution. Also, the indicator, ferroin,
to be used with the eerie sulfate is costly.
2. Potassium Dichromate:
Advantages:
(1) It is the most stable of all oXidizing "solutions,
showing no appreciable change in titer for years.
(2) It is a simple aqueous solution without involVing the
expense and hazard of using sulfuric acid which
is necessary with eerie sulfate.
(3) It can be used with low cost indicators.
* 21 *
(4) Potassium dichromate favors a hydrochloric acid medium
which is neceseary in cement analysis.
(5) There is evidence from a number of sources that the most
satisfactory results of iron determinations are obtained
with potassium dichromate. It was found to be true in
this study. Henry and Gelbach(19) recommend the use of
potassium dichromate rather than eerie sulfate. They
studied the use of potassium dichromate and eerie sulfate
in the determination of iron reduced by a silver reductor
and conclude that lithe stability, purity, low equivalent
weight and comparative low cost of potassium dichromate
render ita very desirable oxidizing agent". The results
reported by the 32 skilled analysts who analyzed the
National Bureau of Standards Sibley iron ore (No. 27b)
are also significant. The average of the dichromate
determinations was 68.22%; the average of the permanganate
determinations was 68.34%; the average of the eerie
sulfate determinations was 68.17%; the value recommended
by the National Bureau of Standards is 68.23%.
Disadvantages:
(1) Because of the lower oxidative power of potassium di-
chromate, the change in potential at the endpoint of a
potentiometric titration is not as easil;y recognized
with potassium dichromate as with eerie sulfate.
(2) The standardization of potassium dichromate is more
difficult than the standardization of eerie sulfate.
3. Iron Ore:
Advantages:
(1) The ore carries a certificate of analysis issued by
the National Bureau of Standards.
(2) As the ore is 68.23% Fe, errors in the weighing of samples
have less effect on the calculated factor of the
solution than would similar errors in weighing samples
of iron wire which are 99+10 Fe.
Disadvantases:
(1) The ore is not homogenous but a mixture of 'Various iron
OXides, some of which are very difficultly soluble in
hydrochloric acid.
(2) Weighing a sample of the ore and transferring it quanti-
tatively to a beaker is difficult because the fine
particles of ore cling tenaciously to whatever they touch.
* 22 *
(3) Solution of the ore ie very time-consuming. Even if
solution is aided by the addition of stannous chloride,
the time required is much longer than that required
by the same weight of iron wire.
(4) Inasmuch as the certificate of anaJ.ysis for the ore shows
a wide variation in the results of the selected analysts
who tested the ore, it is very unlikely that the average
laboratory ohemist will obtain r.esults any more uniform
in his analysis with the ore.
4. Iron Wire:
Advantages:
(1) It is much more convenient to weigh samples of wire than
a powdered ore, or even orystals of a salt such as
sodium. oxalate.
(2) There is no difficulty in handling .the weighed sample
quantitatively; oonsequently, there is little likelihood
of errors due to loss of sample.
(3) Solution of the wire takes place very readily.
(4) The dissolved iron is largely in the ferrous state;
consequently, much less stannous chloride is needed
to reduce the solution. This IllaY be one of the
reasons why better results are obtainable with iron wire.
Disadvantages:
(1) The analysis of the wire is certified by a manufacturer
rather than the N.B.S. However, there are several
manufacturers who are noted for their integrity re-
garding the statement of purity on their products. ,
Consequently, any variation in the lab~:led EWld:actual
percent of Fe in the iron wire will ~J:'obably be less
than the variation in the ore shown by the certificate
of analysis. Moreover, in case of doubt, the iron wire
could be standardized.
(2) The wire when exposed to the atmosphere becomes oXidized
and must be cleaned with emery paper.
* 23 *
(2) The salt is soluble in water.
(3) The indicator may be used over comparatively wide ranges
of acidity.
(4) The hue of the indicator at the endpoint of the titration
is less affected by various substances such as tungsten,
stannic chloride and mercuric chloride, than is the
color change of diphenylamine.
Disadvantases:
(1) The indicator is very susceptible to oxidation, and,
consequently, has a high indicator correction.
(2) The solution of the indicator is affected by heat and
light and eventually becomes discolored. In this
respect it resembles diphenylamine.
(3) The indicator is not suitable for the titration of
dichromate with a ferrous solution. In this reverse
titration the indicator corrections are exceedingly
high end erratic.
* 24 *
RECOMMENDATIONS
In concluB ion it is recommended that the following changes
be made in the current A.S.T.M. procedure (C 114-46) for determining
the ferric oxide content of portland cement: ,
(1) Use diphenylamine barium sulfonate as indicator in place
of diphenylamine. (This is already being contemplated
by the A.S.T .M. and has been adopted by the Federal
Specifications).
Reduce the strength of the stannous chloride solution
from lCl/o to 5'10. (This ha.s also been mentioned by
W. C. Hanna, Chairman, Working Oommittee on Methods of Chemical
Analysis, and has been adopted by the Federal Specifications.
Reduce the amount of saturated mercuric chloride solution
added to oxidize the excess stannous chloride from. 10 ml.
to 5 ml. It is important to add the mercuric chloride
before final dilution of the solution.
(4) Change the phosphoric-sulfuric acid mixture to a 1-1
phosphoric acid solution and reduce the amount to be
added to 10 ml. (This agrees with the new Federal
S-pecifications).
(5) Use a hydrochloric acid concentration of the solution to be
titrated of 1 to 2 N for best results, or approximately
10 to 12 ml. Hel per 100 ml. of solution.
(6) AlthoUgh it is logical from. a theoretical point of view to
consider iron ore as being a superior primary standard to
iron wire, in practical work the average analyst will
obtain better results with iron wire. Therefore, it is
recommended that iron wire at least be retained as an
alternate standard.
(7) A more reliable factor for the solution is obtained by
averaging the results of four or five determinations of
the factor (against 0.030 to 0.035 g. Fe) than to use
various factors determined by one or two titrations whose
volume approximates the volume required by the cement.
Individual determinations of the factor of the standard
solution may vary considerably even though titrated against
the same weisht of Fe, and therefore, single or even
duplicate determinations of the factor may not be accurate.
ACKNOWLEDGMENT
The author is indebted to Mr. C. L. Ford and Dr. L. S. Brown
of the Research Laboratories of the Portland Cement Association, and
to Mr. G. W. Schaeffer of the University of Chicago for information
and helpful suggestions concerning-this investigation.
* 25 *
BEFEBENCES
*26 *
Research Laboratories of the
Portland Cement Association
33 W. Grand Ave., Chicago
INDICATORS POTENTIOMETER
Diphenylamine N-Methyldiphenylamine Weight
Barium Sulfonate Barium Sulfonate Dichromate Normality
Weight Weight
Dichromate Normality Dichromate Normality
0.0110 0.05133 0.0109 0.05029 0.0125 0.05048
0.0124 0.05109 0.0107 0.05040 0.0214 0.05045
0.0202 0.05186 0.0210 0.05021 0.0321 0.05047
0.0203 0.05092 0.0202 0.05024
0.0300 0.05065 0.0320 0.05020
0.0300 0.05056 0.0301 0.05040
Av. 0.05107 Av. 0.05029 Av. 0.05047
June 4, 1947
Series 339
Research Laboratories of the
Portland Cement Association
33 W. Grand Ave., Chicago
Fe...O.,. FACTOR
Primary Indicators·
Standard Diphenylamine N-Methy1dipheny1amine Potentiometer
Barium Sulfonate Barium Sulfonate
Ferrous Ammonium.
Sulfate Solution
Vol.
5 ml. - 0.004014 0.004019
10 " - 0.004015 0.004019
15 " - 0.004035 0.004039
Av. 0.004021 Av. 0.004026
----- ---- - - - - --- --. - -- - - --- - - - - - -- - - -- -
Sibley Iron Ore
(SnC1a Reduction~
~
0.01 0.003995 0.004017 0.004023
0.02' 0.004032 0.004037 0.004028
0.03 0.004044 0.004047 0.004040
0.04 0.004038 0.004046 0.004052
0.05 0.004059 0.004057 0.004053
Av. 0.004034 Av. 0.004041 Av. . 0.004039
- - - .. _. - , - - - - - - - - - - - - - - - - - - - - - - - -------
- -liire
-Iron
.' SnC1a ReQ,ucti9n rj
~ .
0.01 0.004006 0.004003 0.004023
0.02 . 0.004023 0.004025 0.004020
0.03 0.004025 0.004032' 0.004038
0.04 0.004033 0.004046 0.004039
0.05 0.004033 0.004049 0.004049
Av. 0.004024 Av. 0.004031 Av. 0.004034
S:L1ver Reduator
g. Jfe
0.01 0.004008 0.004014 0.004018
0.02 0.004009 0.004030 0.004027
0.03 0.004030 0.004032 0.004031
0.04 0.004040 0.004048 0.004043
0.05 0.004036 0.004056 0.004052
IAv. 0.004025 Av. 0.004036 v. 0.004034
June 4, 1947
Series 339
Research Laboratories of the
Portland Cement Association
33 W. Grand Ave., Chicago
Wt. g.
0.03 7-30 0.003893* 4-11 0.003928*
0.03 0.00390]* 0.003937*
0.04 0.003943*
0.05 0.003934*
0.05 0.003926*
Av. 6.003897 Av. 0.003934
- - - -- -- ---
Sibley Iron Ore
I
(SnCl? Reduction)
g. ·Fe
0.01 6-18 0.003881 4-14 0.003893
0.02 0.003907 0.003912
0.03 0.003920 0.003929
0.04 0.003924 0.003932
0.05 0.003924 0.003933
Av. 0.003911 Av. 0.003920
Iron Wire
Silver Reductor
g. Fe
0.01 6-20 0.003870 6-16 0.003895
0.02 0.003912 0.003899
0.03 0.003912 0.003915
0.04 0.003932 0.003933
0.05 0.003940 0.003933
Av. 0.00391, Av. 0.003915
SnCla Reduction
g. Fe
0.05 7-30
* Single determinations only.
June 4, 1947
Series 339
Ta-ole 4 - DErERMINATION OF THE Fe20s CONTENT OF PORTLAND CEMENTS, PER CENT BY WEIGHT /
Column A: Factor used to calculate the per cent of Fe2 0S was determined with a weight of primary standard that
. yielded a titration approximately equal to that required by the cement sample. .
Column B: Average factor used to calculate the Fe 2 0 S per cent.
Values represent the average of two or more determinations.
TITRATED WITH POTASSIUM DICHROMATE
INDICATORS POTENTIOMETER
Di he lamine Barium Sulfonate \ N-methyldiphenylamine Barium Sulfonate Iron Ore
Cement Iron Ore Used" Iron Wire Used Iron Ore Used Iron Wire Used Used as Iron Wire Used
Lot as Primary as Primary as Primary as Primary Primary as Primary
No. " Standard Standard Standard Standard Standard Standard
stannous Stannous Stannous Stannous Stannous Stannous
Chloride \ Chloride Silver Chloride Chloride Silver Chloride Chloride Silv i
Reduction ! Reduction Reductor*
I
Reduction Reduction Reductor* Reduction Reduction Reduc f J:
A1 B1 i A2 B2 As Bs A4 B4 A5 B5 A6· B6 A B A8- B8 A
1 954 0.36 0. 36 o. 3 o. 3 0 . 3 o. 3 II. 0 ~ 37 o. 37 o. 37 o. 37 0.37 0.37 0·35 0.35 0.35 0.35 0.36 O.
17123 2.11 2.11 ! 2.11 2.11 2.10 2.11 2.10 2.10 2.09 2.10 2.10 2.10 2.07 2.08 2.07 2.08 2.06 2.
17119
17126
3.0~ 3. 0 4 ! 3. , 3.0, 3.0~ 3.
0 ,1
0
3·7 3.7 5 I 3·7 3.7 3.7 3·7 I 3.7 3.73
3.0~ 3.03 3'701 3.0~ 3.02 3.02
3. 3 3·7 3.73 3.73
3.. 01 3~02 3.00 3.01 2.99 3.00
3·72.3.72 3.71 3·71 3.69 }.70
17120 4.70 4.68 I 4.67 4.67 4.68 4.67 4.69 4.68 4.67 4.67 4.67 4.67 4.66 4.66 4.66 4.66 4.63 4.64
17545 4
5.35 5.35 '\5.3 5.33 5.35 5.33 II', 5.35 5.35 5.35 5.33 5.35 5.34 5.34 5.33 5.33 5·32 5.30 5.29
l7348A 3·95 3.94 3.93 3.93 3.93 3.93
l7348B 3.58 3.57 ! 3.57 2.57 3.57 3.57
TITRATED WITH CERIC SULFATE
June 4, 1947
Series 339
Research Laboratories of the
Portland Cement Association
33 W. Grand Ave., Chicago
June 4, 1947
Series 339
APPENDIX
*****
REAGENTS:
4. Miscellaneous Reagents:
APPARATUS:
* 4 *
for a potentiometric titration, they were rinsed with dis-
tilled water, dried and flamed. The factory-made, sealed
platinum electrode was cleaned by dipping it in cleaning
solution, rinsing with water, and finally cleaned by electrolysis.
The electrolytic decontamination was accomplished by connecting
the electrode and a platinum crucible lid by means of battery
clips to a six-volt dry cell battery, placing the two pieces
of platinum one centimeter apart in a beaker containing
N!lO Hel and passing a current through the liquid for one
minute. By means of a two-waY switch, the current was
alternated every five seconds. The sealed platinum elec-
trode was seldom used in this study, the wire electrodes
being preferred.
3. Silver Reductor. A silver reductor was prepared by charging
a Jones reductor tube with 28 g. of metallic silver after
the prescribed method of Walden, Hammett and Edmonds(l).
The metallic silver had been prepared in the laboratory of
the Portlarid Cement Association by reclamation from silver
chloride residues by procedures outlined by Chase(2) and
Spies(3). The metallic silver thus obtained was heated in
'a muffle at 750°C~ to cause agglomeration of the fine
particles. The resultant spoIlBY' mass was ground in an
agate mortar to pass a No. 20 standard sieve. The granular
silver was suspended in water and the mixture poured into
the. reductor column. A plug of glass wool preViously
inserted in the lower end of the reductor column served
to retain the metallic silver. The silver was then washed
several times with dilute ammonia water (1-1) followed by
several washings with water, then washed with dilute
sulfuric acid (1-2). Care was taken never to allow the
liquid in the column to drain below the top of the silver.
The rate of flow through the column was 30 to 35 ml. per
minute depending upon the height of the liqUid in the
column. The silver reductor did not need to be regenerated
inasmuch as less than one-fourth inch of the metallic silver
was blackened with use during the entire investigation.
MEl'HODS:
*5*
titrations. The weighed sample of K2Cr207 was dissolved
in 100 ml. of normal HOL If an indicator was to be used, .10 mL
of a 1-1 HsPO 4 solution were also added. After the \ ichromate
crystals were dissolved, the solution was titrated with the
ferrous ammonium sulfate solution using a 25 ml. calibrated
normax burette. The ferrous solution was added dro~se,
care being taken to allow the solution to tome to equilibrium
between drops, particularly as the endpoint was approached.
During titration, the dichromate solution was agitated With
a mechanical stirrer. The indicator endpoint was regarded
as being reached when one drop of the ferrous solution
caused a permanent fading of the indicator color. The
potentiometric endpoint was reached when one drop of the
ferrous solution caused a sudden break in potential.
The results of standardizing the ferrous ammonium
sulfate solution are shown in Table 1. .
*6*
tiometric endpoint was taken as that point at
which one drop of the dichromate solution caused
a sharp break in potential. The Fe20s factor
of the dichromate solution was calculated by the
following formula.:
. Fe20S factor :: normality of ferrouB solution
x 0.5585 x 1.4297
55.85 == atomic weight of iron (1941)
1.4297 = molecular ratio of Fe20 S to 2 Fe
The Fe20s factors of the dichromate solution
as reported in Table 2 for the N-methyldiphenylamine
barium. sulfonate and the potentiometer were cal-
culated from the normality factor of the ferrous
ammonium sulfate solution determined with the
corresponding indicator or the potentiometer.
(b) Standardization of Dichromate with Iron Ore. The
procedure followed for standardizing the potassium.
dichromate solution against iron ore is given below:
The iron ore was dried in an oven at 105°0.
overnight, cooled in a desiccator, and samples of
ore haVing weights of 0.0147, 0.0293, 0.0440,
0.0586 and 0.OT53 g. were weighed on a glass
weighing dish and transferred to a 250 ml. beaker.
These weights of samples were chosen because when
converted to grams of Fe they ranged from 0.01 to
0.05 g. of Fe in 10 mg. gradations. The samples
were weighed on e. glass dish counterpoised by a
similar glass dish, because it was found to be
impossible to quantitatively transfer the iron
ore from a metal pan to the 250 ml. beaker. A
25 ml. portion of concentrated HOl was added to
each of the s~ples of ore, the beakers covered
with watch glasses and placed on a hot plate.
When the mixture started to boil, the samples were
moved to a cooler section of the hot plate
until they simmered lightly. The samples were
then allowed to remain overnight on the hot plate
at a temperature of 50° to 60°0.
On the following morning the cover glasses
and sides of the beakers were rinsed with distilled
water, the lids were replaced and the iron ore
solution brOUght to boiling. The solution was
boiled lightly until the last traces of the ore
had gqne into solution. When the ore was in solution,
it· was reduced while hot with a '7'/0. stannous chloride
solution. Two drops in excess were added because
occasionally no precipitate was formed upon the
later addition of the mercuric chloride when only
one drop in excess was added.
*7*
The ferrous solution was then cooled to room tem-
perature in a water bath. A 5 ml. portion of saturated
mercuric chloride solution "was added all at once and
the mixture allowed to stand for 5 minutes or if
titrated immediately, the solution was stirred vigorously
one minute with a mechanical stirrer.
After the excess stannous chloride was oxidized
by the addition of the mercuric chloride, the ferrous
solution was diluted to approximately 70 ml. with
distilled water. In the indicator method, 10 ml. of
the phosphoric acid solution were added and 3 drops
of indicator. In the potentiometric method this step
was omitted. The iron ore solution was then titrated
with potassium dichromate. The same precautions re-
garding the dropwise addition of the dichromate were
observed as in the titration of the ferrous ammonium
sulfate solution.
The Fe20s factor was calculated by the formula:
Fe ° factor = Vol.
2 s
Wt. of ore x 68.2~! x 1.4297
of dichromate
68.23 = ~ of Fe in ore
1.4297 = molecular ratio of Fe20s to 2 Fe
(c) Standardization of Dichromate with Iron Wtre: The method
which was used to standardize the potassium dichromate
against iron wire is as follows:
A length of iron wire (3 to 4 inches) was polished
bright wi th fine emery cloth. The wire was then wiped
clean with a soft cloth. A portion at each end of the
wire was cut off and discarded. Samples were taken
by cutting off pieces of the iron wire, the length
depending upon the weight of sample desired. Samples
of wire from 0.01 g. to 0.05 g. were taken in 10 mg.
gradations. The weighed samples were placed in 250 ml.
beakers and dissolved in 25 ml. 1-1 ReI. Solution
took place very readily and if desired, was hastened
by placing the beakers on a warm (60°0.) hot plate.
After the wire was dissolved, the lids and sides
of the beakers were rinsed with distilled water. The
samples were then "reduced by one of two methods. /l. 510
solution of stannous chloride was added dropwise, one
drop in excess being added to the solution of the iron
wire which had been heated to boiling. After reduction,
the samples were cooled to apprOXimately room temperature
in a water bath. A 5 ml. portion of the saturated mercuric
chloride solution was added all at once and the mixture
allowed to stand for 5 minutes or stirred Vigorously for
one minute. It was then diluted to approximately 70 ml.
with distilled water. If an indicator was used to
*8*
determine the endpoint, 10 ml. of the phosphoric acid
solution and 3 drops of the indicator solution were
added. The mixture was then titrated with the solution
of potassium dichromate. The alternate method of re-
duction was carried out by passing a cool solution of
the iron wire through a silver reductor column. The
reductor column wa~ rinsed with 100 ml. of normal Bel
which was added in portions of 10 to 20 ml. at a time.
Each portion was drained to the top of the silver be-
fore the succeeding portion was added. The .rate of
flow through the column was approximately 30 ml. per
minute. The final volume was approximately 150 ml.
which was titrated with the dichromate. If an indicator
was used, 10 ml. of the HsP04 solution was added, 'ille
F:e20 3 'factor of the dichromate was calculated by the
formula:
Fe ° factor = Wt.Vol.ofofwiredichromate
2 S
x 99.8~ x 1 4297
•
*11*
· When the solution of the cement was to be .
reduced by passing it through a silver reductor,
filtration of the sample was necessary to remove
the undissolved silica. The hot solution of the
cement was filtered through a Whatman No. 31,
9 em. filter paper. The filtrate was collected
in a 400 ml. beaker. The 250 ml. beaker was
scrubbed with a policeman and washed several times
with small portions of water. The filter paper
and residue were carefully washed 10 times with
small portions ot water. The final volume in the
400 ml. beaker was 80 to 90 m!. This was poured
into the reductor tube and the beaker rinsed
with distilled water. The solution from the
reductorcolumn was collected into the same
beaker. The solution passed through the column.
at a rate of 30 to 35 ml. per minute. The
reductor column was rinsed with 150 ml. of
normal Hel which was added in 10 to 20 ml.
portions, each being drained to the top of
the silver before the succeeding portion was
added. The final volume was approximately 250 ml.
The samples reduced by this method were titrated
potentiometrically •.•
* 12 *
June., 1947