EPA-600/4-76-008
March 1976
Environmental Monitoring Series
MEASUREMENT OF ATMOSPHERIC SULFATES:
LITERATURE SEARCH AND METHODS SELECTION
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.
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EPA-600/4-76-008
March 1976
MEASUREMENT OF ATMOSPHERIC SULFATES: LITERATURE SEARCH
AND METHODS SELECTION
by
Fred J« Bergman
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
Contract No. 68-02-1728
Michael E. Beard
Quality Assurance Branch
Environmental Monitoring and Support Laboratory
U«S« Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Research Center,
Research Triangle Park, Office of Research and Development, U»S« Environ-
mental Protection Agency, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and policies of the
U«S« Environmental Protection Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use»
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FOREWORD
This program, "Measurement of Atmospheric Sulfates: Literature
Search and Methods Selection," is being conducted under the Environmental
Protection Agency (EPA) Contract No. 68-02-1728, which is Midwest Research
Institute (MRI) Project No. 3948-C. The program is concerned with methods
for analyzing the water soluble sulfates in ambient air samples. The ob-
jectives of the program were (a) to conduct a thorough literature survey,
(b) to select the two most promising methods, and (c) to subject the two
methods to a ruggedness test.
This is the final report of Phase I covering the literature search
and the selection of the two most promising methods. The results of the
literature search for methods of sulfate analysis are included as an appen-
dix*
This program is being conducted under the management of Mr. Paul G.
Constant, Jr., Head, Environmental Measurements Section of MRl's Physical
Sciences Division. The principal investigator is Mr. Fred J. Bergman.
Approved for:
MIDWEST RESEARCH INSTITUTE
L. J. Shannon, Assistant Director
Physical Sciences Division
April 2, 1976
iii
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TABLE OF CONTENTS
Foreword ••••••• ................. iii
List of Tables • ••••••.•••••••••••.••••••• vii
Summary* .••••••••••••••••••••••••••••• ix
Section
I Introduction • 1
II Literature Search 2
III Methods Identification . 5
IV Basic Analytical Procedures* * 6
V Factors Affecting the Analytical Procedure ... 12
VI Criteria for Method Selection* *.. ..... 15
VII Method Evaluation* *... 16
Atomic Absorption. ....... .... 16
Chromatographic* ........ .... 17
Colorimetric •»•....•••••••.......... 17
Conversion-Detection ......... ...... 17
Electrometric 18
Flame-Photometric* 19
Fluorometric ............ .*••• 19
Gravimetric 19
Radiometric* •••• 19
Spectrophotometric ..................... 20
Substituted Benzidines .*.. 21
Turbidimetric. ....* ....... 21
VIII Method Selection 22
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CONTENTS (Concluded)
Appendix - Bibliography of Methods for Sulfate Analysis ....... 23
Atomic Absorption ••••••••••••••••••«...... 24
Chromatographic .................. 25
Colorimetric. ... ...... ..... 27
Conversion-Detection • 61
Electrometric ............ ....... 65
Flame Photometric ............. . 77
Fluorometric. ....... 78
Gravimetric 79
Nephelometric and Turbidimetric ..... •.... 88
Radiometric 95
Spectrophotometric. ........................ 96
Substituted Benzidines 103
Miscellaneous - Methods ...... 107
Miscellaneous - Books ....... 116
Sampling. 128
Addendum 132
vi
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LIST OF TABLES
No. Title Page
1 Potential Interferences Resulting from Insoluble Salt
Formation at a pHof7.0.,............... 14
VII
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SUMMARY
A thorough literature search for methods of sulfate analysis has been
completed. The results of the search with a very brief abstract of each
method is attached as an appendix. The analytical methods have been re-
viewed for strengths and weaknesses and the two most promising methods
have been selected. Based on this review» the two recommended methods are
the methyl thymol blue method described by A. L. Lazrus and the barium
chloranilate method modified by H. N. S. Schafer and developed by R. J»
Bertolacini and J. E. Barney, II.
The results of this phase of the investigation have been submitted to
EPA. Acceptance of the two methods recommended and approval to complete
the investigation was received 15 October 1975.
ix
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SECTION I
INTRODUCTION
Recent health effects studies have shown that the concentration of
sulfate in ambient air presents a significant hazard to human health. The
use of catalytic control devices in automobiles will possibly increase
the level of atmospheric sulfates.
This has led to an increasing emphasis on the measurement of sulfate
concentrations in ambient air. Since the data obtained may subsequently
be used to set an ambient air standard for sulfates and may influence auto-
motive standards for other emissions, it is important that the analytical
methods used for sulfate analysis be reliable.
One method of determining reliability is to subject candidate methods
to a ruggedness test as described by W. J. Youden and Stowe and Mayer.*
The results of a ruggedness test then permit strengthening the methods
and enable EPA to recommend the most reliable of the methods evaluated.
The program for accomplishing the above goals was divided into three
phases. Phase I included a thorough literature search and an evaluation
of the various methods with a recommendation of the two most promising
methods. Phase II covers a familiarization period and a detailed method
write-up for the two methods. Phase III includes the ruggedness test de-
sign and investigation and a qualitative identification of the signifi-
cant and nonsignificant effects. This report presents a complete descrip-
tion of the work performed under Phase I of the program.
Statistical Techniques for Collaborative Tests by W. J. Youden, A.O.A.C.
Publications, Box 540, Benjamin Franklin Station, Washington, D.C.
20044, and Efficient Screening of Process Variables by R. A. Stowe
and R. P. Mayer, Ind. Eng. Chem., ^8:36-40 (1966).
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SECTION II
LITERATURE SEARCH
The first task conducted during this program was a thorough literature
search for available methods for sulfate analysis. This search covered all
available abstracts to the present time, which included: Air Pollution
Abstracts, APCA Abstracts, Chemical Abstracts, and Analytical Chemistry
Annual Reviews. We have also searched Analytical Chemistry, Environmental
Science and Technology, Journal of APCA, and have conducted a keyword search
of the Bay Area Air Pollution Library and the MRI Pollution Library. Listings
of reports from the EPA Library and the National Technical Information
Service were also screened. Texts covering analytical chemistry at the
Linda Hall Library of Science and Technology and MRI were also examined.
A card index was compiled from the literature search. Each card con-
tains the senior author, the article's title, a brief description of the
method, and the source.
The cards were grouped by the analytical technique and each section
was alphabetized by the senior author's name. The methods were grouped
primarily by the method of measurement. For example, a volumetric method '
with a visual end-point is listed under colorimetric, but if conductivity
was used it is listed under electrometric. The following is a list of the
headings and the methods included in each group.
A—Atomic Absorption; Methods based on atomic absorption of either
excess reactants or atomic absorption inhibition titrations*
B—Chromatographic: Methods which use paper or column separation
or electrophoresis to separate anions. Methods using ion-exchange to remove
interfering cations are not included in this section but are reported in
the section related to the detection method.
C--Colorimetric; Methods using acid-base indicators, compleximetric
colored end-points, visual turbidimetric and fluorescent optical end-points.
D--Conversion-Detection; Methods based on converting the sulfate to
SO or H S and measuring the resulting product.
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E— Electrometric; Methods using either current or voltage for measure-
ment. This includes amperometric, potentiometric, specific ion electrode
and pH methods*
F—Flame-Photometric; Methods based on the direct analysis of the
sulfate ion or flame emission of cations such as Ba and Pb used for in-
direct analysis*
G—Fluorimetric; Methods using U-V excitation and fluorescent emis-
sion for analysis.
H—Gravimetric; Methods based on the weight of a precipitate. The
gravimetric methods using substituted benzidines are reported under K.
I—Radiometric; Methods using radio labeled compounds and counting
techniques for analysis.
J—Spectrophotometric; Methods based on concentration measured by
transmission or absorbance using U-V or visible light (200 to 1,000 nm).
K—Substituted Benzidines: Methods based on substituted benzidines
regardless of the analytical detection technique. The substituted benzidine
methods include gravimetric and spectrophotometric as well as procedures
for preparing some of the substituted benzidines.
L--Turbidimetric; Methods based on either turbidimetric or nephelo-
metric measurements.
M—Miscellaneous; Methods not included in the other categories.
N—Books: Listing of some of the texts which contain multiple meth-
ods of sulfate analysis. All of the methods were covered in the previous
sections.
0—Sampling; Methods which contained information on collecting ambient
samples* Articles which consist primarily of sampling techniques appear in
this section only. When a detailed analytical method is covered in the same
article, it is also indexed under the analytical group heading.
After the original search was indexed, duplicates were eliminated
and the bibliographies of the more recent publications were checked to
locate any missing references. The results of the survey are presented
in the Appendix.
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Because of the large number of articles located, the abstracts are
rather cryptic to maintain a manageable document. Information which was
presented in a publication title was generally not repeated in the method
abstract.
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SECTION III
METHODS IDENTIFICATION
The methods located during the literature search were evaluated to
identify the basic analytical techniques employed. These techniques may
be summarized as follows:
1. SO."2 + Ba+2
4
2. SO."2 + Pb+2
4
3. SO."2 + (X) - > (X)SO.
4 ^4
_2
4. SO. + Me(X) - > MeSO. + (x)
4 4
-2 +1
5. SO. + 2Na - > NaSO.
4 24
_2
6. SO, (physical properties)
7 .
8.
These generalized formulas describe the reactions that have been used
for measuring sulfate. In most reaction types, three methods of quantitating
the results are described in the published literature. The procedures used
for quantitating consist of measuring the reaction product, measuring the
reagent consumed or measuring the excess reagent. In some methods, the re-
agent consumed is determined indirectly by measuring the anion released by
the reaction.
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SECTION IV
BASIC ANALYTICAL PROCEDURES
This section presents a detailed discussion of the basic reactions
and the methods employed for analysis.
1. SO ~2 + Ba+2 > BaSO.
4 4
The basic reaction relies on the addition of a barium salt to produce
insoluble barium sulfate. Interferences result from the presence of any
anion producing insoluble barium salts. By carrying out the precipitation
at a low pH, most anion interferences can be minimized.
a. Measuring the barium sulfate: Gravimetric procedures are one
of two techniques generally used for determining the barium sulfate product.
Published techniques using barium are listed in the Appendix under Gravi-
metric and include references 406 to 468 with the exception of 423, 429,
430 and 434« These methods use reagents other than barium and are discussed
elsewhere in the report. Errors, when the precipitation is carried out at
a low pH, are caused primarily by the inclusion of foreign ions in the
precipitate and the production of fine precipitates which are difficult to
filter. A number of papers have attempted to minimize these effects* A
correction for the solubility of BaS04 is sometimes applied for greater
accuracy.
The second technique employed to quantitate the barium sulfate
product is based on opacity.
The same basic barium precipitation reactions are employed for
nephelometric (reflected light) and turbidimetric (transmitted light) pro-
cedures. The same solubility and interference problems apply when using
turbidity that are associated with the gravimetric procedures.
Besides the interference problems resulting from other ions,
nephelometric and turbidimetric methods require a fine, stable, uniformly
sized precipitate. A considerable number of investigations have been con-
ducted to optimize precipitation conditions.469—525_/ under proper conditions,
the system follows the Beer-Lambert law over a reasonable concentration
range• *
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b. Measuring the barium used; There are numerous techniques
reported in the literature for measuring the barium required for precipi-
tation. One technique consists of measuring the excess barium. This can
be accomplished by back titrating the excess barium using a wide variety
of titrants. These titrants have included Trilon BT26,243,262/ K2CrC>4 (13
references), EDTA (11 references), Na2CC>3 (four references), ^SO^Zfl/
NH4OH,2Z/ NH4KCr204,7Z/ Na2HP04,20£/ and Na2S04.i^/ Excess barium has also
been measured by atomic absorption,JLtil^42' flame emissions,^2^zft21/ and
emission spectrophotometry«£fil/
Another measurement technique consists of adding excess barium
ions, filtering the precipitate, dissolving the precipitate and titrating
the barium. These procedures have employed a number of reagents to dissolve
the BaS04 and titrants consisting of EDTA or the addition of sodium thio-
sulfate followed by an iodometric titration.
A third method of measuring barium consumption relies on the
addition of a standard barium solution to produce insoluble barium sulfate.
The excess barium which occurs near the equivalency point of the precipi-
tation is then detected.
. The procedure is generally titrimetric using one of several end-
point indicators. Eriochrome Black T,£Z' tetrahydroxyquinone (17 references),
disodium rhodizonate (17 references), Alizarin Red S (eight references),
nitchromazo (five references), MTB (three references), SPADNS,^;' fluorescein
(three references), and thorin (13 references) have all been used. Various
modifications of the basic method have been developed for end-point improve-
ment. Photometric end-point sensing* ,t*-°Ji\^®' has been used as well as
automatic—' spot plato71^138*139' and high frequency oscillometric tech-
Uiciuc->5.53,l%6.l71.180.1947
The end-point has also been determined amperometrically,3^!' po-
tentiometrically (21 references), and coulometrically.357?358*359,l383/
c. Measuring the anion released during precipitation; A number
of procedures added a barium salt and measured the inorganic anion released
by the barium sulfate precipitation. Barium chromate has been employed with
the released chromate determined iodometrically (eight references) by ti-
trating with phenylcarbazide,—— ferrous sulfate, > 1->J;24U/ ceric ammo-
nium sulfate,-=£-' and tin chloride. ."/ Barium iodate has also been used
with the released iodate determined iodometrically,38?129?23o/ Barium oxa-
late has been employed with the oxalate ion titrated using potassium per-
OQ 1 A 7 1 QQ O1 "\l
manganatei * ?J-07?^-Vf Barium carbonate has been used with the carbonate
ion determined by acidimetry, °i. . . ' and barium thiosulfate used as the
precipitant with the released thiosulfate determined iodometrically« r£'
Barium phosphate has also been employed with the released phosphate neutra-
lized with standard sodium hydroxide and the excess hydroxide titrated
with standard HCl J^i'
7
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2 . SO, "2 + Pb+2 - >PbSO.
4 4
Most of the procedures using lead to precipitate sulfate employ either
a direct titration or a precipitation followed by a determination of the
lead content of the precipitate.
Nine publications determined sulfate by titrating with lead, the end-
point determined using dithizone* Two publications determined lead by ti-
trating with sodium hydroxide, adding sodium or ammonium sulfide and back
"}? 1 9 O/
titrating with sodium hydroxide i I Le- ' Sulfate has also been measured by
titrating with lead nitrate in the presence of KI,l£§lJLZZ/ or erythro-
f4'
A number of publications reported sulfate analysis by precipitating
lead sulfate and determining the lead content of the precipitate by titrat-
ing with EDTA122?123?154!252/ or other chelating agent s!2i/ potassium ferro-
cyanide, 4^ °7'1 8' ammonium molybdatai£2/ or sodium carbonate. 200I255/
The precipitated lead sulfate has also been analyzed by adding an excess
of EDTA and titrating the excess with zinc chloride, i239'
Lead nitrate has been employed to precipitate lead sulfate with the
end-point detected using a lead specific ion electrode ,334l372 i385 I392/
The end-point has also been determined potentiometrically (24 references)
using a Redox indicator«i2£' or by conductiometric and amperometric titra-
tion*
3. SO."2 + (X) - >(X)SO.
4 4
This approach employs a reaction with sulfate ions to form an organic
salt or a colored complex* Two examples are the reaction of a sulfate with
FeS04 in perchloric acid to form a colored complexi-t-L^-tS' and the forma-
tion of a colored complex with hexamminecobalt (ill) bromide [G
A number of procedures are reported in the literature which utilize
organic sulfates* The organic reagents frequently used are benzidine or
the substituted benzidines* Other potential organic materials have been
evaluated* For gravimetric work, the main advantage of using the organic
reagents is a reduced sulfate solubility and a corresponding increased
sensitivity* These advantages are frequently coupled with a significant
increase in interferences* The organic reagents form insoluble complexes
with metallic salts and form insoluble salts with anions. The metallic
interferences can be effectively eliminated by treating the sample with
a hydrogen form ion-exchange resin but preventing anion precipitation is
considerably, more difficult* Phosphate, tellurite. selenate and oxalate
have been reported as forming insoluble salts* °' Of these four, phos-
phate appears to be the most significant interference for ambient work*
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The effective removal of phosphate using calcium or zinc salts has been
coo/ r °
report ed*i2i/
The development of substituted benzidine as gravimetric reagents was
followed by their application to nephelometric determination* The reagent
commonly used was 4-amino-4l-chlorodiphenyl (CAD ).-../ The problem of pro-
ducing a stable precipitate when using CAD appears to be similar to those
associated with BaC^, although not as severe. Fluoride is an interference
at concentrations over 0.18 p,g/ml. Phosphate is also an interference which
may be removed according to Martin. '
The most promising substituted benzidine for nephelometric analysis
appears to be 2-aminoperimidine. ^' This reagent was found to produce a
heavy silky precipitate of uniform small particle size that did not ag-
gregate on standing for several hours.
4. S0"2 + Me(x) MeS0 + (X)
This method utilizes metal lochromic indicators containing polyvalent
cations which react with sulfate to release the ligands. Barium, thorium
and zirconium have all been employed.
The ligands have been employed two ways. One approach consists of re-
acting the sulfate with the polyvalent cations and using the excess cations
to form a colored complex. The alternate approach reacts the metallochromic
indicator with sulfate to release the ligands which are then measured either
by a bleaching reaction or color development.
These methods have employed methyl thymol blue, a thorium borate-
amaranth Hy° ,558,559,5607 methylsulphonazo III, pyrocatechol violet ,;LZ£t'
and SPADNS. One method was reported based on the bleaching of a colored
thorium complex rather than the development of a colored complex*±Zr.'
The barium chloranilate method also is in this group. In this method,
the insoluble barium chloranilate reacts with sulfate to produce barium
sulfate and release the water soluble chloranilic acid. The released chlor-
anilic acid is then measured.
The release of an organic component has also been employed to develop
fluorescent methods. The thorium salts of morin,-!-i=/ flavonol, 403 / and
lnr>T-nno404,405/ have been used in fluorescent methods.
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-2 +1
5. SO + 2Na - > Na2S04
This procedure is based on the determination of sulfate by titration
with standard base* The procedures are primarily methods for converting
the salts to free acids and eliminating other acidic components. Analysis
is normally accomplished by alkalimetry (10 references). Plain coulometry
has been employed to give total acid equivalents and prefilters have been
employed to remove major interferences. The acids have been released from
the salts using hydrogen form ion-exchange resins. Sulfates have also been
separated by microdif fusion, thermal decomposition, and chromatography
using activated alumina.
-2
6. SO (physical properties)
These procedures rely on some physical characteristic of the sulfate.
Methods have employed I-R Qpor.t- -rnphnt-rmiPi- 1^,638 ,639, 65 6/ emission spec-
trophotrometry,^ii/ x-ray defraction and prm' g«H nn.,638,642,660/ an(j refrac-
tive index of the precipitate ."H' Efforts have also been made to identify
sulfates by crystal shape using microscopy .f""?"' with and without
color development.
7. S0"2
This method relies on converting the sulfate to S02 using hot cop-
per * * or Mn.283/ Once the conversion is completed, the S02 may
be measured using flame photometry^i22' gppf-r-rnphnfrmiPt-ry.281,291,300/ or
conversion to S04= with I^*^ and measured using alkalimetry.283/ Or other
sulfate procedure.
Sulfate may also be precipitated as perimidylammonium sulfate which
is then pyrolyzed to produce S02 which is measured. "'
8.
There are a number of publications which convert the sulfate to H-S
which in turn is measured. A number of reducing agents have been employed
which include hydrogen with a platinum catalyst, 285,301,302 ?304/ Znd2 +
w pn 297,3037 Sn + H Pn 2.9.0.296/ and Ti + H,PO. ^25/
• J H1 J f J ^
A number of investigators have employed hydroiodic acid for the reduc-
9Q9 9Q^/
tion combined with formic acid and red phosphorus, t ' hydrochloric
and hypophosphorus acids, ^ i, ' formic acid and hypophosphite,122' acetic
acid and sodium hypophosphite,.£§7_' acetic anhydride and sodium hypophos-
phite,lZl' and 5070 hypophosphite and hydrochloric
10
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The resulting hydrogen sulfide has been collected in a cadmium solu-
tion and measured gravimetricallyJLSf? volumetrically using mercury acetate
with dithizone as an indicator,2°°i2i95' iodine solutionsl£l/ or using polar-
ography* I - i/ Procedures have also measured the hydrogen sulfide by collect-
ing the H2S in zinc sulfate and measuring iodometrically285>290l294l297i304/
or collecting in zinc acetate followed by the methylene blue reaction* °l
289.292,293,2997
11
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SECTION V
FACTORS AFFECTING THE ANALYTICAL PROCEDURE
An analytical procedure usually consists of several steps in obtaining
the desired results. The weakest step in the procedure will therefore limit
the results* To analyze for sulfate, one can either employ a reaction which
is specific, remove or mask the interferences, or separate the sulfate ion
prior to analysis*
The majority of the sulfate procedures utilize the formation of an
insoluble precipitate as the detection method. The sulfate salts must be
insoluble and other salts should be soluble* A review of the literature
shows that barium is the best possible choice of inorganic cations avail-
able* Although lead, strontium, thorium and other cations have been employed,
they will suffer from interferences resulting from the production of other
insoluble salts*
The interferences resulting from the presence of various cations may
be easily eliminated by treating the sample with a hydrogen form ion ex-
change resin* The resulting solution is then essentially a mixture of an-
ions from which sulfate must be selectively measured. The presence of other
anions essentially rules out methods based on alkalinity.
The solubility of barium sulfate is the lowest of any inorganic sul-
fates. Barium is therefore the inorganic reagent of choice for analyzing
sulfate. There are a number of other barium salts which have low solubili-
ties in water. These are potential interferences which are listed in Table
1 with their solubilities.
All of the barium salts in Table 1 become more soluble as the pH is
decreased with barium sulfate being affected only slightly. A procedure
using barium as a sulfate reagent therefore becomes essentially interfer-
ence free at a low pH. An analytical procedure based on barium precipitation
should therefore be performed at a low pH.
These criteria have been used to eliminate from further consideration
analytical procedures using cations other than barium and the colorimetric
12
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Table 1. POTENTIAL INTERFERENCES RESULTING FROM
INSOLUBLE SALT FORMATION AT A PH. OF 7.0
Potential anion
Interference
Arsenate
Carbonate
Chromate
Fluorosilicate
lodate
Molybdate
Oxalate
Phosphate
Selenate
Silicate
Sulfate
Sulfite
Solubility in 1^0 of barium
salt; percent
0.055
0.002
0.0003
0.026
0.033
0.0058
0.009
Insoluble
0.012
Insoluble
0.0002
0.02
13
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procedures using barium in near neutral mediums. The same limitations ap-
ply to methods relying on the precipitation of barium sulfate to produce
or release a colored product.
Golorimetric and spectrophotometric procedures using rhodizonate,
tetrahydroxyquinone or indicators containing sulfo or hydroxy groups in-
cluding carboxyarsenazos are used at a pH of 5.5 to 6.5. Under these con-
ditions, most of the anions in Table 1 interfere with the procedure.
The only known indicators which can be used at a low enough pH to
avoid phosphate and arsenate interferences are carboxyarsenazos with one
of the -GOOH or AsO H groups replaced by an -SO H group.>
14
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SECTION VI
CRITERIA FOR METHOD SELECTION
A requirement of this program was the selection of the two most prom-
ising sulfate methods located during the literature search. To accomplish
this objective, the methods were evaluated using a set of criteria. These
criteria are listed below in descending order of importance:
Precision
Interferences
Sensitivity
Accuracy
Simplicity
Time/Analysis
Automated
Equipment Cost
15
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SECTION VII
METHOD EVALUATION
To accomplish the method evaluation and selection, the best procedure
for each technique was selected. These procedures and their evaluations
are presented in this section.
ATOMIC ABSORPTION
Atomic absorption measures excess barium ions remaining after sulfate
precipitation. Precipitation can be carried out in acid solutions to mini-
mize interferences. Detection limits for excess barium should be around
0.1 ppm with a precision of 5 to 7%. Some interference was associated with
most of the ions investigated.—' The strongest interference was associated
with phosphate. The error produced was related to the phosphate concentra-
tion. A phosphorus level (as phosphate) of 0.125 |Jig added to a 6 ppm sulfate
solution produced a 2% positive interference. The maximum effect was about
9% positive.
The accuracy is estimated to be plus or minus 10%. The procedure is
simple. Time for each precipitation is 15 hr, however, operator time is
minimal. An automated procedure has not been published. The equipment cost,
which includes an AA with automatic background correction and a high speed
centrifuge, is estimated to be $18,000 for the manual method.
Atomic absorption inhibition titration is an alternate method for
analyzing sulfate. Its main advantage over measuring residual barium is a
rapid analysis. The barium precipitation is not required, which eliminates
the 15 hr precipitation and the use of a centrifuge. Experimental results
indicated that the method is only applicable when the sulfate ion concen-
tration is at least twice the combined concentration of all other ions.
In general, Christian and Feldman* have found that most anions inter-
fere with the indirect determination (cation precipitation) using atomic
absorption, the interference being in direct proportion to the concentration
* Christian, G. D., and F. J. Feldman, Anal. Chim. Acta., 40:173 (1968).
16
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of all other anions. The same holds true for indirect titration using either
magnesium or calcium. Interferences have been reported resulting from pro-
teins and sugars as well as anions.
CHROMATOGRAPHIC
Methods listed under the heading Chromatographic are considered as
separation techniques* A color development reaction is generally required.
The technique is more qualitative than quantitative with poor precision
and accuracy.
GOLORIMETRIG
Following the criterion of using a barium reagent at low pH, as dis-
cussed in the previous section, eliminates most colorimetric procedures.
The use of nitchromazo . . / as an indicator with a barium salt titration
at a pH of 2.0 has the highest potential as an interference-free colorimetric
procedure. Arsenate at four times the sulfate concentration and phosphate
at five times the sulfate concentration produce a relative error of -1.970.
Phosphate at the same concentration as the sulfate had no effect. Informa-
tion on other interferences was not presented, however, none should exist
with the possible exception of silicates. The precision of the methods was
not given but titration agreed within 0.3 (ig of barium. The lower limit of
detection was given as 0.04 mg of S as sulfate in a 10 to 15 ml sample.
The method is simple (direct titration), fast, and requires no special
equipment. The procedure has not been automated but has that potential.
CONVERSION-DETECTION
These methods in general are total sulfur methods and are not specific
to sulfate. Interferences would therefore be produced by sulfur, sulfides,
sulfites, and thiosulfates. The procedure must therefore be combined with
a separation technique prior to conversion to HoS or SO^. Only two methods
were located which included a separation step. One method used controlled
thermal decomposition for separation. '
This method was developed to measure sulfuric acid aerosols. However,
the authors provide information on the decomposition temperatures of other
sulfates which permits, by temperature programming, measuring other sul-
fates. As the method is described, only sulfuric acid, ammonium sulfates
and copper sulfates are decomposed and measured. Three methods were de-
scribed for measuring the generated S02» The colorimetric method had a rel-
ative deviation of 2.2% for 23 u-g of l^SO^. The relative deviation was
17
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2.97% for 8,4 y,g of H2SO^ using coulometric detection and 1.05% for 6.0 ^ig
of I^SO/ using flame photometric detection. The sensitivity is more than
adequate for ambient analysis. The procedure is moderately complex, re-
quiring three steps. Time for each analysis is reported as 10 min/sample
with actual analysis probably running around 30 samples/day. The method
could not be easily automated and equipment cost using FPD (best precision)
would be approximately $5,000.
A separation procedure has been published which precipitates perimidyl-
ammonium sulfate. The precipitate is then thermally decomposed to yield
sulfur dioxide which is measured by one of several techniques.
The precipitation step requires about 10 min. From the publication,
it appears that separation of the precipitate is not required. This being
true, the procedure would consist of precipitation, evaporation, pyrolysis
and measuring the liberated SOo • The best results were obtained using the
West-Gaeke procedure for 862 analysis which had a coefficient of variance
of 5.3% at the 10 jj,g level. However, an FPD sulfur analysis could be em-
ployed with a precision of 6 to 10% at a 0.5 ng level of sulfate. The meth-
od is apparently free of any major interferences. No effects were found for
phosphate, carbonate or nitrate. An earlier investigation of aminoperimidine
(PDA)——' found that a 10-fold excess of most common anions would not inter-
fere with the sulfate precipitation. The method appears to have good preci-
sion, to be free of interferences, and to have adequate sensitivity and
accuracy. The procedure is more complex than most of the other sulfate
methods. Time for the analysis is reported as 4 to 5 min/sample. However,
if the West-Gaeke procedure is used considerably more time would be required
for a complete analysis. Automated procedures for SC>2 are available but
this would require an additional capital investment. Depending on which
options are selected, the equipment cost would vary from several hundred
to several thousand dollars.
ELECTROMETRIC
All of the electrometric methods are based on end-point determination
using primarily barium or lead as the titrant. All of the potentiometric,
conductometric, and polarographic titrations suffer from a number of inter-
ferences.
The ion-selective electrodes have also been employed for sulfate anal-
ysis. Both lead and barium have been used with cation selective electrodes.
The interferences produced by cations could be effectively removed using
ion exchange resins. Cations listed as interferences with the lead electrode
P| O | A | O ~j f) I
include Cu , Hg"*"^ and Ag"**!... . ' The anion interferences are a direct re-
sult of insoluble precipitate formationiZZ' and could be minimized by op-
erating at a pH of 2.0. However, since response is related to the ionic
strength of the solutions, there are inherent errors in using a specific
ion electrode.
18
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A divalent electrode was investigated as an end-point indicator for
a barium titration*2=lft' The solubility product of barium sulfate was too
large and the electrode sensitivity too low to give reliable results* Anion-
responsive electrodes based on ion association extraction systems have been
oio7 J
investigated* ' Information on interferences indicates a significant
problem* '
FLAME-PHOTOMETRIC
This technique appears to have no advantage over other methods for
sulfate analysis* The method is based on precipitation of an insoluble
sulfate and measuring the excess barium. Barium would be the reactant of
choice at a low pH. Interference problems would be typical for this reac-
tion mechanism*
FLUOROMETRIC
All of the fluorometric methods employed a thorium salt. This system
suffers from significant interferences by phosphate, tungstate, molybdate,
citrate, arsenate, selenate, vandate and several anions*
GRAVIMETRIC
Gravimetric procedures using barium at a low pH have been intensively
investigated. The technique is still generally considered to be the most
accurate* However, because of the long time required to complete the pre-
cipitation and the problem of coprecipitation, it is seldom employed. The
original investigation of substituted benzidines was initiated to overcome
these shortcomings, a goal which was achieved. The substituted behzidine
sulfates have lower solubilities, precipitation times are shorter, and the
coprecipitation problem is decreased* However, because the substituted
benzidine precipitation was still rather time-consuming and suffered from
interferences, all of the recent publications have employed procedures
other than gravimetric*
RADIOMETRIC
All of the radiometric procedures published were employed to investi-
gate reaction mechanisms* Their weakness as an analytical method lies in
the basic problem of the precipitation reaction. All of the cations util-
ized for precipitation produced serious interference problems.
19
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SPECTROPHOTOMETRIC
Three spectrophotometric methods were selected for consideration be-
cause of basic differences in the approach.
The methylthymol blue method (MTB) employs a barium precipitation re-
action with an indicator which is pH sensitive and will not form the col-
ored chelate in acidic solutions. This deficiency is at least partially
controlled by conducting the precipitation at a low pH (2.6) and then rais-
ing the pH to 12.8 to form the chelate. Interferences are therefore minimized
if the times allowed for precipitation and color development are carefully
optimized. The procedure does suffer from a phosphate interference and also
it must be conducted using automated equipment because the reagent is easily
oxidized*
Data interpretation is more involved using the MTB procedure than it
is with most procedures because the color reaction does not follow the
Beer-Lambert law.
The barium chloranilate procedure relies on the barium precipitation
reaction and measuring the released chloranilic acid. The procedure can
be run as a manual spectrophotometric method or as an automated method.
The greatest sensitivity is obtained using the manual procedure at 327.5
nm. Chlorides, fluorides and phosphates are listed as interferences. It
is reported ' that by using a hydrogen form ion exchange resin and buf-
fering to pH 1.75, the interferences are minimized. Under such conditions,
100 ^g of phosphate and 50 ^ig of fluoride produce an error of 2% when
analyzing 10 \ig of sulfate. Under the same conditions, a sample containing
up to 17.5 p,g of chloride may be analyzed without affecting the results.
The spectrophotometric determination of sulfate using 2-aminoperimidine
has been developed to cover a range of 4 to 120 ppm. ' The method is fast,
simple, and could be automated with the proper colorimeter (305 nm). The
relative standard deviation is 3.7 for 50 p,g/ml of sulfate and 5.0 for
10 p,g/ml. A number of interferences were investigated with 50 ppm of phos-
phate producing a 170 error. Large amounts of acetate, chloride, bromide,
and iodide had no effect. Fluoride, nitrate, and carbonate do interfere.
Fluoride at 500 \ig/ml produced an error of 4% and nitrate at 500 (j,g/ml
produced a 60% error. At 100 ^g/ml, nitrate had no effect. Carbonate inter-
ferences could probably be eliminated by acidifying the solution.
20
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SUBSTITUTED BENZIDINES
The methods employing substituted benzidines are discussed in this
section under the measurement techniques employed.
TURBIDIMETRIG
Two methods were selected for consideration which were based on tur-
bidity.
The turbidimetric method normally encountered employs the barium pre-
cipitation reaction. Barium chloride is normally used in an acid medium
which eliminates most interferences. There is no need to remove either
cations or anions. Silica and phosphate, in large quantities as well as
turbidity and color, are the only reported interferences. Phosphate is
not normally present in sufficient quantities to cause an interference.
A drift in the base line caused by BaSO^ buildup is also encountered when
using an automated method. The major disadvantage of this procedure is
poor precision. A number of stabilizing materials have been investigated
in an effort to obtain improved precision. There are a number of factors
which influence the size of the particles precipitated and therefore the
precision of the method. These factors include sulfate concentration, re-
agent concentration, reaction temperature, presence of other ions, clean-
liness of the system, age of the barium reagent, and precipitation time.
Good results are therefore closely related to the operator's skill. Pre-
cision, as standard deviation, varies from 1.78 ug/ml analyzing 9.2 y.g/ml
of sulfate to 11.8 ng/ml analyzing 19.9 |ig/ml of sulfate »£t§I'
A second turbidimetric procedure uses 2-aminoperimidine (PDA) as the
precipitant. This reagent reacts with sulfate to produce a heavy white
silky precipitatei" 3' The particle size is primarily less than 2 \i across.
The particles do not aggregate and the solubility of the precipitate is
very low. The procedure is capable of easily detecting 0.2 ppm and has the
potential of detecting as low as 0.05 ppm of sulfate. The precipitation
is completed in 1 to 2 min. In the 0.25 to 1 ppm range, it was reported
there was no increase in opacity after 5 min.
The PDA is susceptible to oxidation and precaution should be taken
to avoid undue exposure. The procedure does suffer from some interferences.
The major problem is with fluorides and phosphates. Analyzing a 0.75
|j,g/ml sulfate sample, 1 u.g/ml of fluoride produces an error of 10% and
1 ^g/ml of phosphate produces an error of 25%.
21
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SECTION VIII
METHOD SELECTION
Based on the discussion presented in the previous section, the follow-
ing methods were selected for final consideration as the most promising:
* Volumetric using nitchromazo;
* Conversion using 2-aminoperimidine and detection using West-Gaeke;
* Spectrophotometric using methyl thymol blue;
* Spectrophotometric using barium chloranilate;
* Spectrophotometric using 2-aminoperimidine; and
* Turbidimetric using 2-aminoperimidine.
A final review was made and four methods were eliminated. The volumetric
method was eliminated because of a lack of information on the lower limit
of detection, precision, accuracy, and interference effects. The conversion-
detection method using 2-aminoperimidine was eliminated primarily because
of its complexity and the lack of supporting data. The turbidimetric and
Spectrophotometric methods using 2-aminoperimidine methods were eliminated
because of potential interferences.
It therefore appears that the most promising methods at present are
those using MTB and barium chloranilate. The automated MTB procedure re-
s f\"\l
ported by Lazrus ' is recommended. The barium chloranilate method does
not have sufficient sensitivity at 530 nm using the automated procedure.
We therefore recommend as the second method, the manual procedure with
measurements made using either the 530- or 310-nm absorption peaks as de-
scribed by Schafer JLZ5/
22
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APPENDIX
BIBLIOGRAPHY OF METHODS FOR
SULFATE ANALYSIS
23
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ATOMIC ABSORPTION
1. Borden, F. Y. , "Indirect Method for the Measurement of Sulfate by Barium
Absorption Spectrophotometry," Soil Sci. Soc. Amer. . 34(4) :705-706
(1970). ~~
Excess Ba by atomic absorption.
2. Christian, G. D., "Determination of Nonmetals by Atomic Absorption
Spectrophotometry," Anal. Chem. Acta. 49(2) : 173-179 (1968).
_ o
SOT causes proportional decrease in Ca 4226 A line
3. Dunk, R. , "Determination of Sulfate by Indirect Atomic Absorption
Spectroscopy." At. Absorption News Letter. 8(4): 79-81 (1969).
AA measurement of Ba after precipitation of
4. Forbes, E. A., "Determination of Microgram Amounts of Sulfate by
Emission Spectroscopy of Barium with N£0-Acelytene Flame," Analyst.
98(1168) :506-511 (1973).
Method for 0.5 to 10.0 ppm by Ba emission at 553.55 nm; sensitive
and relatively free of interferences.
5. Lin, C. I., "Determination of Phosphate, Silicate, and Sulfate in
Natural and Wastewater by Atomic Absorption Inhibition Titration,"
Anal. Chem.. 44(13) : 2200-2204 (1972).
Simultaneous detection of silicate, phosphate, sulfate 0 to 30
ppm SO?; Titrate SO, with metal cation, monitoring AA signal for
cation (use Mg
6. Mansell, R. E. , "Industrial Applications of AAS (Atomic Absorbtion
Spectroscopy)." Amer. Lab.. (3):31-32, 34 (1970).
Indirect determination of SOo using a barium salt in air near sul
fonating process. A brief description of methods, and general
usefulness.
24
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CHROMATOGRAPHIC
7. Ackermann, G., "Quantitative Paper Chroraatography of Inactive Substances
Through Radioactive Additions," Talanta. 15(1):63-71 (1968).
Radiometric measurement by adding constant quantity of active
sulfate
8. Brezgunova, I. N., "Thin-Layer Chromatography of Anions," Zh. Fiz.
Khim., 45(7):1785-1787 (1971).
TLC method for separation of phosphate, sulfate, halide, and poly-
thionate anions of organic and inorganic compounds.
9. Canic, V. C., "Thin-Layer Chromatographic Separation of Anions on
Starch." Fresenius Z. Anal. Chem.. 229^2):93-96 (1967).
Qualitative detection.
10. d'Ans, J., "Use of Anion Exchangers in Analytical and Preparative
Chemistry," Chem-Ztg., 76:841-844 (1952).
Nonaqueous solvents and anion resins.
11. De Souya, J. A., "Inorganic Analysis by Electrophoresis," Rev. Quein.
Ind.. 42J489): 11-15 (1973).
Separation of 49 inorganic ions with very simple equipment as
described.
12. Handa, A. C., "Microdeterraination of Sulfide, Sulfite, Sulfate, and
Thiosulfate by Thin-Layer Chromatography and Ring Colorimetry,"
Talanta. 20(2):219-222 (1973).
TLC onmicrocyrstalline cellulose; determined by ring colorimetry.
13. Koscielny, J., "Separation of Selenites, Sulfates, and Tungstates in
the Presence of Condensed Phosphates," Pr. Nauk. Wyzsz. Szk. Ekon.
Wroclaw. . 23^:205-210 (1970).
Paper chromatographic separation as molybdosulfate formed under UV
radiation.
25
-------
14. Lewandowsky, A., "Quantitative Analysis of Anions with Filter Paper
Containing Anion Exchangers," Roczniki Chem., 30:559-567 (1956).
Ion Exchange Paper Chromatography Cl, N03, SO^
15. Lowe, L. E., "The Separation and Determination of Organic and Inorganic
Sulfate in Soil Extracts," Can. J. Soil Sci.. 46(1):92-93 (1966).
Column of Sephadex elute with borate buffer. Good recovery above
10 ppm.
16- Nakano, S., "Behavior and Separation of Sulfate and Fluosilicate by
Paper Chromatography," J. Chem. Soc. Japan. 75:328-330 (1954).
Two parts NH^OH to eight parts MeOH recommended as solvent; success-
ful separations when Na salts used.
17. Rudnicki, R., "A New Color Reaction for the Detection of Sulfate and
Pyrosulfate Ions on Paper Chromatograms," Chem. Anal., 5^:769-744
(1960).
Paper chroraatographed and developed with Hanes-Isherwood reagent..
Separated all sulfur compounds.
18. Tokutomi, M., "Electrophoresis of Inorganic Anions on Anion-Exchange
Paper." Bunseki Kagaku. 21(l):81-87 (1972).
Anion migration was greater than on filter paper at pH 4.0 and 7.0
using H3H04-Na2HP04 at 20 mA/2.5 cm.
19. Tsitovich, I. K., "Organic Reagents and Concentration of Ions by Means
of Ion-Exchange Resins," Trudy Komissii Anal. Khim., Akad. Nauk SSSR
Inst. Geokhim. i Anal. Khim.. 11:411-417 (1960).
S04= determined as I^NCgH^Cgl^NI^-I^SC^
20. Witkowski, H., "Filter Paper with Cation Exchangers," Roczniki Chem..
30:549-557 (1956).
Ion Exchanger Paper Chromatography
21. Zamfir, J., "Analysis of Mixtures of Sulfur Anions Labeled with Sulfur-
35," Rev. Roum. Chlm.. 13(2):219-223 (1968).
Separation of Na2, 803, Na2S, and ^2864 investigated using TLC,
EP and column Chromatography. TLC and EP did not work. Na2S
could be separated on A1203. Separation of N32S03 from Na2S04 not
investigated.
26
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COLORIMETRIC
22. Abrahamezek, E., "Titrimetric Microdetermination of 0.001 N Sulfate
Solutions with Sodium Rhodizonate as Indicator," Mikrochim. Acta,
.U 354-363 (1937).
Titration with Ba4*.
23. Akiyama, T., "Direct Titration of Sulfate," Kyota Yakka Daigaku Gakuho,
5j 48-50 (1957).
Titration with Ba(ClO)^ and thorin.
24. Alicino, J. F., "Microvoluraetric Method for Determination of Sulfur in
Organic Compounds," Anal. Chem. , 2Jh85-86 (1948).
Solution + NaOH, EtOH, and dipotassium rhodizonate; titrated with
BaCl2 until color persists.
25. Andrews, J. R., "Volumetric Barium Chromate Method for Sulfates," Ind.
Eng. Chem. . Anal. Ed. . 3^:361-362 (1931).
Titration with ferrous ammonium sulfate; back titrate with perman-
ganate.
26. Antonova, A. A., "Rapid Complexometric Method for Determining Sulfate
Ion in Potash," Steklo i Keram. 19(12):23-24 (1962).
Acidify (pH of 6); add BaCl2, Na rhodizonate, pH 10 buffer, and
alkali blue indicator. Titrate with Triton B.
27. Archer, E. E., "Titrimetric Determination of Sulfate with Lead Nitrate
as Titrant and Dithizone as Indicator," Analyst, 82j 208-209 (1957).
28. Asada, T., "Determination of Phosphate and Sulfate by the Ion-Exchange
Method." Bunseki Kagaku. 6jlOO-101 (1957).
Using "Amberlite IR-120" and NaOH titration.
29. Ashbrook, A. W., "Volumetric Determination of Sulfate," Analyst, 86j
740-744 (1961).
S0^~ precipitated as PbSO^ by Pb(N03)2 from ac!ueous EtOH; precipi-
tate dissolved in EDTA, excess EDTA determined by ZnCl2 titration,
Eriochrome Black T indicator.
27
-------
30. ASTM, "Standard Methods of Test for Sulfate Ion in Water and Waste
Water (D516); Method C - Volumetric Method," Annual Book of ASTM
Standards. 31.:427,430-433 (1974).
Details of BaCl -thorin titration.
31. Atkinson, H., "The Volumetric Determination of Soluble Sulfates by
Means of Barium Chloride and Potassium Stearate," Analyst, 50:590-
600 (1925); Analyst. 5Jj 81-82,140-141 (1926).
precipitation; add stearate solution; back titrate with
using BHD indicator or bromothymol blue.
32. Babkin, M. P., "Colorimetrie Methods for the Determination of Sulfates,"
Lab. Prakt., 6_: 19-21 (1939).
Benzidine method had errors as much as 50%. Precipitate as PbSO/
in dilute AcOH and EtOH. Dissolve in NaOH and add alkaline sulfide
to color; 10% error.
33. Babko, A. K., "Color Reactions for Sulfate Ion," Trudy Komissii Anal.
Khim., Akad. Nauk S.S.S.R., Inst. Geokhim. i Anal. Khim. . 11^309-322
(I960).
Colored complexes of Zr, Th, and Ce(III) with alizarin, alizarin S,
Red Acid S., Eriochrome Black 7, aluminon, stilbazo, stibbnaphthazo,
Acid Chrome Blue K (I), and acid chrome dark blue studied. EtOH
or acetone enhances. ZnNO^ and Acid Chrome Blue K solution mixed
with HCl. Add 40% acetone to sample and measure color change.
0.2 ug/ml.
34. Bakacs, E., "A Fast Titrimetric Method for the Detection of Sulfate
with Barium Chloride," Magyar Kern. Folv6irat. 6Jj48-50 (1955).
Direct titration of S04= with 0.01 M BaCU in EtOH. Eriochrome
Black T with sequestered Mg ion indicator. Titrated with NlfyOH,
methyl red indicator.
35. BakScs, E., "Fast Titrimetric Method for the Determination of Sulfate
Ions," Magyar Kern. Folyoirat, 62_:135-139 (1956).
Titration with BaCl2 and thorin.
28
-------
36. Balakhovskii, S., "Volumetric Method for the Microchemical Determina-
tion of Sulfates," Z. anal. Chem. . 86j 344-346 (1931).
Sulfate + BaCl2. Titrate with K2CrO^. Phenol red, thymol blue,
or cresol red indicator (any one).
37. Banerjee, D. K. , "Determination of Diethyl Sulfate, Ethyl Hydrogen
Sulfate, and Sulfuric Acid in Mixtures," Anal. Chem., 36(10) : 2016-
2020 (1964).
Ethyl hydrogen sulfate and sulfuric acid determined by titration
with N(C4Hg)4OH. Diethyl sulfate is hydrolyzed at 130°C and H2S04
formed is titrated with aqueous base.
38. Banyai, E., "The Use of Precipitation Exchange Reactions in Analytical
Chemistry," Acta Chim. Acad . Hung. , 8j 383-94 (1956).
exchange with 63(103) 2, BaC2°4> an<^ BaCrO^. lodate and chromate
determined iodometrically; oxilate with
39. Bartoshevich, E. I., "Rapid Method for Determining the Sodium Sulfate
Content in a Complex Solution," Maslo-Zhir. Prom., 35j(2):39-40 (1969).
Neutralize acid; add BaCl_. Titration with I^CrO, , methyl red
indicator.
40. Basargin, N. N., "Analytical Use of Nitchromazo, A New Indicator for
Barium," Metody Anal. Khim. Reaktivov Prep., (12) .-97-102 (1966).
BaCl2 titration with Nitchromazo indicator.
41. Baxi, D. R. , "Estimation of Sulfate by Ion-Exchange Method," Salt Res.
Ind.. £(4): 130-134 (1967).
Ion-exchange S04= to H2S04. Titrate with NaOH.
42. Behr, I., "Simultaneous Analysis by an Ion-Exchange Method of Phos-
phates, Sulfates and Chlorides," Bull. Research Connal Israel, 5A_:
259-262 (1958).
Converts SO/" to acid with ion exchange. Phosphates and chloride
determine volume and SO/= by difference.
43. Belcher, R., "Indirect Titrimetric Determination of the Sulfate Ion
with Ethylenediaminetetraacetic Acid," Chemistry and Industry,
pp. 850-851 (1954).
Acidified sulfate + BaCl2; add excess of EDTA; titrate with MgCl2.
29
-------
44. Belcher, R. , "New Method for Titration of Sulfate," Chem. Anal., 17/3):
497-501 (1972).
Titration with 0.05 M PbCNOj^; back titrate with 0.01 M K4Fe(CN)g.
45. Bien, G. S., "High-Frequency Titration of Micro Quantitites of Chloride
and Sulfate," Anal. Chem.. 2£(5) :909-911 (1954).
Titration with Ba(OAc) with a chemical oscillometer.
46. Birstein, G., "Titrimetric Determination of Aluminum Sulfate and Sul-
furic Acid Present Together," Przemyst Chem. , 1&: 317-321 (1934).
Titration with Ba(OH) . Thymol blue indicator.
47. Bond, R. D. , "Determination of Low Concentrations of Sulfate with
Barium Chloride and Ethylenediaminetetraacetic Acid," Chemistry and
Industry, pp. 941-942 (1955).
Ba precipitation with boiling; titration with EDTA and Eriochrome
Black T as indicator.
48. Bosch, F. de A., "New Detection for Barium and Sulfate Ion. I. Deter-
mination of Barium by lodoimetry," Anales real, soc. espafi. f is . y
quim. , 52B_: 187-198 (1956).
Sulfate + Bad-. add Na^O,. Titrate with I2 .
49. Bovee, H. H. , "Spectro-Visual Method for Determining End Points, Appli-
cation to Titration of Soluble Sulfate," Anal. Chem., 2jh 1353-1355
(1957).
Titration with BaCl^, tetrahydroxyquinone indicator. Light trans-
mitted by Wratten filter No. 45, End point green — *blue for S0^~-
BaCl titration.
50. Bozhevol'nov, E. A., "Determination of Sulfate in Water, Acids, and
Salts with Fluorexon," Metody Analizo Khim. Reaktovov i Preparatov,
Cos. Kom. Sov. Min. S.S.S.R. po Khim., (4):131 (1962).
Sample titrated with EDTA in UV light until solution matches fluo-
rescence of blank; sample evaporated with Ba, KOH, and Fluorexon
in KC1.
30
-------
51. Briwal, A. A., "Change in Jellinek's Method for the Determination of
Sulfate," Z. Anorg. Allgem. Chem., 156^:210-212 (1926).
Add BaCl2; titrate excess with K2CrO^. Methyl red indicator.
52. Bruno, A., "Determination of Sulfates in Solution by Physico-Chemical
Volumetry," Compt. Rend., 154_:984-986; Ann. Fals.. 5^:237-239 (1912).
Determination in wine; titration with Ba(OH)2.
53. Bruno, E., "Oscillometric Determination of a Small Quantity of Sul-
fates," Rass. Chim.. 17j[5) :216-219 (1965).
Benzidine-HCl in iso-PrOH titration ;£ NaOH; sensitive to 9 pg/ml.
54. Budesinsky, B., "Determination of Sulfur and Sulfate by Titration with
Barium Perchlorate. Comparison of Various Color Indicators," Anal.
Chim. Acta, 39(3) :375-381 (1967) and Anal. Chem.. 210jl61 (1965).
4,5-Dihydroxy-3,6-bis(p_-methyl-o-sulfophenylazo-naphthalene)-2,7-
disulfonic acid (Sulfonazo II) superior to thorin.
55. Burg, W. V., "Direct Titration of Sulfate - Erythrosin as Internal
Indicator," Ind. Eng. Chem.. Anal. Ed., _11:28-30 (1939).
Pb(NO )2 titration.
56. Caldwell, W. E., "Reduction Reactions with Calcium Hydride. I. Rapid
Determination of Sulfur in Insoluble Sulfates," J. Am. Chem. Soc.,
^: 2936-2942 (1929).
lodometric titration.
57. Callan, T. P., "Determination of Sulfur in Organic Compounds. Oxida-
tion of Sulfur of Cystine and Methionine, Combination of Parr Oxida-
tion Bomb and Acidimetric Benzidine Method, and Determination of
Small Amounts of Sulfur Compound Present as Contaminant in Organic
Material," Ind. Eng. Chem., Anal. Ed.. 13_:450-455 (1941).
S to H2SO^ (benzidine sulfate method); S oxidized with KMnO^ 804
as BaSO/.
58. Casini, A., "Complexometric Determination of the Sulfate Ion," Ann.
Chim.. 46:697-702 (1956).
Excess BaCl2 titration with EDTA. Naptholphthalein indicator.
31
-------
59. Ceausescu, D., "Improvement of the End Point Determination in the
Titrimetric Determination of Sulfates," Rev. Chim.. 10_:538 (1959).
Ba"1^" titration, Na alizarin sulfonate indicator. Methylene blue
as contrast component.
60. Ceausescu, D., "Indirect Determination of Sulfates in Water by Titra-
tion with Potassium Stearate by Using Eriochrome Black T as Indicator,"
Acad. rep, populare Romine Baza cercetari stiint. Timisoara Studii
cercetari stiint.. Ser. stiint. chim.. 5J1-2) -.77-81 (1958).
SOT precipitates excess Ba. Titrate excess with K stearate.
61. Ceausescu, D., "Indirect Determination of Sulfates in Water by Titration
with Potassium Stearates or Palmitates After Elimination of Calcium
and Magnesium," Acad. rep, populare Romine Baza cercetari stiint.
Timisoara Studii cercetari stiint. Ser. stiint chim., 7_: 37-42 (1960).
SOT determined by Bad- precipitation; titrate excess reagent with
K stearate or palmitate in presence of either phenolphthalein or
Eriochrome Black T as indicator; Ca and Mg interfere.
62. Ceausescu, D., "Rapid Determination of Sulfate, Chloride, and Nitrate
Ions in Water in a Single Sample," Z. anal. Chem.. 165:424-428 (1959).
HCIO^, BaSO^, EtOH, and I added and titrated with Ba(ClO^)2-
63. Chalmers, A., "Volumetric Sulfate Determination. Rapid Method for
Determining Sulfur in Organic Compounds," Ind. Eng. Chem., Anal. Ed.,
4:162-164 (1932).
**»!
S—>SO,. Add BaCl2; titrate with Na2C03, phenolphthalein indica-
tor.
64. Chaque, A. R., "Application of Adsorption Indicators in Volumetric Pre-
cipitation," Anales guim. y farm., pp. 4-8, 11-14. In Rev, quim. farm..
24:4-14, Santiago, Chile (1945).
Investigation of indicators for Ba"1"1" titration.
65. Chatron, "Microdetermination of Sulfates. Application to Sulfur and
Total Bases in Serum," Bull. Soc. Chim. Biol., 13j 300-325; J. Pharm.
inu., L3j244-254,321-327,425-435 (1931).
Precipitated as benzidine-SO.. Titrate with NaOH, bromothymol blue
indicator.
32
-------
66. Chirkov, S. K., "Volumetric Determination of Water-Soluble Sulfates by
the 'Soda1 Method," Zavodskaya Lab., 3j420-424 (1934).
SO? precipitated with BaCl2; excess BaCl2 titrated with
against phenolphthalein; + 0.002%; optimum SOT concentration
0.1 to 0.15%.
67. CIBA, Ltd., "Analytical Procedure with Derivatives of Acid-Base Indi-
cators," CIBA, Ltd., Swiss 298,194, 1 July 1954 (Cl. 67).
3,3' ' ,5 ' ,5 ' '-tetrakis[(bis-carboxymethyl amino) methyl] phenol-
phthalein used to titrate excess Ba from BaClo addition.
68. Ciurlo, R., "Chelatometric Micro Determination of Sulfate in Small
Quantities," Atti. Soc. Pleoritana Sci. Fis. Mat. Natur., 12^3-4):
537-544 (1966).
EDTA - Excess titrated with Mg in 0.1% EtOH. Eriochrome Black T
indicator.
69. Commins, B. T., "Determination of Particulate Acid in Town Air,"
Analyst. 88; 364-367 (1963).
Filter sample titration with sodium tetraborate to ~ pH 7.
70. Cuthbertson, D. P., "The Inorganic Sulfate Content of Blood," Biochem.
J.., Z5jl237 (1931).
Benz id ine -Thymol.
71. Damerell, V. R. , "New Volumetric Method for Determination of Sulfate,"
Ind. Eng. Chem. , Anal. Ed., 6:19-21 (1934).
BaSO, precipitated; time measured for yellow coloration of turpeth
in Hg(NOo)2 on spot plate.
72. Davey, W. , "Analytical Applications of Sodium Lauryl Sulfate. II. The
Volumetric Determination of Sulfates," J. Appl. Chem., 5_:474-476 (1955)
Determination of SO/" by EDTA method; excess Ba precipitated with
sodium lauryl sulfate; excess sodium lauryl sulfate precipitated
with a quaternary ammonium salt.
73. Denk, G. , "Alkalimetric Determination of Calcium, Strontium, Barium
and Sulfate," Z. anal. Chem.. 13^:99-104 (1952).
Titration near the boiling point with Na^CO-.
33
-------
74. De Zombory, L., "Volumetric Determinations of Sulfate with Sodium
Rhodizonate as an Indicator," Magyar Kern. Folyoirat, 41; 189 -192
(1935).
- precipitation; titrate with IC^SO, using Na rhodizonate as
indicator.
75. Dittrich, S., "Microdetermination of Sulfate," Anales Fac. Quim. Univ.
Rep. Oriental Uruguay. 6j 107 -114 (1960).
Benzidine; titration to phenol red end point; anions precipitated
by benzidine, oxidizing substances, and certain others interfere.
76. Dollman, G. W. , "Determination of Sulfate and Phosphate in Water by
lon-Exchange-Titrimetric Method," Environ. Sci. Tech.. 2;. 1027-1029
(1968).
Ion-exchange SO. to H~SO,„ Titrate with
NaOH.
77. Dominikiewicz, M., "Titrimetric Determination of Sulfates," Bull, trav.
dept. chim. inst. hyg. etat. 31/1):3-6; Przemyst Chem.. 14:241-245
(1930).
Bad- titration with NH,K Chromate. Benzidine indicator.
78. Dragusin, I., "Complexometric Determination of Sulfates in the Presence
of Calcium and Magnesium," Rev. Chim.. 12_:303-304 (1961).
Dual EDTA titration to obtain S0,= by difference; uses Na rhodi-
zonate as indicator.
79. Dubois, L., "General Method of Analysis for High Volume Air Samples.
I. Sulfate and Sulfuric Acid," Mikrochim. Acta, (6):1268-1275 (1969).
Titration with Ba(ClO), and thorin. Includes alternate filter
extraction.
80. Dubois, L., "The Determination of Sulfuric Acid in Air: A Specific
Method," Mikrochim. Acta. pp. 269-279 (1969).
SOT determined by barium perchlorate-thorin titration.
81. Effenberger, M., "Chelatometric Determination of Sulfates in Water with
Calcein as Indicator," Chem. Listy. 52j 1501-1505 (1958).
Excess BaCl2 titrated with NaEDTA, calcein indicator.
34
-------
82. Ekedahl, E., "A Volumetric Method for the Determination of Sulfate
Ions," Svensk Kern. Tid.. 58;177-179 (1946).
Treatment of sulfate ions with Na2COo. The resulting carbonate is
dissolved in std. HCl and excess titrated with NaOH.
83. Ellis, W. G., "A Simplified Automatic Photometric Titrator Applied to
the Titration of Microgram Amounts of Sulfate,11 U.S. At. Energy Comm.,
TID-14741, (1961).
Automatic photometric titration of SO^ with Ba(C10,)2. Thorin
indicator. Well-defined end points with 50 to 200 ug SCT in cell.
84. Elsermann, E., "lodometric Titration of Sulfate," Z. anal. Chem., 134;
96-99 (1951).
Sulfate and BaCrO in HC10,, add KI, titrate with Na2S203.
85. Eriksen, T. E., "Determination of Small Quantities of Sulfate and Thio-
sulfate in Aqueous Solution of Sulfur Dioxide," Acta Chem. Scand.,
2^(8):3333-3336 (1972).
Column chromatography. Ba(ClO/)2 titration. HSCL masked with H2CO.
86. Erlich, J., "Volumetric Determination of Sulfate Ion," Ann. Chim. Anal..
Chim. Appl.. 2^:214-215 (1920).
Treatment of sulfate with BaCOo followed by titration of excess
carbonate with 0.1 N H2SO, in presence of Helianthin.
87. Erzsebet, P., "Rapid Titrimetric Determination of Sulfate Ions with
Barium Chloride as a Measuring Solution," Magyar Kern. Foly6irat,
61;48-50 (1955).
Titrate with NH OH using methyl red indicator.
88. Flaschka, H., "The Ethylenediamine Titration: Applications III,"
Chemist Analyst. 47^52-56 (1958).
Discussion.
89. Foldesi, K., "Rapid Method for Sulfate Determination," Bflr - 'es Cipo1
tech.. 11^:20-23 (1961).
Precipitation in solvent solution with BaCl2 and titration of the
excess with EDTA using Eriochrome Black T indicator.
35
-------
90. Foster, M., "Volumetric Detection of Sulfate in Water," Ind. Eng. Chem..
Anal. Ed.. 8;195 (1936).
lodometric titration. Barium chromate back titration with thio-
sulfate.
91. Freeland, M. Q., "Direct Titration of Sulfate," U.S. Atomic Energy
Comtn. ISC 667, pp. 1-32 (1956).
Titration with standard Ba solution using Alizarin Red S or Thorin
as an indicator.
92. Fritz, J. S., "Determination of Sulfate," Anal. Chem., 26(10):1593-
1595 (1954).
Titration with standard Ba solution (BaCl or Ba(ClO,)2) in 30 to
40% EtOH using Alizarin Red S indicator.
93. Fritz, J. S., "Rapid Microtitration of Sulfate," Anal. Chem.. 2£(9):
1461-1464 (1955).
Titration with Ba(ClO)4 in 80% alcoholic solution using thorin
indicator.
94. Fritz, J. S., "Titration of Sulfate Following Separation with Alumina,"
Anal. Chem.. 29(1):158-161 (1957).
Titration with Ba(ClO), using thorin indicator.
95. Fukutomi, T., "Modification of a Spot Test for Sulfate Ion," Anal.
Chem.. 31^(6): 1118 (1959).
Addition of BaCl2 produces pH of 9.4; recommends use of thymol-
phthalein for end point.
96. Funasaka, W., "A Rapid Method for the Determination of the Sulfate
Radical with an Ion Exchanger," J. Chem. Soc. Japan, Ind. Chem. Sect..
54^:355-357 (1951).
H2SO, titration with NaOH. Trivalent ions do not interfere.
97. Geilmann, W., "Microchemical Determination of Sulfate by the Chromate
Method," Z. anal. Chem.. 139j412-423 (1953).
Indirect-exchange titration of chromate with FeSO, and "ferroion"
indicator.
36
-------
98. Geilmann, W. "Notes on Microchemical Volumetric Analysis. I.,"
Z. Anorg. Allgem. Chem.. 167,: 113-127 (1927).
Discussion of methods and procedures.
99. Germuth, F. G., "Volumetric Method for Determination of Sulfate Ion,"
J. Am. Water Works Assoc.. 19.:607-609 (1928).
Precipitation by BaCl , back titration with l^CrO, using Pb(NO.j)2
as outside indicator.
100. Geyer, R., "Sulfate Titration with Barium Chloride and Adsorption
Indicators," Z. anal. Chem.. 146j 174-181 (1955).
Na-alizarin sulfate indicator.
101. Geyer, R., "Volumetric Determination of Sulfate in Water," Z. anal. Chem.,
158_:418-421 (1957).
Na-alizarin sulfonate indicator. Ion exchange column.
102. Giblin, J. C., "Volumetric Method for the Determination of Barium and
Sulfates," Analyst. 58^:752-753 (1933).
Titration with BaCl_ using Na Rhodizonate indicator.
103. Goday, S. R., "lodometric Determination of Sulfates," Bol. Farm. Militar,
1^:361-364 (1934); Chimie and Industrie. 34: 792.
Modifications of Huiman's method; BaCl^ precipitation with I^CrO/
titration.
104. Goddu, R. F., "Photometric Titrations." Anal. Chem.. 26J11);1740-1746
(1954).
Discussion.
105. Grant, J., "Summarized Methods of Analysis. III. The Sulfate Ion,"
Chem. Products. 2j 125-129 (1939).
Review of volumetric methods using benzidine, BaC^, BaCrO-,
Pb(N03)2, BaC03, and BaC^.
37
-------
106. Grant, J., "Summarized Methods of Analysis. IV. The Sulfate Ion,
Quantitative Methods -Color imetric," Chem. Products, .2:157-160 (1939).
General procedures with benzidine; l^C^ and Fed.,; napthaquinone-
sulfonate; and
107. Gregorowicz, Z., "Indirect Volumetric Determination of Anions with
Variamine Blue Indicator," Anal. Chim. Acta, 23j299 (1960).
PbSO, precipitate; titrate excess Pb with K3Fe(CN)g and Variamine
Blue acetate solution.
108. Gregorowicz, Z., "Oxidation-Reduction Indicators in the Indirect Volu-
metric Determination of Anions. Determination of Sulfate Ions with
Lead(II) Nitrate," Z. anal. Chem. , -177_;91-97 (1960).
PbSO, precipitate; excess Pb titrated with K^Fe(CN)g using Vari-
amine Blue indicator.
109. Grigor'ev, P., "Volumetric Determination of the Sulfate Ion," J. Chem.
Ind.. 7^:1004-1006 (1930).
Titration with Pb*"1" with KI indicator.
110. Gwilt, J. R. , "Analytical Applications of Sodium Lauryl Sulfate. I.
The Volumetric Determination of Barium," J. Appl. Chem., 5:471-474
(1955).
Ba precipitation by Na lauryl sulfate; excess Na lauryl sulfate
titrated with quaternary ammonium compound.
111. Haase, L. W. , "Investigation of the Benzidine Method for Determining
Sulfuric Acid," Z. Angew Chem.. 40j595-599 (1927).
Found Raschig method (see 202) good only above 30 mg/ liter.
112. Hallett, L. T., "Microdetermination of Sulfate Obtained from Combustion
of Organic Compounds. Tetrahydroxyquinone as an Indicator in a Volu-
metric Method," Ind. Eng. Chem., Anal. Ed.. 12 360-363 (1940).
» pH 6.5 to 7.0, temperature 15 to 25°C, end point observation
made by transmitted light and color compared with 2 layers of Wratten
No. 21 filter, Br instead of H202 for oxidation.
38
-------
113. Hamburger, H. J., "Contribution to Microvolumetric Analysis. II. Quan-
titative Determination of Small Quantities of Sulfate," Proc. Acad.
Sci. Amsterdam, 19^:115-125 (1916).
Precipitate with BaClo.
114. Hamburger, H. J., "New Methods for Quantitative Chemical Analysis. II.
Microvolumetric Determination of Very Small Amounts of Sulfate," Sitz.
d. Koninklyke Akad. van Wefenschoppen te Amsterdam Ap. 28'16 Biochem.
Z^_, 77j 168-188 (1916).
Precipitate with BaCU.
115. Harada, H., "Determination of Sulfate Ion by Chelating Titration,"
Tokyo to Ritsu Eisei Kenkyusho Nenpo, 13^:195-209 (1961).
NaEDTA titration (Eriochrome Black T indicator) after conversion
of Ba to Mg via MgEDTA.
116. Hauser, 0., "The Sulfate Determination with Barium Chromate," Mitt.
Chem. Forsch.-Inst. Wirtsch. Osterr., 9_:l-2 (1955).
BaSO. + BaCrO. precipitate; titration of I by ^28203.
44
117. Herrig, H. J'. , "Comp lexeme trie Determination of Sulfur in Combustible
Complexes," Brennstoff-Chem., 42:355-356 (1961).
BaCl2. Excess Ba titrated using "Titriplex-IIl" (Merck); phthalein
purple indicator.
118. Hibbard, P. L., "The Volumetric Determination of Sulfates by Oxidation
of Benzidine Sulfate with Potassium Permanganate," Soil Sci., 8j61-
65 (1919).
Titration with KMnO^; discussion.
119. Honda, M., "Ion-Exchange Resins in Analytical Chemistry. XIV. Deter-
mination of Sulfate Ion with Ion-Exchange Resins," Japan Analyst, 2j
451-455 (1953).
Two methods using ion exchangers followed by titration with NaOH
and AgN03 or alkali hydroxide.
120. lokhelison, D. B., "Colorimetric Method for Determination of Sulfuric
Acid in Drinking Waters," Ukrain Khein. Zhur, 9_:25 (1934).
SOf to PbSO, in NaOH solution via Pb(N03)2 precipitate and
for comparison with standard.
39
-------
121. lolson, L. M., "Application of the Volumetric Method of A. V. Vinogradov
to the Determination of the Sulfate Ion in Common Salt and Pickling '
Baths," Zavodskaya Lab.. (10):27-28 (1933).
Precipitation of BaSO^ with BaC^; titration with I^C^O^ with
rosolic acid as indicator; hot solution must be used.
122. Iritani, N., "Determination of Sulfate Ion with EDTA. II. Chelometric
Determination of Sulfate Ion as Lead Sulfate," Bunseki Kagaka, 8:30-
33 (1959). ~
Pb(N03)2. Excess Pb titrated using EDTA with Cu-PAN indicator.
123. Iritani, N., "Determination of Sulfate Ions with EDTA. III. Deter-
mination of Phosphate and Sulfate Ions as Magnesium Ammonium Phos-
phate and Lead Sulfate," Bunseki Kagaku, 9(1): 1-5 (1960).
Discussion of effect of nitrate; excess Pb titrated with EDTA.
124. Iritani, N., "Volumetric Analysis of Sulfate Ion with Barium Ethylene-
diaminetetraacetate," Bunseki Kagaku, 7_:42-46 (1958).
EDTA precipitation; excess EDTA titrated with BaCl2 and EtOH with
metal phthalein as indicator; if salt content high, titrate with
MgCl_ with Eriochrome Black T indicator.
125. Iwasaki, I., "Colorimetric Determination of a Trace of Sulphate Ion,"
J. Chem. Soc. Japan, Pure Chem. Sect., 74j400-401 (1953).
Determination by diphenylcarbazide.
126. Iyer, M. P. V., "Adsorption Indicator in the Volumetric Estimation of
Sulfates," J. Indian Chem. Soc.. 12j 164-167 (1935).
i i
Fluorescein as an indicator with Ba titration.
127. Jangida, B. L., "Microtitrimetric Determination of Sulfate in Thorium
Nitrate and Reagent Chemicals," Indian J. Chem.. 2(4):149-151 (1964).
SO," + Pb(NO ) in Me2CO, EtOH and HOAc, and centrifuged. Dis-
solved in buffer and excess EDTA; titrated with MgCl_ and Eriochrome
Black T. Sample cleaned up with Al 0 . Cl", F", CrO,°, and PO^3"
interfere. Cl~ and F" eliminated by heating to fumes with HC10/.
CrO^~ removed by reducing with 1^2 and complexing with HOAc. Zn
added before A^O-j removed PO,^-.
40
-------
128. Jarkim, A. F. S., "Volumetric Determination of Sulfates," Rev. Soc.
Bra-Sil. Quim. 1£: 104-108 (1941).
Precipitation with Ba. Excess precipitated with
Oxalic acid titrated with
129. Jaselskis, B., "Titrimetric Determination of Semimicro Amounts of
Sulfate in Presence of Phosphate," Anal. Chem. , 36( 10) : 1965-1967
(1964).
Titration with Ba(I03)2. . ,
130. Jellinek, K. , "Hydrolytic Precision Analyses. Determination of Barium,
Lead and Sulfate," Z. Anorg. Allgem. Chem., LMh 253-262 (1923) .
Titration with K^CrOA with methyl red as indicator; need excess
Ba"1""1".
131. Jellinek, K., "Some New Methods of Volumetric Analytical Determination
of Sulfate, Lead, Acid and Ammonia," Z. Anorg. Allgem. Chem. , 124j
185-202 (1922).
Precipitation with Ba(N03)2 followed by excess of K2CrO, . Back
titration with Ba(N03)2.
132. Josephson, B., "Volumetric Method for the Determination of Sulfur and
Sulfate Ion," Analyst. 64^:181-185 (1939).
Added excess BaCl2 and dilute HC1; add NaOAc , HOAc and l^CrO,^;
filter; determine excess CrO/~~ iodometrically .
133. Jones, J. H. , "Semimicro Method for the Determination of Sulfur in
Organic Substances," J. Assoc. Official Agr. Chem.. 26_: 182-186
(1943).
S oxidized to S04= by HN03, HCl, HCK>4; S04= titrated with BaCl2 in
presence of tetrahydroxyquinone indicator; end point observed in
presence of AgCl.
134. Kahler, H. L., "Determination of Sulfate by the Tetrahydroxyquinone
Method. Effect of Sodium Sulfite and Procedure for Its Elimination,"
Ind. Eng. Chem.. Anal. Ed.. 12j266-26.7 (19,40).
Discussion.
41
-------
135. Kahn, B. S., "Colorimetric Determination of Inorganic Sulfate in Small
Amounts of Urine," J. Biol. Chem.. 80^:623-629 (1928).
Add benzidine, filter, and diazotize precipitate with PhOH to
produce yellow color.
136. Kainzner, A., "Determination of Sulfate with Complexon," Zement-Kalk-
Gips, 10:281-283 (1957).
Precipitation with Ba and titration with complexon (MTB).
137. Klinke, K., "The Volumetric Determination of Sulfate in Very Small
Quantities," Biochem. Z.. 154:171-175 (1924).
Addition of K2Cr04 and BaCl2- Filter, add KI, titrate with Na2S203.
138. Kochor, S. J., "Detection of Barium, Sulfur, and Sulfates," Ind. Eng.
Chem.. Anal. Ed., 9j331 (1937).
Bacl2 titration. Spot test for end point.
139. Kochor, S. J., "Determination of Barium, Sulfur and Sulfates. A Rapid
and Accurate Volumetric Method," Ind. Eng. Chem., Anal. Ed., 9_:288-
290 (1937).
Spot reaction with hydroxybenzoquinone derivative.
140. Kolthoff, I. M., "The Determination of Sulfate by Means of Barium
Chromate Suspensions," Rec. Trav. Chim., 40:686-689 (1921).
BaSO- titration; excess CrO^ titrated iodometrically.
141. Korbl, J., "Some New Metallochromic Indicators of the Complexone Type,"
Chem. and Ind.. pp. 233-234 (1957).
Discussion of compounds for complexometric titrations.
142. Koszegi, D., "New Analytical Determination of the Sulfate Ion," Z^_
anal. Chem., 77^203-209 (1929).
Modification of chromate method.
143. Kotik, F. I., "Rapid Analysis of Sulfates in ah Ethy.lenediamine Elec-
trolyte for Copper Plating with the Nitchromazo Indicator," Zavodsk.
Lab.. 34(1) :33 (1968).
Titrate with BaCl2 in 50% EtOH with nitchromazo indicator. Used
ion exchange.
42
-------
144. Krausz, I., "Titrimetric Determination of Sulfate Ions," Magyar Kern.
Folyfiirat. 78^(10) : 502 -503 (1972).
Precipitation with benzidine sulfate and NaOH. Titrate with HCl.
145. Kuznetsov, V. I., "Metal Indicator for Barium in Volumetric Sulfate
Determination in the Presence of Phosphates and Arsenates," Zavodsk.
Lab., 31(5): 538-540 (1965).
Ba salt titration of S0,~ using Nitchromazo as indicator.
146. Kyte, V., "An Inexpensive High-Frequency Titration Apparatus for
General Laboratory Use. Application to Some EDTA and Precipitation
Titrations," Analyst. 84j647-654 (1959).
Description and use in SO," precipitation titration.
147. Lakomkin, I. G., "Oxalate Method of Determining Sulfate Ion," Zavodsk.
Lab.. 8:416-421 (1939).
0.5 mg/ml determined by adding Na2CC>3 and filtering. Neutralized
with HCl; add BaC20, and filter. Acidify and titrate with KMnO, .
148. Lang, K. , "A Colorimetric Microchemical Method for Determination of
Sulfur and Sulfate in Biological Fluids," Biochem. Z.. 2!L3j469 (1929).
Excess BaCrO, determined with phenylcarbazide.
149. Lang, W. R., "An Improved Form of Apparatus for the Rapid Estimation
of Sulfates and Salts of Barium," J. Chem. Soc.. 92_: 1370-1373 (1907).
Titration with BaCl2.
150. Lederc, R. , "Volumetric Determination of Sulfate," Mem. Services Chim.
|ta_l, 32j 15-19 (1945).
Precipitation of PbSO^ and titration of excess Pb*"1" with (Nlfy^MoO^
151. Lee, S. W., "Volumetric Determination of Sulfates. Tetrahydroxyquinone
as an External Indicator," Ind. Eng. Chem., Anal. Ed., 14^:839-840
(1942).
S0,= titrated with BaCl2; transferred to spot of Na salt of tetra-
hydroxyquinone; yellow to pink color change; acid, NaCl and Al
interfere.
43
-------
152. Legradi, L., "Titrimetric Determination of Sulfate Ions," Magyar Kem.
Foly6irat. 64j 29-30 (1958).
Add Bad-. Titrate with Complexon II (analogue of MTB).
153. Leithe, W. , "Oxidimetric Titration of Extremely Small Quantities of
Sulfate," Mikrochemie ver. Mikrochim. Acta, 33:173-183 (1947).
Excess CrO^" titrated with standard FeSO, with diphenylamine-
sulfonic acid with modifications for various amounts of SO*.
154. Li, L., "Complexometric Titration of Sulfate Ion," K'o Hsuch T'ung
Pao, 1; 33-34 (1962).
Indirect from PbSO^ precipitate-Pb titration with EDTA, xylenol
orange indicator.
155. Lovasi, J. , "Rapid Determination of Sulfate in Solutions Used in
Uranium Production," Kohasz. Lapok, 8_(10):477-479 (1965).
Titration with BaCU with Na alizarin indicator.
156. Luchinskii, G. P., "lodometric Determination of the Sulfate Ion,"
Zavodskaya Lab., 10^:263-265 (1941).
o precipitation; excess BaS20o titrated with iodine solution.
157. Lukin, A. M. , "Detection of Sulfur in Organic Compounds," Metody anal.
Khim. Reaktiv Prep., 18: 151-152 (1971).
Titration with Ba(NOo)o using chlorophosphonazo II indicator.
158. Lukin, A. M. , "Titrimetric Determination of Sulfates with Chloro-
phosphonazo III, " Zavodsk_._l,ab_._, 34(9) : 1054- 1056 (1968).
SO," detected by titration in 80% acetone of pH 1 to 3 with Ba
salt solution in presence of chlorophosphonazo III indicator;
Ca and Sr interfere.
159. Macchia, 0., "The Volumetric Estimation of Sulfate Ion," L'lndustria
Chimica, 4j 480-483 (1929).
Treatment with Ba3(PO,)2 and NaOH. Titrate with HCl.
160. MacNevini W. M. , "An Ion-Exchange Experiment for Quantitative Analysis,"
J. Chem. Education, 28j389-390 (1951).
Student exercise, ion exchange SO^ to H2S04. NaOH titration.
44
-------
161. Mahoney, J. F., "Improved Semimicrodetermination of Sulfur in Organic
Materials. Peroxide-Carbon Fusion Followed by a Titration Using
Tetrahydroxyquinone Indicator," Ind. Eng. Chem. , Anal. Ed., 14j97-98
(1942).
S oxidized to inorganic S0^~ by Na202-C fusion; S0^~ determined by
titration with standard BaC^ solution.
162. Manov, G. G. , "Determination of the Sulfate Ion. The Microvolumetric
Chromate Method," Ind. Eng. Chem., Anal. Ed.. 9j 198-200 (1937).
BaSO, precipitated in HC10, with carbonate- free NH-j solution to
lessen danger of co-precipitation of CrO^~ with BaSO^~.
163. Markova, L. V., "Stilbnaphthazo as an Indicator in the Volumetric
Determination of Sulfate," Ukrain. Khim. Zhur., 23j89-91 (1957).
Indicator for BaClo titration. Me2CO or iso-AmOH added to
titration mixture.
164. Marsden, A. W. , "Benzidine Method for the Micro-Determination of
Sulfate — Application to the Determination of Total Sulfur in Soil
Solutions, Extracts, Etc.," J. Soc. Chem. Ind., 56j464 (1937).
Precipitation of S0,~ and eventual titration of benzidine with
KMnO, .
165. Matsui, S., "Rapid Procedure for Determination of Sulfate in Sodium
Chloride Brine for Electrolysis," K6gy8 Kagaku Zasshi, 59^:591-592
(1956).
EDTA indicator with EBT and methyl red to improve sharpness.
166. McCallum, J. R., "Analysis for Small Amounts of Calcium, Magnesium,
Barium, and Sulfate with Phthalein Purple," Can. J. Chem. . 34j921-
925 (1956).
o precipitation; back titrate with EDTA; phthalein purple,
methyl red, and Dianil Green indicator mixture.
167. McKittrick, D. S., "Determination of Sulfate by the Benzidine Method,"
Arch. Biochem. . 6:411-417 (1945).
Benzidine SO^ precipitated at pH 2.8, washed and titrated with hot
NaOH (phenol red).
45
-------
168. Medinskii, K. L. B., "Examination of the Mindalev Method for the
Volumetric Determination of Sulfates," Zavodskaya Lab., 3j 230-231
(1934).
Titration with Pb(N03)2 in presence of KI.
169. Mehlig, J. P., "Ceriometric Method for the Determination of Sulfates,"
Chemist Analyst, 3£:76-78 (1941).
Treat with BaC_0.. Titrate with eerie ammonium sulfate.
2 4
170. Menis, 0., "Automatic Spectrophotometric Titration of Fluoride, Sul-
fate, Uranium, and Thorium," Anal. Chem.t 30(11):1772-1776 (1958).
High sensitivity by titration in 50% isoamyl alcohol—barium
perchlorate/thorin; 520 mu.
171. Milner, 0. I., "Titration of Sulfates with Aid of a High-Frequency
Oscillator," Anal. Chem., 24(8);1247-1249 (1952).
0.1 to 7.0 mg S0^=. 18.5 uH; titrate with BaCl2.
172. Mirdalev, Z., "A New Titrimetric Determination of the Sulfate Ion,"
Z. anal. Chem., 75^:392-395 (1928).
Pb(N03)2 + KI.
173. Mitler, C. C., "Volumetric Determination of Small Quantities of Barium
and Sulfate with Barium Rhodizonate as an Indicator—Determination
of Sulfur in Iron Pyrites," J. Chem. Soc., pp. 401-406 (1940).
* SOT determined using Ba rhodizonate in absolute EtOH.
174. Morgulis, S., "An lodometric Method for Determination of Sulfates in
Organic Material," Biochem. Z., 249j409 (1932).
Excess BaCrC>4 to H2CrO^. Add KI and titrate with Na2S203.
175. Morris, A. G. C., "Dissolution of Barium Sulfate by EDTA and Sodium
Hydroxide," Chemist Analyst. 48j76,84 (1959).
Ba precipitation; EDTA titration.
46
-------
176. Mukai, K., "Simple Determination of Sulfate by Means of Dissolving
Barium Sulfate with Ethylenediaminetetraacetic Acid (EDTA),"
Bunseki Kagaku, 6_: 732-735 (1957).
Precipitate BaSO^ with BaCl ; filter; wash; add EDTA, aqueous NH3
to pH 11; boil; titrate unreacted EDTA with metal phthalein indi-
cator. Cations do not interfere.
177. Mukoyama, T., "Rapid Determination of Sulfate. Titration of Ammonium,
Sodium, and Potassium Sulfate by Use of Sodium Rhodizonate Test
Paper," Japan Analyst, 4_:558-563 (1955).
Titrate using Bad- precipitation and Na rhodizonate test paper
as external indicator.
178. Hunger, J. E., "Volumetric Determination of Sulfate Ion by Using
Barium Ion and a Standard Disodium Dihydrogen Ethylenediaminetetra-
acetate Solution," Anal. Chem., 22_(10): 1455-1457 (1950).
Determination of excess Ba with Eriochrome Black T as indicator.
179. Murakami, T., "A Rapid Determination of Sulfate in Cellulose Acetate,"
K8gakuin Daigaku Kenkyu Hokoku. 7_:47-51 (1959).
lodometric titration of excess CrO^~; 0.02% SO ~ lower limit.
180. Musha, S., "Application of High-Frequency Titration," Science Repts.
Res. Inst. Tohoku Univ. Ser. A, 4:575-581 (1952).
HF
titration of SO" with BaCl2; 40 to 50% MeOH at 6.0 pH.
181. Mutschin, A., "Indirect Titration of Sulfate with Barium Chloride with
Sodium Rhodizonate as Indicator," Z. anal. Chem. . 108^:309-316 (1937).
Determination of SO ~ in presence of various interferents studied;
BaCl2 precipitation.
182. Mutschin, A., "Indirect Titration of Sulfate with Barium Chloride with
Sodium Rhodizonate (or the sodium salt of tetrahydroxyquinone) as
Internal Indicator. I," Z. anal. Chem., 108j8-18 (1937).
General discussion.
183. Nakata, H., "Volumetric Determination of Sulfate by the Use of Sodium
Palmitate," Japan Analyst, 4j621-623 (1955).
Titration with H2SO^-EtOH solution.
47
-------
184. Nastaskina, E. I., "Determination of Sulfates by the Drop Method,"
Elek. Stantsii. 27,(9):55-56 (1956).
Titration with Bad • disodium rhodizonate as indicator.
185. Nastaskina, E. I., "Volumetric Determination of Sulfates in Water,"
USSR Patent 102,780, 25 May 1956.
SOT precipitated with excess BaCl2; excess Ba titrated with
with disodium rhodizonate as indicator.
186. Nazarenko, V. A., "Titration of Barium Salts and Sulfate Ion with
Potassium Chrornate," Zavodskaya Lab., 4:515-518 (1935).
^^^^~ ~J^^^^~^^^^^ ^w
Titration of excess BaCl2 with K2Cr04 in presence of rosolic acid
with EtOH.
187. Nechiporenko, A. P., "Microspectrophotometric Titration of Cadmium and
Sulfate Ion," Zavodsk. Lab., 3J5(4) :432-433 (1969).
Badl- titration with nitchchromazo indicator at 664 mu. One to
20 ug/ml; + 0.1 to 37».
188. Nechiporenko, G. N., "Determination of Sulfate Ions by Direct Titra-
tion with Lead Nitrate and Dithizone as an Indicator," Izvest. Akad.
Nauk S.S.S.R., Otdel. Khim. Nauk., pp. 359-361 (1958).
0.5 to 50 mg SO," detected if Cl not more than 7x S0^=, and Ca"*"1"
not more than l/3x S04=, ± 1 to 27..
189. Neehamkin, H., "Determination of Soluble Sulfate," Chemist Analyst.
1 41^:31-33 (1952).
S0,= solution passed through BaC20^; C20,= titrated with .1 N
KMnO^; 0.13 to 0.31 g 804 detected, ± 0.37..
190. Niwa, U., "Photometric Endpoint in the Precipitation Titration of
Sulfate," Chemist Analyst, 49j 102-103,105 (1960).
Titration with Pb(NOo)2 in acetone-water with dithiazone indicator.
191. Nonova, D., "Complexometric Determination of Barium," Fresenius Z.
Anal. Chem.. 265(1):31 (1973).
Cu(II)-EDTA-PAR as indicator (see Puschel).
48
-------
192. Odler, I., "Complexometric Determination of Sulfates." Chem. Zuesti,
15j563-567 (1961).
Indirect PbSO, titration using Complexone III, xylenol orange
indicator.
193. Ogg. C. L., "Volumetric Determination of Small Amounts of Soluble
Sulfates." Anal. Chem.. 20(1):83-85 (1948).
Titration BaCl2- Indicator: dipotassium rhodizonate or tetra-
hydroxyquinone.
194. Costing, M., "Some Experiences with High-Frequency Titrations," Chem.
Weekblad, 52_:665-670 (1956).
Pro-con discussion, construction details. SOf titration in
boric acid medium.
195. Palat/, V., "Determination of Sulfate," Chem. Ind., p. 176 (1960).
Colorimetric determination of SO," using Pyrocatechpl Violet,
SPADNS, Eriochromecyanine R, and Alizarin Red S dyes possible;
Methylthymol Blue and Thorin not suitable.
196. Peabody, W. A., "Sulfate Titration. Use of Tetrahydroxyquinone in a
Semimicromethod," Ind. Eng. Chem., Anal. Ed., 1£: 651-652 (1938).
BaCl precipitation with tetrahydroxyquinone and 2-methoxyethanol
as an external indicator on a spot plate.
197. Philipp, B., "The Complexometric Sulfate Determination with Phthalein
Complexon," Faserforsch. u. Textiltech., 7^:525-527 (1956).
Comparison of gravimetric and determination with Erio T and
phthalein complexon (MTB).
198. Photiadis, P., "Determination of Sulfate Ions," Z. anal. Chem.. 91:
173-180 (1932).
Precipitating S0= with BaCl2; precipitating Ba with (NH^)2Cr207;
titrating chromate with Na-S^Oo.
199. Polgar, E., "Rapid Titrimetric Determination of Sulfate Ions with
Barium Chloride as a Measuring Solution," Magyar Kern. Foly6irat,
61^:48-50 (1955).
Neutralize solution and titrate to alkaline using
49
-------
200. Polushin, D., "Volumetric Determination of Sulfates," Iskussivennoe
Volokno, 5(2):33-34 (1934).
Add Pb(NO ) . Titrate excess with Na2C03.
201. Ponomareva, L. K., "Rapid Determination of Sulfate in Cryolite," Tr.
Ural'sk. Nauchn.-Issled. Khim. Inst., (ll):54-58 (1964).
A1(N03)3 + EtOH added to sample; titrate with BaCl2'2H20 with
Na rhodizonate as indicator.
202. Puschel, R., "Metal Specific Indicators in Precipitation Titrations.
IV. Rapid Determination of Sulfate by Titration with Standard
Lead Solution," Z. anal. Chem., 166_:401-406 (1959).
SO ~ titration with Pb solution in 50% iso-PrOH at pH 6 with
4-(2-pyridylazo)resorcinol (PAR) indicator or at pH 4 using
dithizone; 2 to 100 mg S04~.
203. Raeder, M. G., "Microtitrimetric Determination of Sulfuric Acid and
Sulfates with Sodium Rhodizonate as Indicator," Kgl. Norske Videnskab.
Selskab Forh.. 5(8):32-35 (1933).
Titration with BaCl2.
204. Randall, M., "Rapid Volumetric Method for the Determination of the
Sulfate Ion," Ind. Eng. Chem.. Anal. Ed.. 14j620-621 (1942).
Sulfate + BaCl2. Titrate with Na^HPO,, methyl red indicator.
205. Rao, G. V., "Estimation of Carboxyl, Sulfate, and Sulfonate Groups
by Direct Titrimetry," Indian J. Chem. . 5J4): 150-152 (1967).
Titration with alcohol-KOH to determine acidity; hydrolysis with
H2SO^, isolation of fatty acid, weighed and titrated to determine
combined carboxyl and sulfonate.
206. Raschig, F., "Determination of Sulfuric Acid in Drinking Water By
Means of Benzidine," Z. Angew. Chem., 4£:864 (1927).
5-liter sample evaporated to 500 cc + 25 cc cone, benzidine.
Filter and titrate precipitate with 0.1 NaOH.
50
-------
207. Rayner, A. C., "A Rapid Titrimetric Method for Sulfate in Lead Dioxide
Exposed to Atmospheric Sulfur Pollution," J. Air Polln. Control Assoc..
16(8):418-421 (1966).
Formation of ammonium sulfate and titration with Ba(ClO)- with
Thorin indicator.
208. Reitmeir, R. F., "Semimicroanalysis of Saline Soil Solutions," Ind.
Eng. Chem.. Anal. Ed.. 15j393 (1943).
Benzidine sulfate precipitate titrated with standard base. Indi-
cator: phenol red.
209. Repiton, E., "Titrimetric Determination of Free Sulfuric Acid and
Sulfate," Mon. Sci. . 24_:382-384
Sulfate + BaCl2 + I^Cr^. Excess K2Cr207 titrated against SnCl2-
HgCl2 indicator.
.210. Ricci, J. E., "Determination of Sulfate. Attempt to Determine Sulfate
by Titration with Lead Nitrate with Eosin as Indicator," Ind. Eng.
Chem.. Anal. Ed., 8j 130-132 (1936).
Titration with Pb(NO~)9; ± 0.5 mg Na9SO,.
J £* fa *T
211. Ringbom, W., "Photometric Precipitation Titration Determination,"
Z. anal. Chem.. 122_:263-279 (1941).
Discussion of factors affecting accuracy of using BaSO^ as example.
212. Riva, B., "Indirect Volumetric Determination of the Sulfate Ion with
Ethylenediaminetetraacetic Acid," Ann. Chim., 47j233-239 (1957).
Eriochrome Black T indicator with Mg"1""1".
213. Rivett, A. C. D., "A Method for the Volumetric Estimation of Sulfates,"
Chem. News. 118^:253-254 (1919).
Sulfate + BaC204. Titrate with KMn04.
214. Robbin, L. A., "Rapid Titrimetric Determination of Sulfate in Mixtures
of Gypsum Anhydrite, Calcium Oxide, and Calcium Sulfide Using Ion Ex-
change," Anal. Chem.. 36(2):429 (1964).
Titration using Dowex 50 or Amberlite IR 120. Sulfate titrated
n c TJ QO
do LifyJ\J/ *
51
-------
215. Roemer, H., "Titrimetric Determination of Combined Sulfuric Acid by
the Barium Chromate Method," Z. anal. Chem. . 49_:490-492
S0,= exchanged via BaCl and K2Cr207 with i^CrO^; K^CrO, titrated
with standard FeSO, (NH^^SO/ using K-FeCNg as indicator; down to
0.1% SO^ with 0.035 to 0.048% error.
216. Roth, H., "A New Rapid Method for the Technical Determination of SO^
in Sulfates," Z. Angew. Chem.. 39^1599-1600,1601 (1926).
Sulfate + BaCl2. Titration with K2CrO^. pp'-diaminodiphenylamine
indicator.
217. Rumler, F., "Complexometric Sulfate Determination," Z. anal. Chem.,
166j 23-24 (1959).
Indirect Ba titration with EDTA.
218. Ryazanov, B. A., "Volumetric Determination of Sulfate Ion," Nauch.
Trudy Moskov Tekhnol. Inst. Legkoi Prom. (16):62-65 (1960).
Titration of S04= as CU2(S04)3 or A12(S04)3 with Pb(N03)2 with
dithizone indicator.
219. Schoch, E. P., "Direct Titrimetric Methods for Magnesium, Calcium, and
Sulfate Ions and their Applicability to Water Analysis," Ind. Eng.
Chem. . 19j 112-115 (1927).
Add BaCU, titrate with Na2C03 solution. Thymolphthalein indicator.
220. Scholle, S., "Determination of Errors at Successive Titrations of
Phosphate and Sulfate Solutions," Vys, Sk. Chem. — Technol., Pardubioe.
Gech. Collect Czech. Chem. Commun. . 37^(9) : 3029-3033 (1972).
Modification of Bakacz-Polgar and Szekeres method.
221. Schroeder, W. C., "Direct Titration of Sulfate: Tetrahydroxyquinone
as an Internal Indicator," Ind. Eng. Chem., Anal. Ed.. 5:403-406
(1933).
Titration with BaCl2. EtOH and KC1 used; 2 to 20 mg S04=.
222. Seidman, E. B., "Determination of Sulfur Oxides in Stack Gases,"
Anal. Chem.. 30:1680-1682 (1958).
Ba-thorin titration of SOo.
52
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223. Serfass, E. J., "Analytical Determination of Trace Constituents in
Metal Finishing Effluents. XIII. The Volumetric Determination
of Sulfate in Effluents," Plating, 43^:500-501 (1956).
Sample precipitated with OH" and Ag+ to remove interferents; F~
removed by evaporation with HC1; organics oxidized with HoOoJ
S0,= titrated with BaC^, tetrahydroxyquinone as indicator;
5 to 50 ppm range.
224. Shcherbachev, K. D., "Rapid Determination of Sulfates in Crude Hydro-
chloric Acid," Zavodskava Lab.. 3:424-425 (1934).
Spot titration with K2Cr207 and p-aminodimethylaniline sulfate
or leucomethylene blue indicators.
225. Sheen, R. T., "Determination of Sulfur in Oil. Tetrahydroxyquinone
as an Indicator in Direct Titration," Ind. Eng. Chem., Anal. Ed..
lOj 206-207 (1938).
S in oil determined after oxidation in bomb by titration with
tetrahydroxyquinone dispersed in organic medium as internal indi-
cator.
226. Sheen, R. T., "Determination of Sulfur in Rubber. Uses of Tetrahydroxy-
quinone as a Titration Indicator," Ind. Eng. Chem., Anal. Ed., 9^:69-
71 (1937).
S oxidized to S0,=; S0^= precipitated by excess BaCl2; heavy metals
precipitated by KOH at pH 8.3; excess Ba determined by back titra-
tion with Na2SO, using tetrahydroxyquinone as indicator.
227. Sheen, R. T., "Direct Titration of Sulfates. Tetrahydroxyquinone as
an Internal Indicator," Ind. Eng. Chem.. Anal. Ed.. 8j 127-130 (1936).
Method of Schroeder but using iso-ProOH; PO," liberated by using
pH 4 by aid of bromcresol green indicator; BaCl2 titrated with
tetrahydroxyquinone; 80 to 3,000 ppm S0^~.
228. Shinkai, S., "New Volumetric Determination of Sulfate Ion," Japan
Analyst. 2:432-433 (1953).
Sulfate + BaCl2, add Na2C03; add HCl, back titrate with NaOH.
229. Shpilev, F. S., "Determination of Sulfate Ion in Water-Soluble Sulfates,"
Trudy Dagestan. Sovef. Inst., 7_: 106-118 (1955).
lodometric titration in buffer solution.
53
-------
230. Shub, M. E., "Volumetric Determination of Sulfates," Farmatsiya,
4(11/12):17-19 (1941).
An improvement of Raschig (benzidine SOT) method.
231. Siegfriedt, R. K., "Determination of Sulfur After Combustion in a
Small Oxygen Bomb. Rapid Titrimetric Method," Anal. Chem., 23j
1008-1011 (1951).
S oxidized, treated, and titrated with BaCl9 using tetrahydroxy-
quinone as indicator using orange light filter; corrections can
be made for Ba and P.
232. Sijderius, R., "Titrimetric Determination of Sulfate by Means of the
Disodium Salt of EDTA," Anal. Chim. Acta, 11_: 28-32 (1954).
Sulfate + BaCl2< Titration with EDTA.
233. Skvortzov, V. N., "Volumetric Determination of Sulfate and Barium
Ions," Trans. Butleroy Inst. Chem. Tech. Kazan. (1):164-167 (1934).
Titration with BaCl2 in a buffered solution containing chromate.
234., Smith, J. L. B., "Volumetric Determination of Barium and Sulfate,"
S. African J. Sci., 16:174-176 (1919).
Sulfate + BaCl2< Add I^CrO,; add I2; titrate with Na2S203.
235. Snyder, S., "Volumetric Determination of Sulfates by the Use of Benzi-
dine Solution," Chemist Analyst, 20_(6):8-10 (1931).
Raschig's method.
236. Soibel'man, B. I., "Semimicrodeterminations of Sulfates by the lodate
Method," Zhur. Anal. Khim.. 3j 258-263 (1948).
Precipitation of S04= with 83(103)2 followed by titration with
Na2S203 (methyl orange indicator); 103" concentration -~ .1 N;
if S0,= < 0.05%, add known amount K2SO^.
237. Sonenberg, F. K. M., "Long Chain Alky 1 Sulfates," Anal. Chem., 22_:
175 (1950).
Complex dye rosaniline HCl extraction via CHCl-j and EtAct. Appli-
cation to alkyl sulfates and other strong organic acids.
54
-------
238. Spiridorova, S. I., "Rapid Determination of the Concentration of Solu-
tions of Electrolytes by Titration with Water in the Presence of
Indicators of Turbidity," Izvest. Uysshikh Ucheb. Zavedenic; Khim.
i Khim. Tekhnol.. (2):51-57 (1958).
Samples titrated with water using 50/50 iso-BuOH and EtOH indicator.
239. Sporek, K. F., "Complexometric Determination of Sulfate," Anal. Chem.,
3£(6)=1032-1035 (1958).
Complexometric Determination of SOT. Back titration of EDTA
solution of PbSO^ using ZnCl^, Eriochrome Black T indicator.
240. Staikov, T., "Determination of Water-Soluble Chloride and Sulfate in
Solonets Soil," Rastenievadri Nauki. 2(10):113-118 (1965).
Soil extracted with NaNC>3, BaCl2 and Cr207=. Excess Cr^O^"
titrated with FeSO^. Diphenylamine indicator.
241. Strebinger, R., "New Volumetric Method for Determination of Barium and
Sulfate Ions," Z. anal. Chem., 79j 1-8 (1929).
Sulfate + Ba**; titrate with
242. Strebinger, R., "Volumetric Determination of Sulfate with the Aid of
Sodium Rhodizonate," Z. anal. Chem., 105j 346-350 (1936).
Discussion.
243. Styunkel, T. B., "Determination of Sulfate by the Trilon B Method,"
Zavodskaya Lab., 72^:653-656 (1956).
Titration with Trilon B.
244. Siimegi, L., "Determination of Sulfate Ion in Soluble Simple Sulfates,"
Magyar Kern. Foly6irat, 39_: 180-181 (1933).
S03~ precipitated with BaCl2 and (NH4)2C03. BaC03 in precipitate
titrated with HCl to methyl orange end point.
245. Sundberg, 0. E., "Microdetermination of Halogens and Sulphur Using
the Grote Combustion Apparatus," Ind. Eng. Chem., Anal. Ed., 18:
719-723 (1946).
S determined by automatic combustion method with volumetric pro-
cedures using di-K rhodizonate as indicator.
55
-------
246. Szekeres, L., "Determination of Inorganic Sulfur Compounds in the
Presence of Other Ions. II. Determination of Sulfate Ions or
Total Sulfur Content of Inorganic Sulfur Compounds by Precipitation
Titration," Microchem. J., 14(1):63-70 (1969).
Titration with BaClo in presence of Mg complexonate and Eriochrome
Black T indicator (includes interference removal).
247. Szekeres, L., "Determination of Sulfate in Presence of Phosphate,
Arsenate, and Other Ions. II," Microchem. J.. 13J3) :349-356 (1968).
Titration with BaCl- in presence of EDTA and DCyTA.
248. Szekeres, L., "Titrimetric Determination of Phosphate, Arsenate, and
Sulfate." Kiserl. Kozlemen A. Novenytepmesz, 57^(3) : 169-172 (1964).
Titrate with MgCl2 with NH^Cl-NH^OH buffer using Eriochrome Black
T, bromopyrogallol red, or MTB as indicators.
249. Szekeres, L., "Volumetric Determination of Sulfate Ions," Magyar Kern.
Folyoirat. 6.U 298-300 (1955).
Sulfate + Na2C03 + EtOH; titrate with BaCl2 solution. Phenol-
phthalein indicator.
250. Szilagyi, M., "Indirect Acidimetric Titration of Sulfate," Chemist
Analyst, 55_(4):109 (1966).
Sulfate + BaCl2, add Na2C03, titrate with HCl,
251. Talenti, M., "Volumetric Estimation of Sulfates," Giorn. Chim. Ind.
Applicata. 8j611-612 (1926).
Benzidine method; semi-quantitative.
252. Tanaka, T., "Determination of Sulfate with EDTA. IV. Chelatpmetric
Determination of Sulfate as Lead Sulfate," Bunseki Kagaku. 8:826-
827 (1959); Bunseki Kagaku, 9:1-6 (1960). ~
Xylenol orange indicator; 1 to 50 mg S04=.
253. Tananaev, I., "Adsorption of Ions of Water by Precipitates. II,"
J. Applied Chem. . 10_:2082-2087 (1937).
Neutralize sample with NaOH to pink color with phenol red. Add
507, alcohol and titrate with BaCl2. Red color increases and
disappears at end point. Boil solution and titrate to end
point again.
56
-------
254. Tananaev, I., "Determination of Plumbous and Sulfate Ions," J_._
Applied Chem.. 9j 1725-1728 (1936).
Titration with Pb(N03)2. "Blue ethyl acidic RR(B)," 2-(ethyl-
aminephenylazo-l,8-dihydroxynaphthalene-3,5-disulfonic acid
Na salt) indicator.
255. Tananaev, N. A., "The Volumetric Determination of Water-Soluble Sul-
fates," J. Chem. Ind.. 8j939-949 (1931).
Sulfate + Pb(N03)2, titrate with Na2C03.
256. Thomson, M. L. "Methods for the Micro-Volumetric Determination of
Sulfate," Metallurgia, 39_: 46-48 (1948).
Review of volumetric methods.
257. Toboleva, A. D., "New Titrimetric Process for Determining Sulfates,"
Energefik, 15J9): 18-20 (1967).
Titration with BaCl2. Nitchromazo indicator.
258. Toei, K., "Surface-Active Agents in Analytical Chemistry. I. Titri-
metric Determination of Sulfate with Sulfonazo III (as an indicator),"
Banseki Kagaku. 17(5):589-592 (1968).
Titration with Ba4^". Use of Dowfax 2A1.
259. Trandafelov, D., "Rapid Determination of Sulfate in Cryolite,"
Godishnik Sofiiskiya Univ., Fiz.-Mat. Fak. Kniga 2-Khim., 49:47-
52 (1956).
BaCrO, titrated by iodometric method; ~ 270 error.
260. Ueno, K., "Determination of Sulfate with Ethylenediaminetetraacetic
Acid (EDTA)," Japan Analyst. 3j331-332 (1954).
Determination of S07 with BaCl2 and di-Na EDTA solution
using Eriochrome Black T and ZnClo'fcl^O, MgCl2'6H20, and Iodine.
261. Ueno, K., "Rapid Analysis of Viscose-Coagulating Liquor Using Schwarzen-
bach Method. Volumetric Determination of Zinc and Sulfate Ion,"
Anal. Chem., 24j 1363-1364 (1952).
Free H SO, determined by titration and remaining Na,,SO, calculated
from total SO/~ and other values.
57
-------
262. Vargina, 0. S., "Volumetric Determination of Sulfates," Elek. Stantsii,
27(9):54-55 (1956).
Trilon B titrated with BaCl2 using water hardness indicator.
263. Vernazza, E., "Rapid Volumetric Estimation of Sulfate Ions," Indus tria
Chimica, 4j 988-989 (1929).
Sulfate + BaCl^, add NaSO of known concentration. Titrate back
excess, congo red + 0.02 N (NH/^C^Oy as external indicator.
264. Vinogradov, A. V., "Direct Titration of Barium Salts with Potassium
Chromate in the Presence of Rosolic Acid as Indicator. Application
of the Method to the Analysis of Sulfates and in Particular to the
Determination of Sulfur in Pyrite and in Slags," Ann. Chim. Anal.
Chim. Appl., 17_:285-288 (1935).
265. Vinogradov, A. V., "Direct Titration of Barium Salts with Potassium
Chromate, with Rosolic Acid as Indicator," Zavodskaya Lab. , (10):
17-19 (1933).
S0,= determined by adding excess BaCl^ and titrating excess Ba
with K-CrO, in presence of rosolic acid; Fe interferes.
266. Vinogradov, A. V., "Volumetric Determination of Sulfates with Lead
Nitrate," Zavodskaya Lab., 4:167-170 (1935).
Pappenheim method (unable to obtain original document).
267. Wanninen, E., "Complexometric Determinations of Sulfate Ion with Di-
ethylenetriaminepentaacetic acid," Suomen Kemistilehti, 296:184-188
(1956).
Add Ba salt and back titrate at pH 10 with tri-N2 salt of EDTA
in presence of Mg complex of EDTA and Eriochrome Black T.
268. Weiner, R. , "Rapid Analysis of Sulfate in Chromic Acid Solutions,"
Metallwaren - Ind. u. Galvano-Tech. , 50(2):66-70 (1959).
Reduce solution, add BaCrO,, NaOAc and water. Filter, treat KI
and acidify. Titrate ^2820.3 using starch indicator.
269. Wellings, A. W., "Direct Titration of Magnesium and Manganous Sulfates
using Fluorescein as an Adsorption Indicator and the Extension of
the Method to the Direct Titration of Other Soluble Sulfates and
Alums," Trans. Faraday Soc., 28_: 56 1-564 (1932).
Mg or Mn SO/~ titration with Ba(OH)2 using fluorescein.
58
-------
270. Wenger, P. E. , "Semiquantitative Determination of Sulfur Anions (sulf-
hydric, sulfurous, sulfuric, thiosulfuric, and persulfuric) , " Helv.
Chim.. Acta, 32_: 1865-1869 (1949).
Acid, step pH titration.
271. Werner, A., "Volumetric Microdetermination of Sulfur After the Carius
Decomposition of Organic Substances," Angew Chem. , 52jl39-140 (1939).
S07 by iodometric titration of chromic acid.
272. Wharton, H. W., "Application of Spectrophotometric Titrations to
Micromolar Solutions of Calcium, Magnesium, Oxalate, or Sulfate,"
Anal. Chem.. 36(8) :1679-1681 (1964).
Improved end point determination (barium perchlor/thorin) 500 to
2,500 ug range.
273. White, D. C., "The Titrimetric Microdetermination of Sulfate Using
Lead Nitrate as Titrant and Dithizone as Indicator," Mikrochim.
Acta. pp. 254-269 (1969).
10 to 100 ug 804; Pb(N03)2 titration.
274. Whiteker, R. A., "Determination of Sulfate and the Analysis of Pyrites.
Application of Cation-Exchange Resins," Anal. Chem., 26^(10): 1602-
1605 (1954).
Solution-treated ion exchange. Titrate NaOH to pH 7. Add dextrin
and dichlorofluorescein and titrate to pink with AgNOo.
275. Wilson, C. W., "Determination of Organic Sulfur in Gas. Titration of
Sulfate in the Sulfur Lamp with Barium Chloride Using Tetrahydroxy-
quinone as an Indicator," Ind. Eng. Chem., Anal. Ed., 10:418-419
(1938).
SC-2 adsorbed in Na2C03 in ASTM sulfur lamp; SO^" determined di-
rectly by titrating with BaCl? solution using tetrahydroxyquinone
as indicator.
276. Zabiyako, V. I., "Determination of Sulfate in Chromium Ammonium Alum,"
Tr. Ural'sk. Nauchn.-Issled. Khim. Inst.. (11):49-50 (1964).
Ion-exchange to remove Cr''', etc.; alkalimetric titration of
H2S04.
59
-------
277. Zavarov, G. V., "Some Improvements in the Direct Titration of Sulfates,"
Zavodskaya Lab.. 23j541-542 (1957).
Titration with BaCl2. Alizarin indicator.
278. Zavarov, G. V., "The Use of Sodium Rhodizonate for Determining Sulfur
and Sulfates in Technical Analysis," Zavodskaya Lab. , 8:993-995
(1939); Khim. Referat. Zhur.. (3):55 (1940). ~
Discussion. Na rhodizonate acceptable as external indicator.
279. Zink, J. , "Determining the Sulfate Ion by the Palmitate Method," Z^
anal. Chem. . 71: 386-387 (1927).
SOA= and BaC^; titrate excess Ba with K palmitate; phenol-
phthalein end point.
60
-------
CONVERSION-DETECTION
.280. Archer, E. E., "Determination of Small Amounts of Sulfate by Reduction
to Hydrogen Sulfide and Titration with Mercuric or Cadmium Salts
with Dithizone as Indicator," Analyst, 8Jh 181-182 (1956).
Titration with Hg(OAc) . Wet reduction, distill into dithizone.
281. Cubero, S. N. , "Determination of Sulfate by Reduction to Sulfur Dioxide,"
Anales Real Soc. Espan. Fiz. Quim.. Ser. B.. 6JJ11) : 1097-1100 (1965).
804" to S02 by powder Cu. Detected using West-Gaeke or iodometrically.
282. Davis, J. B., "Spectrophotometric Microdetermination of SO,," Anal.
Chem. . 44J3) : 524-532 (1972).
SO," to H2S by treatment with HI, AC20, and Na hypophosphite. H~S
reduces Fe^~3 and 1,10-phenanthroline to bright orange ferrous com-
plex. Photo measured at 510 nm. Few interferences. 0-100 ug range.
283. Emery, R. St. J., "Determination of Sulfate Content of Chromium Plating
Solution by Combustion Methodology," Electroplating and Metal Finish-
ing. 1^:253-257 (1960).
Reduce in 0~ stream using Fe and Sn powder. Absorb in ^02 solution
and titrate with NaOH to methyl red end-point.
284. Geilmann, W., "Microanalytical Determination of Sulfates," Glastech.
Ber.. 33j332-338 (1960).
The sulfate is reduced using HI + H3P02 to H S, absorbed in NaOH
and titrated with CdCl2-dithizone indicator.
285. Gel'man, N. E., "Microdetermination of Sulfur in Organic Compounds,"
Zavodskaya Lab., 8:673-677 (1939).
S to H2S using H2 and Pt gauze; H2S absorbed in ZnSO,; S determined
iodometrically.
61
-------
286. Gustafsson, L., "Determination of Ultramicro Amounts of Sulphate as
Methylene Blue - I. The Colour Reaction," Talanta, 4j 227-235 (1960). '•-
SO," as sulphide determined spectrophotometrically as methylene blue;
sulphide reacts with p-aminodimethylaniline and ferric iron.
287. Gustafsson, L., "Determination of Ultramicro Amounts of Sulphate as
Methylene Blue - II. The Reduction," Talanta. 4j 236-243 (1960).
S0,= reduced to sulphide by hydriodic and hypophosphorous acids in
acetic acid solution.
288. Horton, A. D., "Polarographic Determination of Sulfate," Anal. Chem.,
23j 1859-1860 (1951).
Reduction of SO, to H S using hydriodic acid. Precipitation out as
CdS. Dissolve in HCl. Determine Cd by polarography.
289. Johnson, C. M., "Microestimation of Sulfur in Plant Materials, Soils,
and Irrigation Waters," Anal. Chem., 24(4):736-742 (1952)0
SO^=-S reduced by mixture of HI, HC02H, and red P; H2S determined
spectrophotometrically with methylene blue; 1-300 ug determination
limit with + 5%.
290. Kiba, T., "Tin (II) - Strong Phosphoric Acid - A New Reagent for the
Determination of Sulfate by Reduction to Hydrogen Sulfide," Bull.
Chem. Soc. Japan, 28j 641-644 (1955).
Tin plus concentrated H-jPO^ ^ H2S which is titrated with iodine.
291. Larsen, R. P., "Separation and Determination of Microgram Amounts of
Sulfur," Anal. Chem., 31(9):1596-1597 (1959).
Sulfur fused with vanadium pentoxide reduced over Cu; S02 absorbed
in sodium tetrach1oromercurate and determined spectrophotometrically
with pararosaniline and formaldehyde.
292. Lorant, I. S., "A New Colorimetric Microchemical Method for Determination
of Sulfur in Sulfides, Sulfates, Etc.," Z. Physiol Chem.. 185j 245-266
(1929).
Reduction of S using HI, red P and C02H2; distill H2S into Zn(OAc)2
and determine using methylene blue.
62
-------
293. Lorant, I. S., "A New Colorimetric Micro Method for Determination of
Sulfur in Sulfides, Sulfates, Etc.," Z. Physiol Chem. . 193^:56-58
(1930).
Describes additional years experience. Minimum detected 0.5 ug,
51 error.
294. Luke, C. L., "Determination of Total Sulfur in Rubber," Ind. Eng. Chem. ,
Anal. Ed.. 15_:602 (1943).
HI
SO, - > H2S. Then iodometric titration.
295. Quartermain, P. G. , "An Improved Method for Determination of Small
Amounts of Sulfate," Analyst. 85j 211-215 (1960).
Digest with Ti-H-PO^; H2S removed with C02 and absorbed in NaOH
solution. Titrate with Hg(OAc)2 solution with diphenylthiocarbazone
indicator.
296. Ramanauskas, E., "Determination of Trace Amounts of Sulphate Sulfur
with Crystal Violet," Elem. Mikrokiekiu Nustatymas Fiz.-Chem. Metod..
Liet. TSR Chem. -Anal. Mokslines Konf. Darb., 2nd, pp. 145-152
(1969).
Reduction with Sn and H-PO, to H2S and measure crystal violet absorption
with Chloramine B and KI at 400 nm. Beers Law valid 0.161-2.08 ug/ml. .
297. Rancke-Madsen, E., "Determination of Sulfate by Reduction with Stannous
Chloride," Acta. Chem. Scand. . 3_: 773-777 (1949).
Reduction with SnCl2 and HgPO^ to H2S, absorbed in I2, titrate with
298. Rancke-Madsen, E., "Determination of Sulfate by Reduction with Stannous
Chloride. II," Acta. Chem; Scand.. 6:305-306 (1952).
Hg, Cu interfere, Pb++ does not (see above).
299. Roth, H., "Colorimetric Determination of Traces of Sulfur," Mikrochemie
ver. Mikrochim. Acta, 36/37_: 379-392 (1951).
After oxidation reduce to H2S using HI, C02H2 and hypophosphite.
Collect in Zn(OAc)9 and determine with methylene blue.
63
-------
300. Scaringelli, F. P., "Determination of Atmospheric Concentrations of
Sulfuric Acid Aerosol by Spectrophotometry, Coulometry, and Flame
Photometry," Anal. Chem.. 41(6):707-713 (1969).
H2SO^ separated from SO,, and other sulphates. SO., in N2 converted
to S02 with hot Cu. S0? determined by FPD. Method can measure
H2SO, in presence of 100 x as much SOo and other sulphates.
301. Stanford Research Institute, "Size Determination of Atmospheric Sulfate
and Chloride Particles," HEW Contract No. PH-86-64-54.
Thermal sulfur reduction to H-S; determined by microcoulometric
titration.
302. Stratmann, H., "Microanalytical Determination of Various Sulfur Com-
pounds in Gases and in Solids," Mikrochim. Acta.. pp. 1031-1037 (1956)
Reduction by Ho and conversion to H2S on a Pt catalyst. Detection
by Moly Blue reaction and micro-crystal structure.
303. Volkov, I. I., "Determination of Sulfates by Reduction to Hydrogen
Sulfide," Zhur. Anal. Khim.. 13:686-690 (1958).
SO^ reduced with SnCl2 + H-jPO^. H2S + Cd(OAc)2 = CdS, add to
acidified !„, titrate with Na2S 0 .
304. Wiesenberger, E., "Microchemical Determination of Sulfur in Organic
Compounds," Mikrochemie ver. Mikrochim. Acta. 29j73-86 (1941).
S + H9 with Pt catalyst to HoS and idiometric titration.
64
-------
ELECTROMETRIC
305. Agasyan, P. K., "Potentiometric Determination of Lead and. Sulfate Ions. I.,"
Vestnik Moskov. Univ., 8(5) Ser. Fiz-Mat. i Estestven. Nauk, (3):65-68
(1953).
Discusses effects of temperature, pH, etc.
306. Agasyan, P. K., "Potentiometric Determination of Lead and Sulfate Ions.
II.," Vestnik Moskov. Univ., 8(8), Ser. Fiz-Mat.i Estestven. Nauk,
(5):121-124 (1953).
Potentiometric titration with K^Fe(CN)g of S0^= solution.
307. Akhmedov, G., "Amperometric Analysis of Anion Mixtures Containing Sodium
Sulfites and Thiosulfates," Nauch. Tr. Tashkent. Univ., No. 379,
3 :182-188 (1970).
I„ reduction current at rotating Pt electrode used in amperometric
titration of S03= and S203=:. ;
308. Akimoto, N., "Potentiometric Microtitration of Sulfate Ion Using a Sodium-
Selective Electrode in a Nonaqueous Medium," Anal. Chem., 46(6):766-769
(1974).
BaCl2 titration.
309. Anderson, L. J., "Apparatus for Rapid Conductometric Titrations Determination
of Sulfate," Anal. Chem., 1^:264-268 (1947).
Conductometric titration, BaC^-
310. Atanasiu, I. A., "Potentiometric Determination of Sulfate by Indirect
Titration with Benzidine," Z. anal. Chem., 90:337-340 (1932).
Excess benzidine titration with KN02-
311. Baudisch, J., "Direct Potentiometric Determination of Sulfate," Fresenius
Z. anal. Chem., 235J3) : 231-234 (1968). ,
Titration with 10:1 mixture. .1 N Ba and Pb (NC^). Det. delta pH.
Range 100-500 mg/liter. 0.7% ace.
65
-------
312. Boos, R. N., "A Volumetric Microdetermination of Organically Bound Sulfur
and Organic and Inorganic Sulfates," Analyst, 84:633-635 (1959).
Sulfates + BaCl2- Excess determined by potentiometric titration with
Na.EDTA. Hg ref. electrode.
313. Bruno, A., "Analysis of Wines by their Conductivities," Bull. Soc. Chim. ,
1^:24-34 (1913).
Found conductivity measurement did not agree with precipitate results.
' Butenko, G. A., "Polarometric Determination of Sulfate Ion," Zavodskaya
Lab., 9:634-635 (1940); Kim. Referat. Zhar. , 4(l):88-89 (1941).
»*•* *+~
Pb(N03)2 titration.
315. Cassidy, N. G., "Electrometric Method for Determining Sulfate Ion,"
Analyst. 81^:169-175 (1956).
PbS04 precipitate with Pb(N03)2 in ETOH .Titrate excess Pb with
K2Cr04- Delta pH end point.
316. Chounyk, N. G., "Use of a Limiting Current of Lead Ions in Polarography
and Amperometry," Metody Kontr. Khim. Sostava Neorg. Org. Soedin.
pp. 52-58 (1966).
Rotating Pt anode; NaNO,, supporting medium for S0^= determination.
317. Christensen, B. E., "Rapid Potentiometric Method for Determination of
Sulfate," Ind. Eng. Chem. . Anal. Ed., 10:413-414 (1938).
BaClo titration. Best results with 25-60 alcohol.
318. Coetzee, C. J., "Anion-Responsive Electrodes Based on Ion Association
Extraction Systems," Anal. Chem. , 40(13) -.2071 (1968).
1 v*r~
Direct reading electrodes - SO^3, 10"1 to 10~5 M.
319. Coetzee, C. J., "Liquid-Liquid Membrane Electrodes Based on Ion-Associ-
ation Extraction Systems," Anal. Chem., 41^(8) : 1128-1130 (1969).
pH dependency and effect of interfering anions.
320. Cortellessa, G. C., "Potentiometric Microdetermination of the Sulfate
Ion," Analyst, 93J 1109) -.546-547 (1968).
Titrated with lead nitrate.
66
-------
321. Davies, W. C., "Amperometric Determination of Sulfates," Ind. Chemist,
1.9:167-169 (1943).
Polarographic titration with
322. Dolgaleva, A. A., "Semiautomatic Instrument for Amperometric Titration
(of Sulfates and Chlorides in Paper)," Bum. Prom., 9:15 (1967).
Soviet pulp and paper industry standard test method. No chemical
details in C.A.
323. Dutoit, P., "Simultaneous Determination of Sulphates, Acidity on
Tanning Substances in Wine," Schweiz Wochschs., 46:690-694 (1909).
Used pt electrode. Titrated to first break in curve with Ba(OH)2-
324. Duval, R., "Differential Electrometric Titration," Compt. Rend.,
205j 1237-1238 (1937).
Comparative electrical measurement with bridge circuit.
325. Freak, G. A., "The Effect of Dilution in Electro-Titrimetric Analysis,"
J. Chem. Soc.. 115:55-61 (1919).
Discussion of early methods and limitations.
326. Galkin, D. E., "Electrometric (Potentiometric) Method for the Determina-
tion of Sulfate Ions," Trudy Tomsk. Gosudarst Univ. im. V. V.
Kuibysheva, Ser. Khim., 14js (5-ya) Nauch. Knof.. pp. 163-172 (1954).
Konf. Pub. 1957.
SOT determination with bi-metallic electrodes combined with
Fe(CN)2~/Fe(CN)£~electrode to detect excess Pb.
o o
327. Gardner, G. L., "Complex Formation in Lead Sulfate Solutions," Anal.
Chem.. 42(7):794-795 (1970).
Determined dissociation constants of PbSO,.
328. Gladyshev, V. P., "Direct Oscillopolarographic Determination of Sulfates,"
Zavodsk. Lab.. 28j 1063-1065 (1962).
10-3 to iQ-4 M SOT; 7 to 8% accuracy.
67
-------
329. Goldstein, G., "Conductometrie Determination of Sulfate by the Non-
aqueous Barium Acetate Method," Anal. Chem., 3JK1169-1170 (1962).
SO^"precipitate with BaAc in HAc. Excess BaAc determination by
electrotitration with perchloric acid.
330. Goldstein, G., "Indirect Determination of Sulfate by Nonaqueous Titri-
metry," Anal. Chem., 33(2):266-268 (1961).
Sulfate precipitated by barium acetate. Potentiometric titration
determines the excess acetate.
331. Gordon, B. E., "Determination of Sulfite and Sulfate (as Sodium Sulfate)
in Sodium Petroleum Sulfonates - An Amperometric Titration," Anal.
Chem. . 25^:897-901 (1953).
Amperometric titration with lead ion in alcohol solution.
332. Harned, H. S., "Titration of Some Bivalent Metal Sulfates by the
Conductance Method," J. Am. Chem. Soc., 39:252-266 (1917).
Titration with Ba(OH)2.
333. Havas, j., "Potentiometric Determination of Sulfate by Ion Selective
Membrane Electrode/' Proc. Conf. Appl. Phys. Chem., 2nd Ed., 1:625-
629 (1971).
Combined S0^= electrode(Pbl2 precipitate as auxiliary material with
renewable surface and iodide-selective membrane electrode) used for
S0^= determination; iodide-selective electrode also useful for SCv=
determination by determination of I" after ion-exchange between
PbI2 and S0^=.
334. Henscheid, T., "Application of Ion-Selective Electrodes in the Beet
Sugar Industry," American Soc. Sugar Beet Technol., 16(6):482-495
(1971). ~~
Potentiometric titration of S0^= - Beet Sugar.
335. Heyrovsky, J., "Analytical Method of Electrolysis with a Cathode of Drop-
ping Mercury," Bull. Soc. Chem., 4^:1224 (1927).
Mentioned that it would be possible to titrate 50^= amperometrically -
History.
68
-------
336. Heyrovsky, J., "Bibliography of Publications Dealing with the Polaro-
graphic Method from 1940-1945," Collection Czechoslov. Chem. Commun. ,
12^:156-192 (1947).
337. Hokhstein, Y. P., "Polarographic Determination of Sulfate Ion III.,"
Zavodskaya Lab. . 5:1444-1447 (1936).
Ba by polarimetric titration.
338. Humphrey, R. E., "Polarographic Determination of Chloride, Cyanide,
Fluoride, Sulfate and Sulfite with Metal Chloranilates," Anal. Chem.,
: 1895-1897 (1971).
o c
Range 10 to 10 M; linear curve (ua/ppm) ; Polarographic -(Me)
cellulose acetic acid, Ba chloranilate.
339. ishibashi, M. , "Amperometric Titrations. III. Studies with a Short
Circuited System," Sbornik Mezinarod. Polarograf . Sjezda, Praze, 1st
Congr. Pt. I, pp. 115-116 (1951).
by excess Pb using dropping Hg electrode. No experimental details.
340. James, H. J., "Electrode for Potentiometric Measurements," Ger. Of fen,
2,215,378, U.S. Appl.. 219,119, 19 January 1972.
Patent papers .
341. James, H. J., "Coated Wire Ion Selective Electrodes," Anal. Chem.,
44(4):856-857 (1972).
**s*~
PVC coated Pt wire. S04=- fast linear response - .1 to 100 m M.
342. Jamieson, G. R. , "Volumetric Determination of Sulfate by Using a High-
Frequency Conductimetric Method," J. Appl. Chem. . 7:81-86 (1957).
NOo interferes, Cl does not. Ba, Pb, octa-ammino-u-nitrocobaltic
tetra nitrate and hexa-amminocobaltic bromide as precipitates,
poor sensitivity (2 mg) .
343. Jander, G., "Conductivity Titration with Visual Observance: A Conducto-
metric Determination of Sulfate in a Boiling, Aqueous Solution,"
Z. Angew. Chem., 4£: 1037-1038 (1929).
Lecture on electrometric titration (1929). S04=as example.
69
-------
344. Jasinski, R. , "Application of a Sulfate-Sensitive Electrode to Natural
Waters." Anal. Chem. . 45J7) : 1277-1279 (1973).
150 mg. SC>4/liter.
345. Jasinski, R. , "Potent iometric Titration of Sulfate Using an Ion-Selective
Iron Electrode," Anal. Chem., 44(14) :2373-2376 (1972).
Indirect sulphate electrode based on ferric iron/ 504= complex. No Cl,
N03, HC03 interference.
346. Johannesson, J. K., "A Note on the Determination of Low Concentrations
of Sulfate in Rain and Other Waters," New Zealand J. Sci. , 1:423-424
(1958).
0-10 ppmSO,=; ion exchange S04= to 112804, add mercuric oxide;
determine SO /=by conductivity.
347. Keller, R. E., "Titrimetric Determination of Sulfates by Diazo Titration
of Benzidine Sulfate," Anal. Chem.. 26(9) : 1518-1519 (1954).
SO^* determined by presence of sulfonates by benzidine sulfate preci-
pitation; precipitate titrated potentiometrically with KN02; W-calomel
electrode.
348. Kling, A., "Physico-chemical Determination of Sulfates," Compt . Rend . ,
15^:487-489.
Investigated Dutoit's method and found to be subject to large
interferences.
349. Kokina, T. A., "Electrometric Ultramicrotitration of Sulfate Ion,"
Zh. Anal. Khim. , 2(11) : 2237-2239 (1971).
Potentiometric Pb(N03)2 titration for trace amounts of SO^. Total
volume 3-5 u liter.
350. Kolthoff, I. M., "Amperometric Titrations. VI. The Titration of Sulfate
and Some Other Anions with Lead and the Reverse Titrations," J. Am.
Chem. Soc., 6^:3332-3335 (1940).
SO^" titration with Pb(N03)2 using dropping Hg electrode.
70
-------
351. Kolthoff, I. M. , "Conductometric Titration of Sulfate and Barium,"
Ind. Eng. Chetn. . Anal. Ed.. 3 129-133 (1931).
titration alkali and ZnSO^. Best results--very dilute solu-
tions with 30% ETOH; investigations of "knickpoint" versus equivalence
point deviations.
352. Kolthoff, I. M. , "The Use of Conductivity Titrations in Precipitation
Analyses. V. Conductivity Titrations with Barium Salt," Z. Anal.
Chem. . 61^:433-438 (1922).
Al, Fe, Ca, and NO^ interfere.
353. Kreshkov, A. P., "Determination of Sulfuric Acid, Bisulfates, and Sul-
fates," Zavod. Lab., 34J11) : 1295-1296 (1968).
Potentiometric titration in 2:1 Ifc^CO-Cl^OHCl^OH with KOH.
354. Lukkari, U. 0., "Membrane Electrodes. I. Barium Chromate-Impregnate
Silicone Rubber Membrane," Suom. Kemistilehti B. 45(5-6) : 182-185
(1972). ~~
May be used in precipitation titrations for SOT.
355. Lyalikov, Y. S., "Polarimetric Method of Anion Analysis. Amperometric
Titration with Lead Ions," Zhur. Anal. Khim. . 1(2): 147-157 (1946).
General theory review.
356. Majer, V., "Polarimetric Titrations," Z. Elektrochem. 42j 120-123 (1936).
Description of early polarimetric titration.
357. Mather, W. B., Jr., "Coulometric-Acidimetric Titration of Fluoride in
Acetic Anhydride," Anal. Chem., 53j 132-134 (1961).
Discussion; potentiometric determination of end-point.
358. Mayer, J., "Detection Limit in the Polarographic Microdetermination
of Sulfates in Water," Fortschr. Wasserchem. Ihrer Grenzgeb. , 11:
181-188 (1969).
SCrf replacement by CrO, ; Cr determined polarographically; compares
well with gravity and titration.
71
-------
359. Mayer, J., "Polarographic Microdetermination of Sulfate," Anal. Chem. ,
39_:1460 (1967).
Polarographic method using conversion of SOT to CrO^. Range 0 to
50 mg/liter.
360. Miller, A. D., "Direct Potentiometric Titration of Sulfate Ion with an
Indicator Electrode Mo(Mo03)BaS04 I.," Zhur. Anal. Khim. , llj 615-620
(1956); J. Anal. Chem., 11^:655-660 (1956).
Preparation of the electrode. Ba titration. Range 0.008 to 0.100 N
S0=.
361. Mohan, M. S., "Preparation and Properties of the Sulfate Ion-Selective
Membrane Electrode," Anal. Chem., 45(8) : 1323-1326 (1973).
Construction details.
362. Mu'ller, E., "The Electrometric Determination of Soluble Sulfates,"
"Z. Arong. Chem., 133j411-416 (1924).
SO? precipitated with Pb. Excess Pb determination by electrotitra-
tion with K^Fe(CN)6.
363. Mukai, S., "Potentiometric Determination of Barium, Lead, and Sulfate,"
Bull. Tech. Coll. Kyasha Imp. Univ., 4:17-21 (1929).
SO^ precipitate with excess Pb (1^03)2 • Excess Pb determination by
Potentiometric titration with I
364. Murakami, S., "Short-Circuit Amperometric Titration of Sulfate Ion,"
Kobe Daigaku Kyoikugakubu Kenkyu Shuroka, (4n);ll-15 (1968).
Ba at pH 5.3-7.3 using S.C.E as reference electrode and chromate
indicator.
365. Myers, S. A., "Automatic Amperometric Titrations Using a Mercury
Cathode," Talanta, 12(2) :133-138 (1965).
Apparatus described. Auto-titration of SO, = with Pb(NOo)2 in detail.
Sens. 0.001 millemole SO, =
4
366. Ohlweiler, A. 0., "Indirect Polarographic Determination of Sulfate,"
Anal. Chim. Acta, 9:476-488 (1953).
• • • -- *^,
SO, by polarographic determination of Pb.
72
-------
367. Pasovskaya, G. B., "Conductometric Titration of Sulfate Ions," Lab. Delo. ,
4(3): 30-33 (1958).
Method for natural waters. Excess BaCl2 titrated with Na2SO,. Not
good for less than 12 mg/liter SOT.
368. Peniston, Q. P., "Sulfite Waste Liquor Analysis," Anal. Chem., 19:332
(1947).
Conductometric. BaC^ cation exchange; Na replaces Ca; 50% IPA.
369. Pungor, E., "Membrane Electrodes in Chemical Analysis," Z . Chem . ,
5(1):9-14 (1965).
Permselective and reversible. SO/ "concentration 10 -10 M.
370. Rechnitz, G. A., "Potentiometric Measurements with Sulphate-Ion and
Phosphate-Ion Sensitive Membrane Electrodes," Anal. Lett., l(l):29-33
(1967).
Preliminary evaluation of SO^ -PO^ electrodes.
371. Rechnitz, G. A. , "Sulphate Ion-Selective Membrane Electrode," Anal. Chem.,
44 (6) -.1098-1099 (1972).
SOA= selective crystal membrane (Ag-S, PbS, PbSO,, Co?S).
372. Ross, J. W. , Jr., "Potentiometric Titrations of Sulfate Using an Ion-
Selective Lead Electrode," Anal. Chem.. 41^(7) : 967-969 (1969).
Titration of S04= with Pb(C10, )„ with Pb-selective electrode in
50% dioxane media; Cu, Hg, Ag,PO^, Cl, NO-, and HCO, may interfere.
373. Salzano, F. J., "Determination of Sulfur Oxides in Gases," Ger. Of fen.,
2,260,193 (Cl. Goln), 14 June 1973, U.S. Appl., 206,352, 9 December 1971.
Electrochem cell for determination of S02> 803 in air. Test and Ref.
electrodes in closed quartz tubes connected and filled with molten
eutectic. Cell EMF was linear function of log SOX in PPM range.
374. Saunders, A., "Specific Ion Electrode for Sulfate," HEW, U.S.
3,709,811 (Cl. 204-195M; Goln), 9 January 1973.
in Silicone rubber membrane.
73
-------
375. Selig, W., "Micro and Seraimicro Determination of Sulfur in Organic
Compounds by Potentiometrie Titration with Lead Perchlorate,"
Mikrochim. Acta., 1:168-175 (1970).
Absorption in NaNOs; boil, add 1,4-dioxane, titrate potentiometrically
with Pb(ClOA)o and a Pb-sensitive indicator electrode.
376. Shartukov, 0. F., "Potentiometric Determination of Small Amounts of
Sulfate Ions and Lead Ions," Zh. Anal. Khem., 26(10):1967-1972
(1971). ~~
Potentiometric determination in a flow concentration cell. Range
1-200 mg/liter.
377. Sierra, F., "Potochemical Redox Indicators in Amperometry. Indirect
Determinations of Anions with Disodium Dihydrogen Ethylenediamine-
tetraacetate," Inform. Quim. Anal.. 27(2):93-98 (1973).
Thionine (I) used as photochemical redox indicator in indirect
amperometric titration of SOT.
378. Sinha, S. K., "Potentiometric Titrations with Resin Membrane Electrodes,"
J. Indian Chem. Soc., 32:35-38 (1955).
Reversible resin membrane electrodes; from ion-exchange resins;
used for S0^= determination.
379. Summers, P. W., "Source and Budget of Sulfate in Precipitation from
Central Alberta, Canada," J. Air Poll. Cont. Assoc., 23(3):194-199
(1973).
Precipitation samples analyzed for S0^~ by conductometric titration
against barium trichloroacetate.
380. Spalenka, M., "Polarographic Studies with the Dropping Hg Electrode,"
Coll. Czechoslov. Chem. Commun.. 11:146 (1939).
Improvement of polaragraphic titration using 33.370 ETOH.
381. Spillner, F., "Conductometric Sulfate Determination," Angew. Chem.,
66^198-201 (1954).
63(1^03)2 - "Overtitration" is measured directly - "giving results
in a 3 min period."
74
-------
382. Takagi, K. , "A Simple Potentiometric Method for the Rapid Determination
of Sulfate," J. Electrochemical Soc.. 18j 123-125 (1950).
BaCl titration with MeOH and (NH^) 2S Og bi-metallic electrodes.
383. Ten'Kovtsev, V. V., "Amperometric Determination of Sulfate Ion," J. Anal.
Chem., 12_:523-526 (1957). -.
double titration.
384. Tockstein, A., "Use of Complexones in Chemical Analysis. XXXIV. Polar-
ographic Determination of Sulfates and Barium," Chem. Li sty, 45:539-542
(1951); Collection Czechoslav. Chem. Communs., 16:398-404 (1951).
Indirect SQ{. determination via Ba-H- interchange with Ag- in complex.
385. Trachtenberg, I., "Ion-Selective Electrochemical Sensors," U.S. Office
Saline Water, Res. Develop. Progr. Report No. 761, (1972).
Cation sensors - Fe, Cu.
386. Ugol'nikov, N. A., "Electrometric Determination of Sulfates in Mineral
Waters," Tr. Tomskogo Cos. Univ.. Ser. Khim., 154:262-263 (1962).
Acidify HC1, add K3[Fe(CNe)], K4[Fe(CN)fc] and ETOH. Titrate with
using Pt, Ag electrode.
387. Vail, E. I., "Potentiometric Determination of Sulfate Ions," Zhur. Anal
. Khim. , 15j 369-370 (1960).
Titration with Na^S.
388. Visyagin, N. I., "Electrometric Determination of Soluble Sulfates,"
Byull. Inst. Haluigie, 12:3-11 (1939).
0.02-4% SO? in brine. Potentiometric titration with quinhydrone and
BaCl~; calomel-Pt electrodes.
389. Wagner, A., "Rapid Potentiometric Determination of Sulfate, Nitrate,
and Chloride Ions in Water and Aqueous Solution," Mitt. Ver.
Grosskesselbesitzer. 5!2: 50-53 (1958).
Simultaneous SO,, NO-,, Cl determination. Ion-ex conversion to acids.
Then titration in sequence with Ba(OH)2> K palmitate, and AgNO-j to
specified pH values.
75
-------
390. West, L. E., "Vacuum-Tube Voltmeter, Application to Potentiometric
Precipitation Titrates," Ind. Eng. Chem., Anal. Ed.. 1^:476-478
(1940).
Description of construction and use of one-tube VTVM (obsolete);
BaCl2 titration.
391. Woods, R., "Polarographic Kinetically Controlled Currents in Systems
Containing Persulfate, Copper (II), and an Agent which Reacts with
Sulfate Free Radical," Anal. Chem., 38J10) :1297-1302 (1966).
Cation (Cu,As) effects on persulfate curves.
392. Young, M., "Potentiometric Determination of Sulfur Dioxide in Flue Gases
with an Ion-Selective Lead Electrode," Anal. Chem., 45(13):2283-2284
(1973).
Collection in 370 H202. 804 precipitate with Pb. Excess H202
elimination with Zn.
393. Zando, A. M., "Electrical Conductivity as a Basis for Physiochemical
Analysis," Sci. Mag. Chem. Cath., Katerinoslav, pp. 79-91 (1926).
Early work with "electrical" titration end-points. ^0-4 determination •
Good results only with bivalent cations.
394. Zhukov, I. I., "Potentiometric Determination of Sulfates," J. Ger. Chem.,
4:962-968 (1934).
Pb(N03)2 titration with K4Fe(CN)6 and K3Fe(CN)& added in ETOH/H20
solution.
76
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FLAME PHOTOMETRIC
395. Burriel, F. , "Indirect Flame Photometric Determination of Sulfate Ions,"
Anal. Chim. Acta.. 17_: 559-569 (1957).
804" determined by precipitation with Ba++ or Sr"1"*; flame photo
determination of cation in filtrate or centrifugate; Ba++ -
0 to 70 ppm S04=; Sr++ - 0 to 110 ppm
396. Burriel, F. , "The Indirect Flame Photometric Determination of Sulfate
Ion." Rev. Cien. C. Apl. . 12:16-25 (1958).
Discussion of standard curve anomalies and causes thereof.
397. Cullum, D. C. , "The Flame-Photometric Determination of Barium and
Sulfate - An Improved Technique," Analyst. 85:688-689 (1960).
Conversion of detergent 864 to Ba-NH4 EDTA suspension.
398. Herb ol she imer, R. , "Flame Photometric Determination of Sulfate,"
Z. anal. Chetn. , 20^(6) : 418-419 (1964).
Ba emission - EDTA-triethanolamine solvent.
399. Odler, I., "Flame-Photometric Determination of Sulfates," Chem. Zvesti,
15:568-570 (1961).
804" precipitated with excess BaCl2 and disolved in ammoniacal EDTA.
Ba determined by flame.
400. Robinson, G. A., "A Micro Method for the Determination of Sulfate by
Flame Photometry," Can. J. Biochem. and Physiol., 38:643-648 (1960).
Barium emission intensified by addition of LiCl.
401. Shaw, W. M. , "Indirect Flame Spectrophotometric Determination of Sulfate
Sulfur," Anal. Chem.. 30:1682-1689 (1958).
Ba emission with Ca, Sr, Mn interference.
77
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FLUOROMETRIC
402. Guyon, J. C., "Fluorometric Determination of Microgram Quantities of
Sulfate," Anal. Chem.. 38(1):155 (1966).
Based on SOT interference with Thorium/Morin reaction. Simple
sens, method (0 to 40 ug range). Adaptable to large numbers of
samples.
403. Nasu, T. (see Spectrophotometric listing).
404. Nazarenko, V. A., "Fluorometric Determination of Sulfate Ion and Spectro-
photometric Determinations of Thorium with the Help of Trihydroxyfluorene
Derivatives," Zavodsk. Lab., 24j 1344-1346 (1958).
Sample plus Th, detect excess Th with 9-(0-hydroxyphenyl)trihydroxy-
fluorone (salicylfluorone).
405. Yangsheva, V. S., "The Determination of Sulfates in Distilled Water
with Salicylfluorone," Metody Anal. Kim. Reakt. Prep. Tos. Kom.
Sov. Min. SSSRpoKhim., 4(1962):135 (1962).
Sulfate plus Th(NOo), plus indicator; measure fluorescence.
78
-------
GRAVIMETRIC
406. Alcino, J. F., "Microanalytical Determination of Sulfur. A Modified
Bomb Method," Ind. Eng. Chem.. Anal. Ed.,13:506-507 (1941).
Na2 0.1% as a source of error in precipitation with BaCl9.
79
-------
415. Dhandhukia, M. M., "Rapid Method of Sulfate Estimation," Salt Res. Ind..
Ml): 17-18 (1968).
BaSO, precipitate-wash and weigh.
416. Environmental Protection Agency, "Methods for Chemical Analysis of
Water and Wastes," EPA-625/6-74-003, p. 283 (1974).
Sulfate-gravimetric method uses APHA and ASTM methods.
417. Fales, H. A., "Factors Influencing the Determination of Sulfate as
Barium Sulfate," Ind. Eng. Chem.. Anal. Ed.. U;206-213 (1939).
Can remove KNOj interference by addition of HC1.
418. Fischer, R. B., "Rapid Precipitation of Barium Sulfate," Anal. Chem.,
25^:1544-1548 (1953).
In-depth study of precipitation of BaSCy,. with BaCl2.
419. Friend, J. A. N., "Determination of the Sulfate Ion by Precipitation
as Barium Sulfate," Analyst,57:559-562 (1932).
Early BaCl2 procedure for 80^= in I^SO^," SO = £ 0.02 N.
420. Gerarde , H. W., "lexicological Studies on Hydrocarbons. VII. A
Gravimetric Method for the Determination of Inorganic and Ethereal
Sulfate in Urine," Amer. Ind. Hyg. Assoc. J.. 21^511-514 (1960).
Rapid simplified method using quantitative self-regulating pressure
filtration technique with barium.
421. Germuth, F. G., "The Occlusion of Barium Chloride by Barium Sulfate,"
Am. J. Pharm.. 99.: 271-274 (1927).
Discussion of temperature factor in precipitation of SO ~.
422. Girman, "A Rapid Method for Determining Sulfates," Novoe v Praktike
Hidrogenizatii Zhirov» Sbornik Vsesoyuz. Nauch.-Issledovatel. Inst.
Zhirov.. pp. 127-129 (1939), Khim. Referat. Zhur. No. 3, p. 55 (1940).
S0^=in Ni catalysts by volume of BaSO, precipitate in centrifuge
tube.
80
-------
423. Gottschalk, G., "Gravimetric Determination of Sulfate as Benzidine
Sulfate," Z. anal. Chem.. 155;. 251-263 (1957).
Sulfate detected by analysis of Ni wire, Fe plate, Zn02, HoO, and
methylene blue; metal ions removed by ion exchange and POg as
MgNH4P04; S to + 0.05 mg.
424. Hahn, F. G., "Composition of Analytical Precipitates of Barium Sulfate,"
Z'Anorg. Allgem. Chem., 206;398-406 (1932).
Precipitate weight error due to formation of HoSO/.
425. Isakov, P. M., "Rapid Gravimetric Method of Determining Sulfate Ion,"
Nauch. Byull. Leningrad. Gosudarst. Univ., 13:8-10 (1946).
Adds picric acid to hasten BaSO^ precipitation, improve size and
form of crystal, and ease filtration.
426. Karoglanov, Z., "Causes of Contamination of Precipitates. I. Precipi-
tation Reactions in which Barium Compounds Participate," Z. anal.
Chem., 10(5:129-146 (1936).
Examines contamination of precipitate; believes errors due to con-
tamination during early stages rather than adsorption phenomena.
427. Kolthoff, I. M., "The Determination of Sulfate as Barium Sulfate," Z^_
anal. Chem., 5j3:49-69 (1919).
428. Kolthoff, I. M., "The Gravimetric Determination of Sulfate as Barium
Sulfate," Pharm. Weekblad.. 56^:122-142 (1919).
Literature review of BaSO- determinations with conclusions.
429. Kolthoff, I. M., "The Determination of Sulfates as Strontium Sulfate,"
Z. anal. Chem., 5J3: 20-23 (1919).
430. Kolthoff, I. M., "The Determination of Sulfates as strontium Sulfate,"
Pharm. Weekblad., 5j6:159-161 (1919).
Free acids and certain salts are disturbing factors and use of 5070
EtOH makes solubility sufficiently low.
431. Kolthoff, I. M., "Determination of Sulfate According to F. Hahn at
Extreme Dilution," Z. anal. Chem.. 63:392-404 (1923).
81
-------
432. Kolthoff, I. M. , "Sulfate Determination According to Hahn at Great
Dilutions," Pharm. Weekblad., 60:1177-1190 (1923).
Hahn's method (S04~ + Ba salt in boiling H20) combined with Winkler's
method (filtering on asbestos); Precipitation in AcOH better than HCl;
codeine-HCl, P04=, Ca all interferents .
433. Ledoux, L. , "Application of Mechanical Precipitation to the Determina-
tion of Sulfuric Acid, Sulfates, Calcium, and Potassium," Bull. Soc.
Chim. Belg.. 2£: 51-52 (1914).
Mechanical agitation in cold with pure HCl and 2% BaCl2'2H20;
filtered, washed with H,,0 and ignited.
434. Mahr, C., "A New Method for Determining Sulfate," Z. anal. Chem.. !L28:
477-484 (1948).
SO/= detected by precipitation of [^(NH^glBrSO^; precipitated
S0,= may be determined gravimetric or dissolved in water and Br
detected by titration with AgNOo or Co detected colorimetrically.
435. Majdel, I., "Effect of Phosphoric Acid on the Determination of Sulfate
with Barium Chloride," Bull. Soc. Chim. Roy. Yougoslav. , 1_(2): 25-28
(1931).
S04= determined with BaCl2 in presence of P20s and HCl; increase in
P20,- or BaCl2 increases error while increase in HCl decreases error;
recommends removal of P20c prior to analysis.
436. Majer, V., "Practical Importance of Winkler's. Procedures for Determining
Calcium, Lead, Sulfate and Phosphate," Chem. Zentr. , 1_:782 (1942).
437. Majer, V., "The Practical Significance of the Winkler Procedure," Z_._
anal., Chem., 122: 257-262 (1941).
Winkler method useful in some cases but not as good or bad as some
feel.
438. Margolina, S. S., "Analysis of Products of Chlorination of Oxides and
Sulfides of Copper," Zavodskaya Lab . , 4:861-863 (1935).
With BaCl2 and Na^SO^.
82
-------
439. Marjanovic, V., "Determination of Sulfate Ion as Barium Sulfate," Arhiv
Hemilu, 1:5-18 (1927).
Cl~, N03~, Na, K, Mg, Fe, Cu, Al, and NH^ do not interfere; P0^=
gives high value and Ca low value. Uses HC1 and BaCl^; solution
< 0.3 g S04=.
440. Matsui, M., "The Determination of the Sulfate Content of Sodium Sulfate,"
J. Chem. Ind., 24j 1039-1053 (1921).
Examined five methods of BaSO, precipitation using pure Na^SC^.
441. Meillere, G., "Determination of H2S04 and Sulfates," J. Pharm. Chem.,
19;296-297 (1919).
Precipitation by BaCl~ in slightly AcOH medium and near 100°.
442. Meldrum, W. B., "Determination of Sulfate in the Presence of Chromate,"
Ind. Eng. Cehm.. Anal. Ed., 13^:456-457 (1941).
Precipitate BaC^, weigh, fuse NaCO^, detect CrO^ in precipitate
iodometrically.
443. Montequi, R., "Systematic Investigation of Anions," Anales Soc. Espan.
Fis. Quim., 3£:567-599 (1932).
SO," precipitate in AcOH solution by Ba(OAc)2«
444.- Oka, S., "Rapid Analysis by Centrifugal Methods," Japan Analyst, l^: 136-
140 (1952).
Quantitative analysis by volume measurement of BaSO^ after centrifuging
studied.
445. Orlov, I. E., "Rapid Method for Determining the Sulfate Ion by Means
of a 'Coupled' Precipitation," Z. anal. Chem.. 98^326-329(1934).
BaSO, precipitated with BaCl« in presence of AlClo; Al precipitated
by NH/OH to methyl redjAl precipitate coagulates BaSO^.
446. Dwells, B. R., "Estimation of Barium Sulfate in the Presence of Silica,"
Chemist Analyst, 31;6 (1942).
BaSO. weight in Gooch crucible.
83
-------
447. Owen, E. C., "Determination of Sulfates. A Study of the Conditions
Necessary for the Precipitation of Benzidine Sulfate, with Special
Reference to the Estimation of Sulfates in Urine," Biochem. J., 30_:
352-360 (1936).
Use pH of 2.75, must remove phosphate before precipitate; chlorides
do not interfere.
448. Pel'sh, G. K., "A Rapid Semimicromethod for the Determination of Ions
by Weighing the Precipitates in Centrifuge Tubes," Uchenye Zapiski
Leningrad. Gosudarst. Univ. im. A. A. Zhdanova; No. 211, Ser. Rhim.
Nauk,(15):105-115 (1957).
Simplified method of gravimetric determination; BaSO^ precipitate
centrifuged, dried, weighed.
449. Peskova, V. M., "Rapid Determination of the Sulfate Ion," Zavodskaya
Lab.. 9; 1329-1330 (1940); Chem. Zentr., .2:571 (1942).
Adds saturated picric acid and excess 57o BaCl~.
450. Pil'nik, R. S., "Rapid Gravimetric Method for Determination of Sulfate
in Sodium Dichromate and Chromic Anhydride (in technical grade
products)," Tr. Ural'sk. Nauchn.-issled. Khim. Inst., (ll):46-48 (1968)
_ _|_O
SO/~ precipitation as BaSO, in presence of NaOAc to mask Cr
451. Pribil, R., "Use of Complexions in Chemical Analysis. XXXV. Gravimetric
Determination of Barium and Sulfates," Chem. Listy, 45j542-544 (1951);
Collection Czechoslav. Chem. Communs., L6j 398-404 (1951).
Interfering Al, Cr,-and Fe bound in acidic EDTA solutions during
precipitation with barium nitrate.
452. Rabovskii, G. V., "Determination of Sulfate in Presence of Chromates,"
Zavodskaya Lab., 3_:592-593 (1934).
BaSO, precipitation.
84
-------
453. Radmacher, W. , "Determination of Sulfur Dioxide and Sulfur Trioxide
in Boiler Gases," Staub (Dusseldorf) . 1.8:174-176 (1958).
Gravimetric determination of SOo and BaSO/ expedient rather than ,
nephelometric; need to provide absorbent with 0.1 N I^SO/ for
quantitative precipitation.
454. Rudnev, N. A., "Effect of Nitric Acid on Precipitation of Barium Sulfate,"
Uchenuie Zapiski Kazan. Gosudarst. Univ.. 90:1054-1061 (1930).
Increasing NC>2~ concentration gives increasing error to a definite
limit, whereupon error decreases; washing with hot water frees
Ba+ ion.
455. Rudnev, N. A., "Precipitation of Barium Sulfate in the Presence of
Chloride and Bromide Ions," Trans. B. Inst. Chem. Tech. Kazan, I:
143-156 (1934).
Effect of HC1 or HBr on precipitate is investigated.
456. Schleicher, A. , "A New Possible Source of Error in the Determination of
Sulfate as Barium Sulfate," Z. anal. Chem. , m.:90-92 (1942); Neues
Jahrb. Mineral., Geol. Ref. I. p. 15 (1942).
Adsorption of BaC^by filter paper; wash filter with cold HC1 and
hot HO prior to use.
457. Shereshevskii, I..L., "Methods of the Analysis of Sulfide-Hydrosulf ide
Liquors," Z. anal. Chem., 105j 110-112 (1936).
Treats sample consecutively to determine C03=, HCO^, Cl~,
(as BaSO) , S0=, S=.
458. Shinkai, S., "A New Method of Chemical Analysis. I.," J. Soc. Chem.
Ind.. 40_:348 (1937).
Improved method using
Shinkai, "A New Method of Chemical Analysis. II. Determination of
Anions," J. Soc. Chem. Ind.. 40_: 349 (1937).
Comparative results of analyses.
85
-------
460. Shinkai, S., "Rapid Determination of Sulfate in Common Salt," Japan
, Analyst. .3:330-331 (1954).
BaSO, precipitation.
461, Shlapin, V.'M. , "Precipitation of Barium Sulfate in the Presence of
Ferric Salts," Uchenuie Zapiski Kazan. Gosudarst. Univ., 88^:461-464
(1928).
Errors due to presence of Fe may be partially compensated for by
•having a large excess of Fe' ' ' .
462. Specker, H., "Quantitative Separation of Inorganic Ions by Ion-Exchange
on Alginic Acid," Z. anal. Chem. , Ul^: 33-38 (1954).
Separation of Fe, Cu, et al., for gravimetric determination of
SO, using BaCl2. '
463. Spencer, G. C., "Report on Chemical Reagents (Determination of Sulfates
in Ammonium Nitrate)," J. Assoc. Of fie. Agr. Chem.. JJ.:421 (1928).
SOA= sample digested with concentrated HC1 in Kjeldahl flask--Ba++
precipitate.
464. Toth, A., "Apparent Volume of the Solid Phase of Centrifuged Precipi-
tates. III. Rapid Analysis' of Sulfates by Measuring the Volume of
Centrifuged Precipitates of Barium Sulfate." Acta Chim. Acad. Sci.
Hung., JLjx 251-266 (1958).
4.65. Toth, A., "The Volume of Centrifuged Precipitates. III. A Rapid
Method for the Estimation of Sulfate by Measuring the Volume of the
Centrifuged Barium Sulfate Precipitate," Magyar Kern. Folyoirat, 61:
239-245 (1955).
0.1 N HCl + 25% NH4C1 + 17, BaCl2 at 85° plus sample; after cooling
and centrifi
calculated.
and centrifuging, volume of precipitate read directly and SO,
466. Vasil'eva, L. A., "Precipitation of Barium Sulfate in Presence of
Hydrochloric and Nitric Acids, in the Cold," Trans. Kirov Inst. Chem.
Tech. Kazan. 4(5):97-105 (1935).
HNO~ and HCl are interferences (coprecipitators).
467. Winkler, L. W., "Gravimetric Analysis. XII. Estimation of Sulfuric
Acid," Z. Angew Chem.. 33U): 59-60 (1920).
Add K2C03, boil and add BaCl2 solution; weigh precipitate x 1.0045.
86
-------
468. Winkler, L. W., "Gravimetric Analysis. XIII. Determination of Sulfuric
Acid," Z. Angew Chem.. 33/1):159-160, 162-163 (1920).
1% NH^Cl prevents interference with BaCl2.
87
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NEPHELOMETRIC AND TURBIDIMETRIC
469. Adams, D. F., "Tentative Method of Analysis of the Sulfation Rate of
the Atmosphere," Health Lab. Sci.. 8(4): 243-247 (1971).
Added sulfaspend reagent and determined absorbance at 450 run.
470. Alekseeva, M. V., "Methods for the Determination of Small Concentrations
V. Determining Sulfate, Sulfite, and Sulfide," J. Applied Chem.,
7:616-622 (1934).
BaS04 - Visual comparison with standards in flat bottom test tubes.
471. Aoyama, S., "Colorimetric Estimation of Turbidity of Silver Chloride
and Barium Sulfate," J. Pharm. Soc. Japan, 48:702-712 (1928).
AgCl standard cannot be used for BaS04 precipitate.
472. APHA, "Turbidimetric Method (156 C)," in Standard Methods for the
Examination of Water and Wastewater, 13th ed., pp. 334-335 (1971).
Details of 864 turbidimetric method using barium.
473. ASTM, "Standard Methods of Test for Sulfate Ion in Water and Wastewater
(D 516); Method B-Turbidimetric Method," in Annual Book of ASTM Stan-
dards. 31-A2 1 -430 (1974).
Details of turbidimetric method using barium.
474. Baumann, A. N. , "Automated Sampling and Analysis of Wet Process Phosphoric
Acid Digestion Systems," in Automation in Analytical Chemistry, Techni-
con Symposia, 1967, Vol. I., pp. 257-260, Mediad, Inc., White Plains,
N. Y. (1968).
Turbidimetric determination using BaC^ at 520 mu; hot slurry sampling.
475. Blanc, P., "A Semimicromethod for the Determination of the Sulfate Ion,"
Trov. Soc. Pharm. Montpellier, 14^:333-334 (1954).
5 to 50 mg/liter BaSC^ in 20% "Tween 20."
476. Boutwell, P. W., "Determination of Sulfur in Urine," Ind. Eng. Chem.,
Anal. Ed., 4:117 (1932).
Early BaCl2 - photometric.
88
-------
477. Boyars, C. , "Turbidiroetric Method for Determination of Potassium Sulf ate
in Propellent Powders," Anal. Chem., 20:87 (1940).
BaS04 against standardized curve.
478. Claudy, H. N. , "Automatic Sulfate Ion Analyzer," Anal. Chem.,
31^(7): 1255-1258 (1959).
BaS04 colloidal solution; 804 concentration of 1 to 4%.
479. Coleman, R. L. , "Turbidimetry Via Parallel Photometric Analysis
Determination of Sulphate," Anal. Chem., 44(6): 1031 (1971).
(GeMSAEC) technique using CAD and BaCl.
480. Denis, W. J., "Sulphates in Blood," J. Biol. Chem., 49:311-317 (1921).
method for blood sulphate.
481. Environmental Protection Agency, "Methods for Chemical Analysis of
Water and Wastes," EPA-625/6-74-003, pp. 277-278 (1974).
Sulfate-Turbidimetric method; uses APHA and ASTM methods.
482. Ferrara, L. W., "Turbidimetric Determination of Sulfate by the
Auto- Analyzer : Sulfur in Plant Materials by Digestion with Nitric
and Perchloric Acid," in Automation in Analytical Chemistry, Technicon
Symposia, 1965, pp. 109-111, Mediad, Inc., White Plains, New York (1966),
Turbidimetric method at 420 mu; 10-50 ppm; BaS04 in gelatin.
483. Gelman, C., "Estimation of Water-Soluble Chlorides, Sulfates, and
Nitrates in Suspended Atmospheric Dusts," J. Air Poll. Cont. Assoc.,
7:216-219 (1957).
Sample through Whatman 41H paper, weighed, extracted with CgHs, ion-
exchanged and 80)4 determined by 63864- turbidimetric method.
484. Haff, A. C., "An Automated Procedure for the Analysis of Total and In-
organic Sulfate in Serum and Urine," in Advances in Automated Analysis,
Technicon International Congress, 1969, Vol. I., Clinical Research,
Mediad, Inc., White Plains, N. Y. (1970).
Turbidimetric procedure using BaC^ precipitation and gelatin; 420 mu .
89
-------
485. Hibbard, P. L. , "Turbidimetric Estimation of Precipitates," Ind. Eng. Chem. ,
1£:804-807 (1924).
Construction and use of early optical instrument.
486. Hobin, N. K., "Turbidimetric Determination of Soluble Sulfates in
Water-Soluble Color Additives," J. Ass. Offic. Anal. Chem., 53(2):
242-243 (1970). ~~
precipitation, turbidimetric measurement at 440 mu; color
additives adsorbed on activated charcoal.
487. Hofer, K., "A New Rapid Determination of Sulfate by the Method of Tur-
bidity Measurements," Chem. Zentr., 2:3372 (1931); warme . 54 ; 803-804
(1931).
Instrument for approximation of sulphate in boiler water and fuels (Ba*"1")
488. Holy, H. W., "Automated Turbimetric Techniques," in Automated Analytical
Chemistry, Technicon Symposium, 1963, pp. 113-116, Technicon instruments
Company, Ltd., Chertsey, England (1964).
SOT by turbimetric barium method; comparison with gravimetric and volumetric.
489. Huey, N. A., "Determination of Sulfate in Atmospheric Suspended Partic-
ulates; Turbidimetric Barium Sulfate Method," U.S. Pub. Health Serv.
Publ., 999-AP-ll ,1-1-1-4 (1965).
Turbidimetric method limit is 50 y SOT; nephelometric method limit
is 2 y $04.
490. Huey, N. A., "The Lead Dioxide Estimation of Sulfur Dioxide Pollution,"
J. Air Poll. Contr. Assoc.. 1£(9) : 610-611 (1968).
Lead sulfate converted to lead carbonate; SO^ determined by
turbidimetric method at 450 mu.
491. Jackson, D. D., "Turbidimetric Determination of Sulphate," J. Am. Chem.
Soc., 23j799 (1901).
Range 1-60 mg using Ba(OH)2..
492. Keily, H. J., "Nephelometric Determination of Sulfate Impurity in Certain
Reagent Grade Salts," Anal. Chem.. 27:759-764 (1955).
SOT precipitate with BaCl2 crystals in EtOH - 0.2 to 10.0 ppm.
90
-------
493. Koteneva, T. V., "The Use of a Colorimeter-Nephelometer in the Analysis
of Very Soluble Salts," Trudy Nauch.-Issledovatel. Inst. Geol. Arktiki,
Ministerstva Geol. i Okhrary Nedr S.S.S.R.. 98/1) : 130- 138 (1959).
SO^ precipitate with Ba(N03>2 compared with standard solution
containing 20 rag. SOT.
494. Lebedeva, M. I., "Turbid imetric Titration of Sulfate Ion in Mixed
Solvents," Tr. Tambov. Inst. Khim. Mashinostr. , (7):128-131 (1971).
Phototurbidimetric titration of SO^ in presence of Na2C03
, Na-jP04, and yi^C^O-j based on precipitation of SO^ as
in HOAc-EtOH, by titration with Cd4"1", and measurement of
absorbance.
495. Lindsay, F. K., "Method for Analysis of Boiler Scales and Sludges,"
Ind. Eng. Chetn., Anal. Ed.. 12:461 (1940).
Turbidimetric, BaCl2, HCl.
496. Lopez-Rubio, F. B., "Rapid Determination of Sulfates by Nephelometry,"
Ion. 5:689-693 (1945).
Obsolete BaS04 techniques.
497. Milton, R. , "Determination of the Mineral Content of Foods by Wet
Oxidation and Absorptiometric Methods," Analyst, 69:299-302 (1944).
Sample oxidized in NH4N03-HN03 solution; SO^T by turbidity using Ba"1^
498. Narozhnykh, E. A., "Phototurbimetric Determination of Small Amounts of
Sulfuric Acid in a Chromium Electrolyte," Khim Khim. Tekhnol. pp. 102
105 (1970), from Ref. Zh. Khim. (1971).
Reduction of Cr to Cr before BaSO^ precipitate.
499. Nelson, G., "The Automatic Determination of Phosphate and Sulfate in
Wet Process Phosphoric Acid," Proc. ISMA, Tech. Conf.. Edinburgh,
1965.
Iso-PrOH inhibits precipitation of 63804; turbidimetric procedure
using
91
-------
500. Omiti, S., "Hygienic Chemistry of Dust in Air. II. Turbidimetric
Determination of Sulfate Ion in Water- Soluble Matter Collected by
Deposit Gauge," Bunseki Kagaku. 1^(11) : 1032-1037 (1963).
turbidimetrically at 370 mu; + 5% in 10-150 ppm
501. Osborn, R. A., "Turbidity and Color Measurements. I. A Photoelectric
Cell Arrangement for Measuring Small Quantities of Certain Impurities
in Reagent Chemicals," J. Assoc. Official Agr. Chem., 1^:135-141 (1934),
Early photo-cell experiments.
502. Ozaki, T., "Phototransistor for the Turbidimetric Determination of
Sulfate," Bunseki Kagaku. 8:672-673 (1959).
Replacement of photocell with phototransistor in photometer.
503. Parr, S. W., "Determination of Sulfur by Means of Turbidimeter,"
Ind. Eng. Chem.., Anal. Ed., 3:66 (1931).
Turbidimetric of Sulfates using BaCl2. Boiler water, circa 2,000
ppm. SO^.
504. Pieters, H. A., "Nephelometric Determination of the Sulfate Ion,"
Chem. Weekblad. 29:188-189 (1932).
Construction details and preparation of standards (Ba"1"4" method) .
505. Pucherna, J., "The Determination of Sulfates with an Objective Photo-
meter," Li sty Cukrovan, 54:376 (1936).
Coal analysis 40-160 mg/liter. BaCl2-Turbidimetric-67o error.
506. Rossum, J. R. , "Suggested Method for the Turbidimetric Determination
of Sulfate in Water," J. Am. Wat. Works Assoc.. £3:873-876 (1961).
Discussion of procedure and interferants; BaCl2 precipitation; color,
turbidity, organic matter, and some inorganics interfere.
507. Rubia, P., "Turbidity of Barium Sulphate," Inform. Quim. Anal., 5:1-6
(1951).
Beer's law validation.
508. Rudy, R. B., "Sulphuric/anhydride in Portland Cement," J. Research Natl.
Bur. Standards. 16:555 (1936).
Early photometric development -
92
-------
509. Sheen, R. T., "Turbidimetric Determination of Sulfate in Water,"
Ind. Eng. Chem. . Anal. Ed.. 7(4) -.262-265 (1935).
Turbidimetric - Application of Tyndall Effect; BaSO^
510. Singer, E., "Turbidimetric Estimation of Sulfates," Chem. Prumsyl,.
1^:526-527 (1961).
Precipitate with EtOH and glycerol using Bad™.
511. Steinbergs, A., "Determination of Sulphur," J. Australian Inst. Agr. Sci.,
.17:155 (1951).
Sample digested; turbidimetric determination of BaSO, against
standards.
512. Steinbergs, A., "Determination of Total Sulfur in Soils," Analyst. ,
8£:457-461 (1955).
i |
Ultimate determination as 804 by turbidity using Ba .
513. Steinbergs, A., "Rapid Turbidimetric Method for the Determination of
Small Amounts of Sulfur in Plant Material," Analyst. 78j47-53 (1953).
Sample digested; turbidimetric determination of BaS04 against standards.
514. Takiyama, K., "Electron Microscopic Study on the Suspension in the Nephelo-
metry of Sulfate Ion," Japan Analyst. 3:291-293 (1954).
Particle-size control with EtOH and gelatin using BaC^.
515. Technicon, "Sulfate in Water and Wastewater," Technicon Industrial Method
No. 39-69W, Tarrytown, N. Y. (1969).
Turbidimetric at 520 mu; silica and color interfere using BaC^.
516. Thomas, J. F. , "A Turbidimetric Sulfate Determination," Wat, and Sew.
Works, 10^:462-465. (1954).
S0£ solution; NaCl, BaCl2; determined at 380 mu; 864 concentration
determined from calibration curve.
517. Toennies, G., "Pho tone phelome trie Microdetermination of Sulfate,"
Anal. Chem.. 2(1) :160-165 (1953)..
in H20-EtOH-glycol system. 01-100 ppm.
93
-------
518. Treon, J., "Rapid Turbidimetric Method for Determination of Sulfates,"
Ind. Eng. Chem., Anal. Ed., 14:119 (1942).
] |
Turbidimetric method using Duboscq colorimeter and Ba
519. Umemoto, H., "Simple Semiquantitative Determination of Sulfate Ion,"
Japan Analyst, 2:34 (1953).
Graduated black bar with brass disc for immersion in BaSO/^. slurry.
520. Verduyn, G., "Automatic Determination of Sulfates by an Improved
Nephelometric Method," Atmos. Environ., 8:707-715 (1974).
Automatic nephelometric determination of SO^ using Barium perchlorate
ppm; as low as .1 ppm/ml SOT.,
521. Vladimirov, L. V. , "Simplified Nephelometric Method of Determining Sul-
fate in Acid Extracts," Zavodskaya Lab.. 3:707-710 (1934).
Procedure described for BaSO^.
522. Voth, J. L., "Coprecipitation of Sodium in Sulfate Determination. A
Spectrographic Method," Anal. Chem., 31(6):1094-1095 (1959).
Examination of Na co-precipitate in SO^ precipitate with BaC^.
523. Wickbold, R., "Photometric Precipitation Titration for Determining
Traces of Sulfate," Angew Chem., 65^:159-161 (1953).
.03-1.5 mg. SOjif General discussion of factors affecting precipitation
titration. BaSO^ as example.
524. Wimberley, J. W., "The Turbidimetric Determination of Sulfate Without the
Use of Additives," Anal. Chim. Acta., 42(2):327-329 (1968).
SO^ in rock samples turbidimetrically using BaCl^ at 380 mu; Beer's
law obeyed for 10-100 ppm S04 (1 cm cell) and 5-25 ppm S0| (4 cm cell)
525. Zdybek, G., "Determination of Microgram Quantities of Sulfate in
Organic Linkages," Anal. Chem., 32(4):559 (1960).
in EtOH-Dipropylene Glycol-Chloric acid system.
94
-------
RADIOMETRIC
526. Armento, W. J., "Determination of Sulfate with Chromium- 51,"
Anal. Chem., 35/7) :918-920 (1963).
SO? precipitated with BaCr5^ in HC1. Neutralization with NH^ pre-
cipitates excess BaCr^-'-Oy and remaining excess Cr^ 0^ is gamma counted.
527. Bruna, A., "Development of a Radiometric Method for the Automatic
Determination of Phosphates and Sulfates in Aqueous Solution,"
Communicate Eur. Energ. At.-EURATOM (Rapp.). EUR-3738F (1968).
oq
Sulfates to Sro:7SO^ in the presence of dioxane which reduced the
solubility of SrSO^ in H20.
528. Ehrenberg, R., "Radiometric Microana lysis, " Mikrochem. Pregl. Festschr.,
pp. 61-68 (1929).
Uses ThB as radioactive material. Radiotagged titration.
529. Ehrenberg, R., "Radiometric Micro -Ana lysis. II, " Biochem. Z.. 172;
10-16 (1926).
Radiotagged titration Pb isotope.
530. Forrest, J., "Sampling and Analysis of Atmospheric Sulfur Compounds for
Isotope Ratio Studies," Atmos . Environ., 7(5): 561 (1973).
Sulfur concentrations measured by Ag tracer.
531. Owens, C. W., "Rapid Ion-Exchange Separation of Radioactive Sulfur
Anions." Radiochem. Radioanal. Lett.. 13(5-6) : 325-327 (1973).
S-jij-contg. anions (S07 incl.) separated on Rexyn 201; monitored by
passing effluent through quartz tubing packed with plastic scintil-
lator beads mounted on photomultiplier tube.
532. Tolgyessy, G., "Radiometric Titration with Tagged Potassium Ferrocyanide
Measuring Solution," Magyar Kern. Folyoirat, 65^:149-152 (1959).
Discussion of classical method and automatic activity-measuring device,
533. Yatsimirskii, K. B., "Radiometric Titration with Solutions of Complex
Compounds of Cobalt- 60," Trudy Komissii Anal. Khim. , Akad. Nauk
S.S.S.R. Inst. Geokhim. i Anal. Khim. , 9j 194- 199 (1958).
SO^ precipitated with [Co60(NH3)6]ci3
95
-------
SPECTROPHOTOMETRIG
534. Agterdenbos, J., "Theoretical Considerations on the Indirect De-
termination of Anions. Determination of Sulfate with Barium
Chloranilate," Talanta, 11:875-885 (1964).
Ba Chloranilate at 332 nqi.
535. Andersen, L. "Spectrophotometrie Method for Determining Sulfate
and Organic Sulfur on the Micro- and Ultramicro Scale," Acta.
Chem. Scand., 7:689-692 (1953).
Spectrophotometrie Modification of Benzidine Method.
536. Barney, J. E., II, "Determination of Sulphate with Barium Chol-
ranilate," Talanta. 12:425 (1965).
Discussion
537. Basargin, N.N., "Photometric Determination of Traces of Sulfate
Ions and Sulfur by Using Nitchromazo," Zh. Anal. Khim., 23(5)
732-735 (1968). ~~
S05 determined using a Barium-nitchromazo complex and a green
filter (640 mu); absorbance compared with standards.
538. Bertolacini, R. J., "Colorimetric Determination of Sulfate with
Barium Chloranilate." Anal. Chem., 29(2) :281-283 (1957).
Absorption at 530 mu. 50% EtOH solution.
539. Bertolacini, R. J., "Ultraviolet Spectrophotometric Determination
of Sulfate, Chloride, and Floride with Chloranilic Acid," Anal.
ehem., 30:202-205 (Correction 498) (1958).
Absorption at 332 mu. Useful up to 150 ppm.
540. Bostrom, E. E., "Improvement in Automatic Colorimetric Determination
tion of Low Concentrations, of Sulfate," Atmos. Envirn., 1(5);
599 (1967). ~
Use of flourosilicone tubing for pumping diozane on technicon.
541. Carlson, R. M., "Modification to Increase Sensitivity of Barium
Chloranilate Method for Sulfate," Anal. Chem.. 39(6):688-690 (1967)
Absorbance in visible region 50% EtOH. Buffer of H3P04 and Kf^PO
intensifies the color.
96
-------
542. Egarai, F., "Sulfate Microdetermination," Bull. Chem. Soc. Japan, 30:
442-457 (1957).
— i i
SO/ precipitated as BaSO^; excess Ba precipitated as BaCrO/;
excess CrOT estimated in alkaline solution at 375 mu; 30 to
900 Y SO^.
543. EPA, "Methods for Chemical Analysis of Water and Wastes," EPA-625/6-
003, pp. 279-282 (1974).
Sulfate-Automated Chloranilate Method.
544. Eriksen, T. E., "Direct Spectrophotometric Determination of Sulfate
in Aqueous Solutions of Sulfur Dioxide," Acta Chem. Scand., £6(8):
3337-3341 (1972).
SO]" determination by FeSO^ method; S02 and HSOj masked with I^CO.
Modification of Goguel Method.
545. Gales, M. E., "Determination of Sulfate by Automatic Colorimetric
Analysis," Analyst, £3/1103);97-100 (1968).
Technicon method using Ba Chloranilate determination at 520 mu
designed for 5 to 400 mg SOT/J& in water.
546. Goguel, R., "Direct Spectrophotometric Detection of Sulfate in Natural
Water by Formation of the Ferric Sulfate Complex," Anal. Chem., 41(8)
1034-1038 (1969).
10 to 500 mg SO^/ir using absorption of FeSO* complex at 325 and
360 nm.
547. Haslam, J. "The Detection of "Additional Elements' in Plastic Materials
by the Oxygen Flask Method," Analyst, 86^:239-248 (1961).
Sample burnt in oxygen; combustion products absorbed in NaOH;
SO^ detected colorimetrlcally by barium Chloranilate or 4-amino-
4'-chlorodiphenyl hydrochloride method.
548. Hinze, W. L., "Spectrophotometric Determination of Sulfate Ion with
Barium lodate and the Linear Starch Iodine System," Anal. Chem.,
45^(4):814-815 (1973).
SOT detected spectrophotometrically by precipitation in EtOH
with 63(103)2; reduction of I0~ with I" in starch and measure-
ment of absorbance of starch - I complex at 625 or 587 nm; low
ppm range.
97
-------
549. Iwasaki, I., "Spectrophotometric Determination of a Small Amount of
Sulfate Ion. I. Solid and Aqueous Barium Chromate Method," Nippon
Kagaku Zasshi. 79:32-38 (1958).
Acid suspension of BaCrO^ used to precipitate 804. Excess Ba
precipitated with NH^OH. Exchanged excess CrO^ determined
with diphenyl carbohydrazine by absorption at 545 mu; 0.2 to
12 y SOT to 20 to 100 ppm.
550. Iwasaki, I., "Spectrophotometric Determination of a Small Amount of
Sulfate Ion. II. Barium Chromate Suspension Method," Nippon
Kagaku Zasshi, 7_9:38-44 (1958).
Sample, BaCrOA suspension, ammonia, CaCOo, alcohol; centrifuge;
compare filtrate at 370 mu with standard; 0.3 to 100 ppm to 100
to 500 mg SO^.
551. Iwasaki, I., "Spectrophotometric Determination of a Small Amount of
Sulfate Ion. III. Determination of Traces of Sulfate, 0.2-5 ppm,"
Nippon Kagaku Zasshi, 7J9:44-50 (1958).
BaCrOA, sample, acetate buffer, alcohol; centrifuge; filtrate;
diphenyl-carbazide reagent, HCl; determine absorbancy at 545 mu
with 5 mm cells; PO, and Fe interfere.
552. Iwasaki, I., "Spectrophotometric Method for the Determination of
Small Amounts of Sulfate Ions," Bull. Chem. Soc. Japan, 30_:847-851
(1957).
0.3 to 100 ppm SO^; 804 as BaSO^ using BaCrOA; if < 20 ppm SO^ -
545 mu, if > 20 ppm SO^ - 370 mu.
553. Kanno, S., "Improvements in the Barium Chloranilate Method [for
Sulfate Determination]," Eisei Kagaku. L3(4) :217-218 (1967).
Method improved with pH 5.2 instead of pH 4.0 buffer.
98
-------
554. Kato, T., "Chemical Analysis by Ultraviolet Filter-Photometer. I.
Determination of a Small Quantity of Sulfate Ion," J. Chem. Soc.
Japan, Pure Chem. Sect.. 7£:373-376 (1955).
BaCrO Method. CrO, absorption measured at 366 or 405 mu; 2 to
120 per ml.
555. Klein, B., "Microdetection of Sulfate," Ind. Eng. Chem., Anal. Ed.,
1(6:536 (1944).
Benzidine sulphate, diazotized, and coupled with N(l-naphthyl)
ethylenediamine-2HCl. Intense purple color.
556. Klipp, R. W., "Determination of Sulfur Traces in Napthas by Lamp
Combustion and Spectrophotometry," Anal. Chem., 31(4):596-597
(1959).
Sample burned in ASTM lamp; resulting I^SO^ detected by barium
chloranilate method at 330 or 530 mu; 1 to 400 ppm.
557. Klockow, D., "Amplification Method for Determination of Particle-
Sulfate in Background Air." Atmos. Environ., 7(2):163-168 (1973).
SO? converted with 63(103)2- 6 x amount of iodine is obtained.
Absorbed at 504 or 366 nm. Working range 0.4 to 4.0 ug. Sulfur.
558. Lambert, J. L., "Colorimetric Determination of Sulfate Ions," Anal.
Chem.. 2^:800-801 (1955).
S07 determined by amount of dye released from an insoluble thorium
borate-Amaranth lake; measured at 521 mu; up to 400 ppm SO?; HCO-
and Fe interfere.
559. Lambert, J. L., "Colorimetric Determination of Sulfate Ion," Anal.
Chem.. 27^:1835 (1955).
Thorium borate-Amaranth dye. Direct proportional dye release
with SOT. 0 to 400 ppm.
560. Lambert, J. L , "Determination of Fluoride Ion Using a Monohydroxy
Azo Dye-Thorium Lake," Anal. Chem.. 26(3):558-560 (1954).
Use of dye. (Related to SOjj ion work.)
99
-------
561. Lambert, J. L., "Simplified Preparation of Cadmium Iodide-Linear
Starch Reagent for Colorimetric lodometry," Anal. Chem., 3J5(3):
405 (1963).
Preparation of reagent.
562. Laxton, J. W., "Automatic Monitor for Recording Sulfur Trioxide in
Flue Gas," J. Inst. Fuel, 37/276): 12-17 (1964).
Ba chloranilate at 535 rap; 0.2 to 100 ppm SO^; automatic system.
563. Lazrus, A. L., "A New Colorimetric Microdetermination of Sulfate Ion,"
in Automation in Analytical Chemistry, Technicon Symposia, 1965,
pp. 291-293, Mediad, Inc., White Plains, New York (1966).
Colorimetric-methylthymol blue method at 480 mu; 0.5 to 50 ppm
S0=.
564. Lazrus, A. L., "New Automated Microanalyses for Total Inorganic Fixed
Nitrogen and for Sulfate Ion in Water," Advan. Chem. Ser., (73):
164-171 (1968).
BaSO^-methylthymol blue; 0.5 to 50 ppm SOT.
565. Lloyd, A. G., "The Use of Barium Chloranetate in the Determination of
Enzymically Liberated Sulphates," Biochem., 72_: 133 (1959).
566. Marenzi, A. D., "A Micromethod for the Determination of Sulfates and
Its Application to Plasma, Serum, and Urine," Anales Farm Bioquim..
8j62-74 (1937).
SOT determined colorimetrically as difference between sample
phosphotungstomolybdic acid solution and unprecipitated benzidine.
567. Marenzi, A. D., "Application of the Palfrich Photometer to the Deter-
mination of Sulfates by the Method of Marenzi and Banti," Anales
Farm Bioquim.. 1£: 77-81 (1939).
Blood sulfates. Benzidine-phosphotungstomolybdic acid.
568. Matsuo, T., "Application of Benzidine and Its Derivatives in
Analytical Chemistry," J. Japan Chem.. £:588-592 (1954).
Review of use of benzidine as precipitating reagent for colori-
metric determination of SO^.
569. Mendes-Bezerra, A. E., "Determination of Sulfate by Titrimetric and
Colorimetric Measurement of Equivalent Displaced Zinc Ion," Anal.
Lett.. l^(6):355-358 (1968).
100
-------
200 ug to 100 mg SOT; .two methods titration of excess EDTA with
Zn and spectrophotometric determination of Ba-EDTA complex with
excess Zn (treated with Zincon) . .
570. Morgan, G. B., "Automated Laboratory Procedures for the Analyses
qf Air Pollutants," Anal. Instrum., 4_: 101-112 (1966).
Sampling on glass-fiber filter; preparation; SO? determination
by automated methylthymol blue method. .
571. Nasu, T., "Spectrophotometric and Fluorimetric Determination of
Micro Amounts of Sulfate Using Thorium-Flavonol Complex," Bunseki
Kagaku. 19(5): 673-680 (1970).
Measure decrease in absorbance at 390 nm or fluorescence at
... , 3_
470 nm of fluorescence complex. F~ and PO^ interfere.
572. Pacheco, J. de la R. , "Photometric Applications of the Chromate-
Meta-bisulfite Reaction," Infom. Quim. Anal., 4:119-126 (1950).
Chromate-meta-bisulfite reaction can be applied to determination
of Ba, PG, Hg, and SO^.
573. Persspn, G. A., "Automatic Colorimetric Determination of Low Concen-
trations of Sulfate for Measuring Sulphur Dioxide in Ambient Air,"
Air and Water Pollut. Int. J.. 1(3:845-852 (1966).
SO? precipitated with Ba^lO^; excess Ba indicated with Thorin.
Technicon procedure 0 to 10 y/ml. 0.3 y threshold.
574. Prevost, S. , "Spectrophotometric Study of Pyrocatechol Violet-Thorium
Complexes in Aqueous Solution of pH 3.2 and the Reaction of Sulfate
Ions with These Complexes," J. Chim. Phys., 64-(10) : 1533-1539 (1967).
Method for determination of SO^ in 0 to 100 y/ml range.
575. Schafer, H. N. S., "An Improved Spectrophotometric Determination of
Sulfate with Barium Chloranilate as Applied to Coal Ash and Related
Materials," Anal. Chem. , 3£(14):1719 (1967).
80% IPA as solvent. Absorbance of chloranilate 310 nm.
576. Stanford Research Institute, "Size Determination of Atmospheric
Sulfate and Chloride Particles," HEW Contract No. PH-86-64-54.
Ba chloranilate method evaluated.
101
-------
577. Stoffyn, P., "Spectrophotometric Micro and Submicro Determination of
Sulfur in Organic Substances with Barium Chloranilate," Anal. Chem.,
36^(2):397-400 (1964).
Sample mineralized by oxidation; S07 determined by Ba chloranilate;
interferences removed by ion exchange with ammonium Dowex 50; 0.3
to 100 ug S.
578. Technicon, "Sulfate in Water and Wastewater," Technicon Industrial
Method No. 118-7lW/Tentative, Tarrytown, New York (1972).
BaSO,-methylthymol blue.
579. Werner, 0., "Colorimetric Determination of Nonmetals," Z. Ver. Chem.,
Beih, 48:113-120 (1944); Chem. Zentr., 2_:1305 (1944).
Critical review on determination of F, Cl, Cl", H2S, S0£, P, PO^,
etc.
580. Wharton, W. H., "Application of Spectrophotometric Titrations to
Micromolar Solution of Calcium, Magnesium, Oxilate, or Sulfate,"
Anal. Chem.. 3£(8) .-1679-1681 (1964).
Titration with Ba(0104)25 80% EtOH, Thorin indicator. See endpoint
at 550 mil.
102
-------
SUBSTITUTED BENZIDINES
581. Belcher, R., "Substituted Benzidines and Related Compounds as Reagents
in Analytical Chemistry. Part I. Solubilities of the Sulfates," J^
Chem. Soc., pp. 544-546 (1951).
Development of new reagents for SO^ determination.
582. Belcher, R., "Substituted Benzidines and Related Compounds as Reagents
in Analytical Chemistry. Part II. Reaction with Oxidizing Agents,"
J. Chem. Soc.. pp. 546-547 (1951).
Reactions of new reagents with oxidizers.
583. Belcher, R., "Substituted Benzidines and Related Compounds as Reagents
in Analytical Chemistry. Part XII. Reagents for the Precipitation
of Sulphate," J. Chem. Soc.. pp. 1334-1337 (1953).
Sulfates of 4-amino-4'-halogenodiphenyls prepared; discussion.
584. Belcher, R., "Some Factors Influencing the Solubilities of Amine
Sulfates," Anal. Chim. Acta.. 8j 122-129 (1953).
Discussion and development of 4:4'-diaminotolane.
585. Belcher, R., "4,4'-Diaminotolan as a Reagent for the Titrimetric De-
termination of Sulfate," Anal. Chim. Acta., £: 146-149 (1953).
Replaces benzidine; phosphate and cremate interfere.
586. Belcher, R., "The Titrimetric Determination of Sulphate with 4-Amino-
4'-Chlorodiphenyl Hydrochloride as Reagent," Analyst, 81^:4-8 (1956)..
25 to 100 mg 804 in 100 ml or 2.5 to 25 mg SO^ in 50 ml; P04
interferes.
587. Coleman, R. L., "Turbidimetry via Parallel Photometric Analysis,"
Anal. Chem., 44,: 1031-1034 (1972).
864 determined by parallel photometry using BaCl2 and 4-amino-
4'-chlorodiphenyl hydrochloride.
103
-------
588. Dodgson, K. S., "The Determination of Inorganic Sulphate in the Study
of Sulphatases." Biochem. J.. 55:436 (1953).
Add benzidine and filter. Unreacted benzidine measured colori-
metrically after thymol addition.
589. Dodgson, K. S., "A Preliminary Account of the Glycosulphtase of
Littorina Littorea," Biochem. J.. 57j310 (1954).
Add benzidine and filter. Add thymol and measure colorimetrically.
590. Dodgson, K. S., "A Preliminary Account of the Chondrosulphatase of
Proteis Vulgaris," Biochem. J., 65_:131 (1957).
Add benzidine and filter. Unreacted benzidine and thymol and
measure colorimetrically.
591. Haslam, J., "The Detection of 'Additional Elements' in Plastic Mate-
rials by the Oxygen Flask Combustion Method," Analyst, 86^:239-244
(1961).
S reduced to 804; SO^ detected with barium chloride (700 mu),
barium chloranilate (530 mu) or 4-amino-4'-chlorodiphenyl hy-
drochloride (700 mu) methods.
592. Hovorka, V., Chem. Listy. 36jll3 (1942).
Monoacetylated and monobenzoylated benzidines give precipitates
with sulfates. N,N'-diacetylbenzidine give only a faint precipi-
tate. Vanillyledenebenzidine used as a sulfate reagent reported.
Other mono- and di-methines derived from benzidine were reported
as giving precipitates with sulfate.
593. Jones, A. S., "A Spectrophotometric Method for the Determination of
Sub-micro Quantities of Sulphur with 4-Amino-4'-chlorodiphenyl,"
Analyst. 8Jj 15-18 (1956).
30 to 120 ug 804; determined by UV spectrophotometry of reagent
difference between blank and sample after precipitation.
594. Jones, A. S., "A Submicro Method for the Estimation of Sulfur," Chem.
and Ind.. 662/23):662-663 (1954).
Precipitate with 4-amino-4'-chlorodiphenyl hydrochloride in pres-
ence of surface-active agent; determined by UV at 254 mu.
104
-------
595. Jones, P. A., "The Indirect Spectrbphotometric Determination of the
Sulphate Ion with 2-Aminoperimidine," Anal. Chim. Acta.. 64:85-92
(1973).
Precipitation of 864 with 2-aminoperimidine hydrochloride; measure
excess reagent at 305 nm; 4-120 ppm SO^.
596. Maddalone, R. F., "Determination of Sulfate by Thermal Reduction of
Perimidylammonium Sulfate," Anal. Chem.. 47/2):316-319 (1975).
804 precipitation as perimidylammonium sulfate; thermal decompo-
sition of precipitate and excess reagent yields SQ2', determined
by West-Gaeke or flame photometric procedures.
597. Martin, J. M., "An Improved Colloidal Stabilizer for Use in the Nephelo-
metric Determination of the Sulfate Ion," Anal. Chim. Acta.. 3Jh252-
258 (1967).
S07 determined using 4-amino-4'-chlorodiphenyl hydrochloride and
acid gum ghatti; determined to 1 ppm SO^.
598. Martin, J. M., "The Nephelometric Determination of Small Amounts of
Sulphate Ion," Anal. Chim. Acta.. 39^:175-180 (1967).
804 determined nephelometrically using 4-amino-4'-chlorodiphenyl
hydrochloride, peptone, and gum ghatti; 2.5-25 ppm SOT in 10 ml
aliquots.
599. McClure, G. L., "An Improved Synthesis of 2-Perimidylammonium Ion for
' Use as a Sulfate Reagent," Anal. Chim. Acta.. 64^:289-291 (1973).
Description of synthesis procedure.
600. Nietzki, R., Ber.. 18j3255 (1805).
Solubility of naphlhedine sulphate reported to be less than benzi-
dine sulphate.
601. Raistrick, H., "A Survey of Fungal Metabolism of Inorganic Sulphates,"
Biochem. J.. 43:90 (1948).
Add benzidine, dissolve precipitate in NaOH and titrate ppt with
standard BaClo and Na rhodizonate.
105
-------
602. Slack, H. G. B., "The Metabolism of Sulphated Polysaccharides," Biochem.
£.., 65j459 (1957).
Unreacted, add benzidine and filter benzidine and thymol and measure
colorimetric.
603. Stephen, W. I., "A New Reagent for the Detection and Determination of
Small Amounts of the Sulfate Ion," Anal. Chim. Acta.. 50:413-422
(1970).
Discussion of 2-aminoperimidine synthesis and use; determination
of 0.2 ppm SO^.
604. Van Loon, J. P., Chem. Zent., Volume II, 1669 (1908).
Solubility of substituted benzidines and related compounds given.
0-tolidine sulfate solubility was 1.2 g/liter at room temperature.
605. Welcher, F. J., "Specific and Selective Organic Reagents." Proc., Int.
Symp. on Microchemistry, Birmingham University, England, 20-27 August
1958, pp. 6-21 (1960).
Theory. Discussion of properties, synthesis and use of organic
reagents. Makes example of Belchers work.
606. Wilkinson, H. C., "The Use of 4-Amino-4'-chlorodiphenyl Hydrochloride
for the Determination of Sulphur in Coal," Analyst. 81^:9-11 (1956).
Bomb combustion of coal; add 4-amino-4'-chlorodiphenyl hydrochloride
solution, filter; titrate precipitate with NaOH using phenol red-
bromothymol blue indicator.
106
-------
MISCELLANEOUS-METHODS
607. Albee, A. L. , "Correction Factors for Electron Probe Microanalysis of
Silicates, Oxides, Carbonates, Phosphates, and Sulfates," Anal. Chem. .
42(1 2): 1408 -1414 (1970).
Discussion of correction parameters.
608. Altshuller, A. P., "Atmospheric Sulfur Dioxide and Sulfate: Distribu-
tion of Concentration at Urban and Nonurban Sites in the United States,"
Environ. Sci. and Tech.. 7(8):709-712 (1973).
Comparisons of S0,~ concentration over country.
609. Antisari, 0. V., "Research in Chemical Composition of Some Forms of
Atmospheric Particles," Chicago Univ., Dept. Meteorol., Tech. Note 5
(1956).
Identification of particle size and chemical composition by Liesegang
Rings in treated gel.
610. Anyz, F., "A Contribution to the Detection of the Aerosols Containing
Sulphate Particles," Tellus. 18j 216-220 (1966).
Sulphate aerosol detection by Liesegang Rings in treated gelatin
(BaCl2).
611. Bavika, L. I., "Determination of Sulfuric Acid in Air by a Vanadate
Method," Neftepererab. Neftekhim. . 9j40-41 (1971).
Air sample passed through ammonium vanadate solution; yellow color
formed with
612. Becka, J., "Quantitative Analysis by Means of the Refractometer and
Interferometer," Z. Physiol. Chem.. 121^288-299 (1922).
Calculating percentage of substance precipitated from solution by
difference in refraction.
613. Braun, T., "Applications of Precipitation Membranes in Analytical
Chemistry," Talanta. 11(11) : 1543-1544 (1964).
Precipitation membranes eliminate need for separation of precipitate
in colorimetric, radiometric titrations, and radioactive precipitate
exchanges .
107
-------
Cadle, R., "Micrurgic Identification of Chloride and Sulfate," National
Acad. Sci.--National Res. Council Pub. No. 652, pp. 18-21 (1959).
Microscopic identification of particulates.
615. Crider, W. L., "Hydrogen Flame Chemiluminescence Detector for Sulfate
in Aqueous Soltuions," Anal. Chem. Acta., 47_( 2) : 237-241 (1969).
S0^~ determination to 2 ug SO^/ml solution; specific S0,= analyzer
in H2C>2 determination of S02-
616. Deniges, G., "Rapid Identification of the Two Ions in Barium Sulfate,"
Bull. Soc. Chim.. 27^560-564 (1920).
Microscopic qualitative for Ba and SO/=; violet color from SO^ +
Na2(CN)5NO.
617. Deniges, G., "Silver Nitrate as a Microchemical Reagent for the Sulfate
Ion," Bull. Soc. Pharm. Bordeaux, 64j57-60 (1926).
Dry sample and add 3% AgNOo. Crystals are characteristic in photo-
micrograph.
618. Dube, G., "Semi-Automated Thermometric Titration of Sulfate," Anal.
Chem. . 47_(2):285-289 (1975).
BaSO^ precipitation using BaCl2; thermometric titration.
619. Duval, C., "Thermogravimetry of Analytical Precipitates. XLIII. De-
termination of Sulfur," Anal. Chim. Acta., 4:623-628 (1950).
Pyrolysis curves traced; discussion.
620. Environmental Protection Agency, "Air Quality Data for 1968 from the
National Air Surveillance Networks and Contributing State and Local
Networks," EPA Pub. No. APTD-0978 (1972).
Sampling; determination by automated methylthymol blue method at 480
nanometers.
621. Forbes, E. A., "Determination of Microgram Amounts of Sulfate by Emis-
sion Spectroscopy of Barium with a Nitrous Oxide-Acetylene Flame,"
Analyst. 913(1168):506-511 (1973).
SO/= determined indirectly in aqueous solutions by Ba emission at
553.55 nm; K^C-O, (NH^)2C20,, Na3VO,, NiCl2, NaF, and HC10, inter-
108
fered if in S0^= solution.
-------
622. Francis, W. E., "The Measurement of the Dewpoint and Sulfuric Acid
Vapor Content of Combustion Products," GRB 64, The Gas Research
Board, The Abbey, Southend Road, Beckenham, Kent. '
Dewpoint measured by electrical conductivity; ^SO, estimate un-
successful due to trapping difficulty.
623. Frey, H., "Determination of Sulfate," Anal. Chem. Acta.. 6j 126-132 (1952)
Various methods described (volumetric, turbidimetric, microvolu-
tnetric, colorimetric, ignition, photometric) ; ion exchange to re-
move metal interference.
624. Freze, N. A., "Determination of Sulfate Ion by Filtration Titration,"
Zavod. Lab.. 8/10-11): 1181-1182 (1939); Khim. Referat. Zhur. . 5:68
(1940). ~~ "~
Addition of BaCl2 to 804 solution with repeated filtration until
no precipitation formed.
625. Freze, N. A., "Determination of Sulfates by Hydrostatic Suspension,"
Zavod. Lab.. 14997-998 (1948).
suspension subjected to a d. determination; BaSO, filtered
off and d. of filtrate measured.
626. Fukae, M. , "Determination of Sulfates," Rinsho Byori. Rinjizokan.
',(17) : 116-123 (1970).
Review of determination of biologic and inorganic sulfate.
627. Green, W. D., "Identification of Chemical Constituents in Single Aerosol
Particles," Amer. Chem. Soc., Div. Water Air Waste Chem., Preprints,
7_(2):83-90 (1967).
SOA= identified by precipitation of BaSO^ in glycerol-gelatin films
containing a soluble Ba salt.
109
-------
628. Gurevich, V. G., "Chronometric Microanalytical Method," Nekotorye
Voprosy Farmatsii, Sbornik Nauch. Tru'doy. Vyssh. Farm. Ucheb.
Zavedenli Ukr. S. S. R. . pp. 89-93 (1956).
Measuring the time taken to form a precipitate with BaCl^.
629. HEW, "Air Pollution Measurements of the National Air Surveillance Net-
work. Vol. I. Analyses of Suspended Particulate, 1953-1957," Pub.
Health Ser. Pub. No. 637 (1958).
Determination by turbidimetric method using BaCl2 at 500 mu; also
determination in a glycerin-alcohol solution.
630. HEW, "Air Quality Criteria for Sulfur Oxides," NAPCA Pub. No. AP-50
(1969).
Sampling; determination by colorimetry (MTB) and turbidity.
631. Hogstrom, U., "Residence Time of Sulfurous Air Pollution from a Local
Source During Precipitation," Ambio. 2_(l-2) :37-41 (1973).
Weather conditions affect residence time.
632. Huygen, C. , "The Determination of Sulfate by the Ring Oven Technique and
Its Application to Air Pollution Measurement," Mikrochim. Ichnoanal.
Acta. pp. 6-9 (1963).
Qualitative detection to 0.1 ug. :
633. ivlev, L. S., "Optical Constants for Atmospheric Aerosols," Izv. Vyssh.
Vcheb. Zaved. Fiz.. 15J5): 91-97 (1972).
Optical constants for compounds present in atmosphere (including S0^
determined using spectrometry.
634. jahr, K. F., "Dilatometrically Indicated Titrations. I. Precipitation
of Sulfate Ions as Barium Sulfate," Fresenius Z. Anal. Chetn. . 241(2) :
110-121 (1968).
A using dilatometer to indicate volume changes; Na and NH, inter-
fere.
635. Karekar, N. V., "Adsorption of Sulfate Ion by Thorium Hydroxide Solutions,
Dialyzed to Different Degrees," Kolloid-Z.. 68j 286-289 (1934).
Coagulation of Th(OH)^ hydrosol determined for K, Mg, and Al sulfates
in presence of MeOH, EtOH, and iso-proOH.
110
-------
636. Kellogg, W. W., "Sulfur Cycle," Science. 175^ (4022):587-596 (1972).
Broad discussion.
637. Kenny, F., "Volumetric Determination of Sulfate by Titration of Excess
Lead Nitrate with Potassium Chromate with Siloxene Indicator," Anal.
Chetn., 29^(4): 543-546 (1957).
S0,= precipitate as PbSO,; excess Pb titration in dark chamber with
^C^O, ; end-point determined by photometric determination of siloxene-
emitted light.
638. Kullbom, S. D., "Combined Infrared and X-Ray Spectrometric Method for
Determining Sulfonate and Sulfate Concentrations of Detergent Range
Alkylbenzene Sulfonate Solutions," Anal. Chem.. 37(8):1031-1034 (1965).
Special application for determination of Na.nSO^ in detergent slurry.
639. Lawson, J. R., "Infrared Determination of Trace Amounts of Polyatomic
Inorganic Ions," Anal. Chem.. 40(3):636-639 (1968).
Solid solutions in alkali, halide crystals; fusion in KBr disks for
spectrophoto at 9 and 16 u.
640. LeGuyon, R. F., "Micro - Titration of Sulfate Anions and Barium Cations
with the Aid o;f the Micro. - Centrifuge," Bull. Soc. Chim.. 41:1387-
1389 (1927).
Discussion of BaSO/ precipitation using centrifuge.
641. LeGuyon, R. F., "Volumetric Micro-Analysis and Centrifugo-Volumetry,"
Ann. Chim., 10^:50-112 (1928).
Discussion of various centrifuge-volumetric methods.
642. Leroux, J., "Average Composition of Particulate Air Pollutants as Dis-
closed by X-Ray Techniques," Int. J. Environ. Anal. Chem., 1(2):131-
140 (1971).
General discussion and collection of data.
643. Lodge, J. P., "An Improved Method for the Detection and Estimation of
Micron Sized Sulfate Particles," Anal. Chim. Acta. 29_(4) :372-374
(1963).
Identification limit 2 x 10"15 g SO^ using filters treated
with BaCl2 and K2 rhodizonate.
Ill
-------
644. Lyshkow, N. A., "Apparatus and Method for Analysis of Gas Streams,"
U.S. Patent 3,712,793 (Cl. 23-232E; G oln) , 23 January 1973.
Chemiluminescent reaction of sample and thin-layer reagent; S(>2
by ozone reagent.
645. Miyahe, Y., "The Chemical Nature of the Saline Matter in the Atmosphere,"
Geophys. Mag. Japan, 16J1): 64-65 (1948).
General discussion.
646. Monkman, J. L., "Gas Champer Microapparatus in Identification of Air-
Borne Pollutants," Anal. Chem. . 27(5) : 704-708 (1955).
Slides coated with glycerol- and benzidine-treated water sulfate
show under polarized light all sulfates react.
647. Nebbia, L., "Determination of Sulfur Trioxide in Mixtures Containing
Sulfur Dioxide and Air," Chim. Ind. . 5( 2) : 158-160 (1970).
Samples determined by potentiometric titration and gas chromatography
for S03; 1-10% S03 content.
648. Ngo, H. D., "Separation of Some Cations and Anions by the Ring Oven
Technique," Mikrochim. Acta, 6^:935-938 (1972).
Description of multiple ion (Fe, Ni, Mn, Al, Cd, Cu, Co, SO^, Cl,
NOo) separation method.
649. Novakov, T., "Chemical Composition of Pasadena Aerosol by Particle Size
and Time of Day. III. Chemical States of Nitrogen and Sulfur by
Photoelectron Spectroscopy," J. Colloid. Interface Sci.. 3JK1) : 225-
234 (1972).
Determination of chemical state of S in smog particles as function
of particle size and time of day; S0^= in larger particles, predomi-
nating during day; S02 in smaller particles, predominating at night.
650. Pearson, F. J., "Chemical Composition of Atmospheric Precipitation in
Northeastern United States," U.S. Geol. Surv, , Water Supply Paper
No. 1535-P (1971).
Discussion of monthly bulk precipitation rates at 18 northeastern
sites.
112
-------
651. Perchec, H., "Thermal Determination of Sulfate," Bull. Soc. Chim. France.
3;619-620 (1964).
Precipitation of SO/~ with 63(^3)2 done in covered Dewar; exothermic
temperature plotted versus total volume; break at end-point,
652. Pieters, H. A. J., "Determination of Sulfate," Chem. Weekblad. 39j 20-23
(1942).
Review of nongravimetric methods (benzidine method of Raschig, tetra-
hydroxyquinone indicator, colorimetric with BaCrO^, nephelometric,
conductometric, measurement of BaSO, precipitate in graduated centri-
fuge tube) .
653, Ponomareva, L. K., "Photochronometric Determination of Sulfates," Zavod.
: Lab.. 32(1):-16-17 (1966). .
Add to sample HCl and heat to boil, add HoBO^ and filter. Add BaCl2
and measure time to absorbance change of 0.1.
654. Popoff, S., "Microscopic Examination of Precipitation as an Aid to Pre-
cise Analysis. I. Estimation of Sulfates as Barium Sulfate," Ind.
Eng. Chem.. Anal. Ed;. 2j45-54 (1930).
Effects of titration technique on crystal formation.
655. Pribil, R., "Contributions to the Basic Problems of Complexometry. I.
The Blocking of Indicators and Its Elimination," Talanta. 3;91-94
(1959).
Discussion.
656. Rissmann, E. F., "Infrared Method for Rapid Analysis of the Sulfate Con-
tent in Reacted Lime and Limestone Materials," Anal. Chem.. 42(13):
1628-1632 (1970).
SO,= in saturated EDTA/t^O solution in 0.003 mm liquid cell for spec-
photo at 1,110 cm~l.
657. Samuelson, 0., "The Use of Base-Exchanging Substances in Analytical
Chemistry. III.," Svensk. Kern. Tid.. 52^115-125 (1940).
Review of S0^= interferences and effect of using H charged organo-
lite. •-....
113
-------
658. Sander, A., "A New Simple Procedure for the Identification of the Most
Important Sulfur-Oxygen Compounds," Chem. Ztg.. 4pjl73 (1919).
as reagent for spot test.
659. Shaw, R. W. , "Sulfate Deposition by Precipitation into Lake Ontario,"
Water. Air. Soil Pollut., £(1): 125-128 (1973).
General .discussion.
660, Stork, G., "Indirect Determination of Light Elements by X-Ray Fluores-
cence Analysis. II. Determination of Sulfate, Chloride and Bromide
in Presence of Each Other, and Beryllium," Fresenius Z. Anal. Chem..
2fe2(3):161-166 (1972).
Precipitate with BaC^; measured Ko? lines; 48 ug.
661. Swinarski, A., "Rapid Methods for the Volumetric Determination of Sul-
fates and Phosphates with the Centrifuge," Przemysl Chem.. 9j 119-122
(1953).
Precipitation with BaCl2, 0.4 M HC1; removal of Fe"*"1"1" and Al"1"4"*"
not necessary.
662. szal, J., "Determination of Sulfates," Wiad. Chem., 26(10) ; 685-705
(1972).
A review.
663. Tai, H. , "Infrared Spectrophotometry of Sulfate," Anal. Chem.. 29(10):
143 (1957).
Freeze dry with KBr disk for IR Spectrophotometry.
664. Tockstein, A., "Complexonate - Exchange Reactions as a Basis of Analyti-
cal Micromethods," Sbornik ved. praci. Vysoka skola Chem. Technol.
Pardubice, pp. 139-154 (1959).
Discussion of EDTA-metal complex formation.
665. Tufts, B. J., "Chemical Identification of Halide and Sulfate in Submicron
Particles," Anal. Chem.. 30j3001 (1958).
Electron microscope; 25 ml H20, SAT with BaNO, PbNOn.
666. Urone, P., "Chemistry of Sulfur Compounds in the Atmosphere," Air Water
Poll.. Proc. Summer Workshop. 1970, pp. 587-598 (1972).
A review.
114
-------
667. Underwood, A. L., "Infrared Spectrophotometry of Aqueous Nitrate,
Nitrite, and Sulfate Solutions," Anal. Chim. Acta., 29j 79-81 (1963).
S0^= band is cation dependent. CO-j, NIL , and most organic compounds
interfere.
668. van Den Heuvel, A. P., "The Formation of Ammonium Sulfate in Water Drop-
lets Exposed to Gaseous Sulfur Dioxide and Ammonia," Quart. J. Roy.
Meteor. Soc.. 89j 271-275 (1963).
Mass of S0,~ proportional to product of drop surface area and ex-
posure time.
. Van Slyke, D. D., "A Gasometric Micromethod for the Determination of
lodates and Sulfates, and Its Application to the Estimation of Total
Base in Blood Serum," J. Biol. Chem.. 74j659-675 (1927).
S0^= determined by gasometric estimation of iodate dissolved when
S0^= solution equilibrated with excess solid 63(103)2*
670. Weisz, H., "A Color Reaction for Sulfates," Mikrochim Acta. 1:26-28
(1959).
Add one drop of 0.1% Ba(NO-) on filter paper plus Na rhodizonate,
then one drop AgN03« Sulfate changes red to blue.
671. West, P. W., "Analytical Methods for the Study of Air Pollution,"
J. Chem. Educ.. 46(2):96-98 (1969).
A review; emphasis on ring oven methods.
672. Williams, M. B., "Thermometric Titration of Sulfate," Talanta.
548-551 (1970).
Titration with B
115
-------
MISCELLANEOUS - BOOKS
673. Allport, N. L., Colorimetric Analysis, 2nd Ed., Vol. I, pp. 326-327,
Chapman and Hall, Ltd., London (1957).
SOT in blood by benzidine precipitation.
674. Ayres, G. H., Quantitative Chemical Analysis, 2nd Ed., pp. 146, 219-223,
420, 582-585, Harper and Row, New York (1968).
Various methods (gravimetric: BaSO^; titrimetric: reduction to ^S
which is determined iodometrically).
675. Bark, L. S., Thermometric Titrimetry, 1st Ed., pp. 57-58, Pergamon Press,
Oxford, England (1969).
BaS04 precipitation and thermometric titration.
676. Belcher, R., New Methods in Analytical Chemistry, pp. 71-75, 84-86,
88-89, Reinhold Publishing Corporation, New York (1955).
Various methods and reagents (gravimetric: hexa-aminocobalt-III
bromide, octa-amino-u-amino-u-nitrodicobalt-III nitrate; titri-
metric: 4-chloro-4'-aminodiphenyl, 4:4'-diaminotolane).
677. Belcher, R., New Methods of Analytical Chemistry, 2nd Ed., pp. 72,
206-207, 284-285, 338-341, Reinhold Publishing Corporation, New
York (1964).
Various methods, reagents, and indicators (titrimetric: rhodizonic
acid, EDTA-Solochrome Black, Alizarin Red S; spectrophotometric:
4-amino-4*-chlorodiphenyl).
678. Berka, A., Newer Redox Titrants. 1st Ed., pp. 176-177, Pergamon Press,
Oxford, England (1965).
Titration with hydroquinone.
679. Blaedel, W. J., Elementary Quantitative Analysis; Theory and Practice,
pp. 213, 220-225, 343-344, 517, 650-651, Row, Peterson and Company,
Evanston, Illinois (1957).
Various methods (gravimetric, turbidimetric, volumetric: benzidine).
116
-------
680. Blaedel, W. J., Elementary Quantitative Analysis; Theory and Practice.
2nd Ed., pp. 213, 221-225, 290, 737-741, 884, Harper and Row, New
York (1963).
Various methods (gravimetric; volumetric: thorin or dithizone;
turbidimetric).
681. Blaedel, W. J., "High-Frequency Method of Chemical Analysis," in Physi-
cal Methods in Chemical Analysis. W. G. Berl, Ed., Vol. Ill, p. 130,
Academic Press, Inc., New York (1956).
Titration of S04= with Ba(N03)2.
682. Blasius, E., "Analytical Chemistry of Sulfur Compounds," in Inorganic
Sulphur Chemistry, G. Nickless, Ed., pp. 201-205, Elsevier Publishing
Company, Amsterdam (1968).
Various (gravimetric: Ba, Sr, benzidine; volumetric: Ba, Pb, etc.;
polarographic; photometric; nephelometric; flame-photometric; radio-
metric) .
683. Burkhalter, T. S., "High Frequency Conductometric (Impedimetric) Titra-
tions," in Comprehensive Analytical Chemistry, C. L. Wilson, Ed., pp.
245-246, Elsevier Publishing Company, Amsterdam (1964).
With barium acetate.
684. Brezina, M., Polarography in Medicine, Biochemistry, and Pharmacy, pp.
118-120, Interscience Publishers, Inc., New York (1958).
S04= determined indirectly by effect on lead or barium ion wave.
685. Britton, H. T. S., Conductometric Analysis, p. 109, Chapman and Hall,
Ltd., London (1934).
Titration with Pb(N03)2-
686. Britton, H. T. S., "Conductometric Analysis," in Physical Methods in
Chemical Analysis, W. G. Berl, Ed., Vol. II, p. 96, Academic Press,
Inc., New York (1951).
in drinking water; titration with lithium oxalate.
117
-------
687. Brumblay, R. U. , A First Course in Quantitative Analysis, pp. 297-304,
362-366, Addison-Wesley, Reading, Massachusetts (1970).
Gravimetric as BaS04; volumetric with Calmagite or Erio-T as indi-
cator and EDTA as titrant.
688. Chariot, G. , Colorimetric Determination of Elements, pp. 74, 389-390,
Elsevier Publishing Company, Amsterdam (1964).
Discussion and listing of methods but no procedures (adsorption
chromatography; rhodizonate photometry; turbidimetric ; colori-
metric: barium chloranilate; reduction to S(II)).
689. Christian, G. D., Atomic Absorption Spectroscopy, pp. 440-441, Wiley-
Interscience, New York (1970).
Indirect AA using excess cation determination.
690. Conley, R. T., Infrared Spectroscopy, 2nd Ed., pp. 202-203, 207, Allyn
and Bacon, Inc., Boston (1972).
S0^= bands at 1,130 to 1,080 cm'1 and 680 to 610 cm"1.
691. Crow, D. R. , Polarography, p. 106, Methuen and Company, Ltd., London
(1968).
Amperometric titration with
692. Gumming, A. C., in Quantitative Chemical Analysis. R. A. Chalmers, Ed.,
llth Ed., pp. 104-105, 202-203, 260-262, Oliver and Boyd, Edinburgh,
Scotland (1956).
Volumetric (after reduction to H2S, H2S determined with methyl red
as indicator; as BaS04 using sodium rhodizonate as indicator); grav-
imetrically as
693. Davis, D. G. , "Conductometric Titrations," in Comprehensive Analytical
Chemistry. C. L. Wilson, Ed., Vol. ILA, p. 205, Elsevier Publishing
Company, Amsterdam (1964).
Conductometric (barium acetate) .
118
-------
694. Davis, D. G., "Potentiometric Titrations," in Comprehensive Analytical
Chemistry, C. L. Wilson, Ed., Vol. IIA, pp. 132-135, Elsevier Pub-
lishing Company, Amsterdam (1964).
Potentiometric (Pb, Ba, membrane electrodes).
695. Dean, J. A., Flame Photometry, p. 267, McGraw-Hill Book Company, Inc.,
New York (1960).
Indirect determination of SOT by excess barium.
696. Dick, J. G., Analytical Chemistry, p. 347, McGraw-Hill Book Company, Inc.,
New York (1973).
General discussion of EDTA titration of excess barium.
697. Donbrow, M., Instrumental Methods in Analytical Chemistry. Vol. I.
Electrochemical Methods, p. 256, Sir Isaac Pitman and Sons, Ltd.,
London (1966).
Conductometric titration of metal sulphate with BaCl2 or acetate.
698. Donbrow, M., Instrumental Methods in Analytical Chemistry. Vol. II.
Optical Methods, pp. 234-237, Sir Isaac Pitman and Sons, Ltd., London
(1967).
Nephelometric determination.
699. Erdey, L., "Chemiluminescent Indicators," in Indicators, E. Bishop, Ed.,
Pergamon Press, Oxford, England (1969).
Chromatometric determination of S0^= in presence of siloxene indi-
cator.
700. Ewing, G. W., Instrumental Methods of Chemical Analysis, 3rd Ed., pp.
581-582, McGraw-Hill Book Company, Inc., New York (1969).
General textbook, turbidimetric experiment for SOT.
701. Feigl, F., Chemistry of Specific, Selective and Sensitive Reactions, pp.
312-314, Academic Press, Inc., New York (1949).
Benzidine precipitation.
119
-------
702. Flaschka, H. A., "Titrations with EDTA and Related Compounds," in
Comprehensive Analytical Chemistry, C. L. Wilson, Ed., Vol. IB,
pp. 365-366, Elsevier Publishing Company, Amsterdam (1960).
Titration of excess barium with EDTA.
703. Fowles, G. , Volumetric Analysis, pp. 108-110, 153, 201, G. Bell and
Sons, Ltd., London (1957).
Volumetric using barium oxalate, barium chromate, and benzidine.
704. Fritz, J. S., Quantitative Analytical Chemistry, 2nd Ed., pp. 54,
208-209, 513-515, 537-539, Allyn and Bacon, Inc., Boston (1969).
Gravimetric, volumetric (Alizarin Red S as indicator).
705. Furman, N. H. , Ed., Standard Methods of Chemical Analysis. Vol. I.
The Elements, 6th Ed., pp. 1007-1015, 2483-2484, D. Van Nostrand
Company, Inc., Princeton, New Jersey, (1962).
Various SO, = methods (BaSO^: gravimetric; BaC^: K2Cr04 titrations;
BaCr04: KI titration; benzidine hydrochloride titration; combustion;
turbid ime trie) .
706. Gilbert, P. T., "Nonmetals," in Analytical Flame Spectroscopy, R.
Mavrodineanu, Ed., pp. 295-296, MacMillan and Company, Ltd.,
London (1970).
Indirect flame-emission determination of excess barium, AA spec-
troscopy.
707. Grant, J., Ed., Clowes and Coleman's Quantitative Chemical Analysis,
15th Ed., pp. 65-67, 172-174, J. A. Churchill, Ltd., London (1947).
Various methods (gravimetric: BaSO^.; volumetric: iodometric,
benzidine) .
708. Guilbault, G. G., Practical Fluorescence, pp. 228, 257, Marcel Dekker,
Inc., New York (1973).
Quench by SC>4= of fluorescence of Th-morin complex.
120
-------
709. Haddock, L. A. "Sulfur," in Comprehensive Analytical Chemistry. C. L.
Wilson, Ed., Vol. 1C, pp. 282-290, Elsevier Publishing Company,
Amsterdam (1962).
General discussion of methods.
710. Haff, L. V., "Oxygen-Containing Inorganic Sulfur Compounds," in The
Analytical Chemistry of Sulfur and Its Compounds, J. H. Karchmer,
Ed., Part I, pp. 203-207, 210-212, 236, Wiley-Interscience, New
York (1970).
Various methods (gravimetric; turbidimetric; spectrophotometric;
by reduction to I^S); separation by ion-exchange.
711. Headridge, J. B., Photometric Titrations, pp. 92, 99-100, 104, Pergamon
Press, New York (1961).
Turbidimetric with BaCl2 precipitation; automatic spectrophotomet-
ric titration at 520 mu with barium perchlorate using thoron as in-
dicator.
712. Hendrickson, E. P., "Air Sampling and Quantity Measurement," in Air Pol-
lution, A. C. Stearn, Ed., 2nd Ed., Vol. II, pp. 3-52, Academic Press,
Inc., New York (1968).
General sampling procedures.
713. Herrmann, R., "The Applications of Flame Photometry in Biology and Medi-
cine," in Analytical Flame Spectroscopy, R. Mavrodineanu, Ed., p. 502,
MacMillan and Company, Ltd., London (1970).
Indirect determination using excess barium in 873 nm band (BaOH).
714. Hillebrand, W. F., Applied Inorganic Analysis. 2nd Ed., pp. 711-723,
John Wiley and Sons, New York (1953).
Discussion of methods (including errors) (gravimetric; volumetric;
turbidimetric; colorimetric).
715. Hochgesang, F. P., "Nephelometry and Turbidimetry," in Treatise on
Analytical Chemistry. Part I. Theory and Practice. I. M. Kolthoff,
Ed., Vol. 5, pp. 3313-3314, 3317-3320, John Wiley and Sons (Inter-
science Publishers), New York (1964).
Automatic turbidimetric of
121
-------
716. Holy, H. W., "Automated Analytical Techniques in Water and Air Pol-
lution," in Automated Analytical Chemistry, Technicon Symposium,
1963, pp. 9-14, Technicon Instruments Company, Ltd., Chertsey,
England (1964).
General automated procedures including
717. Huber, W., Titrations in Nonaqueous Solvents, pp. 136, 188-189, Academic
Press, New York (1967).
Acidimetric using barium acetate which is back titrated potentio-
metrically; conductometric.
718. Ingram, G., "Micro-Analysis of Organic Compounds," in Methods of Quanti-
tative Micro-Analysis, R. F. Milton, Ed., 2nd Ed., pp. 91-94, Edward
Arnold (Publishers), Ltd., London (1955).
Gravimetric; volumetric.
719. Jacobs, M. B., The Chemical Analysis of Air Pollutants, pp. 41, 90,
116-117, Interscience Publishers, Inc., New York (1960).
Turbidimetric; sampling.
720. Katz, M., "Analysis of Inorganic Gaseous Pollutants," in Air Pollution,
A. C. Stearn, Ed., 2nd Ed., Vol. II, pp. 54-80, Academic Press, Inc.,
New York (1968).
General analysis for sulfur compounds (West-Gaeke; H202: titration;
conductimetric; iodometric; 63804: turbidimetric; H2S: methylene
blue).
721. Klockow, D., "On the Determination of Sulphate in Background Air," in
Abstracts, IUPAC International Congress on Analytical Chemistry, 3-7
April 1972, Kyoto, pp. 581-582 (1972).
Various methods (volumetric; nephelometric; iodometric; radiometric)
and sampling.
722. Kolthoff, I. M., Polarography, 2nd Ed., Vol. II, pp. 558, 917-919, Inter-
science Publishers, New York (1952).
Indirect polarographic measuring effect on diffusion current of
barium ion; amperometric titration using
122
-------
723. Kolthoff, I. M., Quantitative Chemical Analysis. 4th Ed., MacMillan
Company, London (1969).
General textbook.
724. Kolthoff, I. M., Volumetric Analysis. Vol. I. Theoretical Fundamentals.
2nd'Ed., p. 98, Interscience Publishers, New York (1942).
Titration using BaCl2 or lead; discussion.
725. Kolthoff, I. M., Volumetric Analysis. Vol. II. Titration Methods.
2nd Ed., pp. 163-165, 190-191, 203, 306-316, Interscience Publishers,
Inc., New York (1947).
Determination with benzidine; BaCl2 (hydrolytic precipitation);
palmitate; Pb(N03)25 sodium rhodizonate; tetrahydroxyquinone;
flubrescein; methyl red.
726. Kolthoff, I. M., Volumetric Analysis. Vol. III. Titration Methods, pp.
292-293, 338-340, Interscience Publishers, Inc., New York (1957).
Reduction to H2S with iodometric determination of sulfide; titration
of chromate.
727. Kucharsky, J., Titrations in Non-Aqueous Solvents, pp. 73, 130-131,
136, 141, Elsevier Publishing Company, Amsterdam (1965).
Various methods (conductometric; potentiometric).
728. Landis, P. S., "Tetra- and Hexavalent Organosulphur Compounds," in The
Analytical Chemistry of Sulfur and Its Compounds. J. H. Karchmer, Ed.,
Part II, pp. 792-793, 809, Wiley-Interscience, New York (1972).
Various methods (paper chromatography; IR spectroscopy; hydrolysis).
729. Lyalikov, Y., Physicochemical Analysis, pp. 366-368, Mir Publishers,
Moscow (1968).
Conductomertic titration.
730. MacDonald, A. M. G., "Determination of Halogens and Sulphur in Organic
Compounds," in Comprehensive Analytical Chemistry. C. L. Wilson, Ed.,
Vol. IB, pp. 533-539, Elsevier Publishing Company, Amsterdam (1960).
Gravimetric; volumetric; reduction of S; conductometric; ampero-
metric; turbidimetric.
123
-------
731. Milner, G. W. C., The Principles and Applications of Polarography and
Other Electroanalytical Processes, pp. 317-318, 646-648, Longmans,
Green and Company, London (1957).
Indirect polarographic by reduction to HoS; amperometric titration.
732. Milton, R. F., "Colorimetric Analysis," in Methods of Quantitative Micro-
Analysis. R. F. Milton, Ed., 2nd Ed., pp. 330, 406, 413-414, Edward
Arnold (Publishers), Ltd., London (1955).
Colorimetric (diazotisation of benzidine); nephelometric.
733. .Milton, R. F., "Illustrative Examples of Micro-Volumetric Procedures,"
in Methods of Quantitative Micro-Analysis, R. F. Milton, Ed., 2nd Ed.,
pp. 172-173, 195, 227-228, Edward Arnold (Publishers), Ltd., London
(1955).
Volumetric using benzidine, tetrahydroxyquinone; BaCr204: diphenyl-
carbazide; EDTA.
734* Mitchell, A. D., Modern Methods in Quantitative Chemical Analysis, pp.
38-39, 136-137, Longmans, Green and Company, London (1932).
Volumetric (determination of excess Ba).
735. Passwater, R. A., Guide to Fluorescence Literature, Vol. I, II, Plenum
Press, New York (1967, 1970).
Bibliography.
736. Patterson, G. D., Jr., "Sulfur," in Colorimetric Determination of Non-
metals, D. F. Boltz, Ed., pp. 267-270, 278, Interscience Publishers,
Inc., New York (1958).
Turbidimetric; Colorimetric determination using benzidine.
737. Price, W. J., Analytical Atomic Absorption Spectroscopy,' p. 178, Heydon
and Son, Ltd., London (1972).
Determination of excess barium.
738. Pungor, E., "Adsorption Indicators," in Indicators, E. Bishop, Ed., 1st
Ed., p. 465, Pergamon Press, Oxford, England (1972).
Determination of 804" by titration using sodium alizarine sulphonate
as surface precipitation indicator.
124
-------
739. Pungor, E., Oscillometry and Conductometry, pp. 181-183, Pergamon Press,
Oxford, England (1965).
Precipitation as 63804; oscillometric determination.
740. Reilly, C. N., "High-Frequency Methods," in New Instrumental Methods in
Electrochemistry, R. Delahay, Ed., p. 342, Interscience Publishers,
Inc., New York (1954).
General discussion.
741. Sawin, S. B., Organic Reagents for Determining Barium and Sulfate Ions,
Nauka, Moscow (1970).
Review.
742. Schwarzenbach, G., Complexometric Titrations, 2nd Ed., pp. 123, 315-318,
Methuen and Company, Ltd., London (1969).
Volumetric (EDTA).
743. Skoog, D. A., Fundamentals of Analytical Chemistry, pp. 203-205, 631,
Holt, Rinehart and Winston, New York (1963).
Gravimetric; amperometric titration.
744. Snell, F. D., Colorimetric Methods of Analysis, 3rd Ed., Vol. II, pp.
767-775, D. Van Nostrand Company, Inc., New York (1949).
Turbidimetric (63804); nephelometric (63804); colorimetricslly
(chromste: diphenylcsrbszide, benzidine).
745. Snell, F. D., Colorimetric Methods of Anslysis, 3rd Ed., Vol. IIA, pp.
671-674, D. Vsn Nostrand Company, Inc., New York (1959).
Reduction to H2S (methylene blue); turbidimetric; nephelometric;
Colorimetric (thorium: amaranth lake, benzidine in UV, 4-amino-
4"-chlorodiphenyl).
746. Snell, F. D., Commercial Methods of Analysis, 2nd Ed., pp. Ill, 157-160,
166-168, 230-231, Chemical Publishing Company, Inc., New York (1964).
Various methods (barium rhodizonate; gravimetric; volumetric).
125
-------
747. Steyermark, A., Quantitative Organic Microanalysis, 2nd Ed., pp. 110,
126, Academic Press, New York (1961).
Volumetric (BaSO^: tetrahydroxyquinone).
748. Stock, J. T., Amperometric Titrations, p. 555, John Wiley and Sons
(Iriterscience Publishers), New York (1965).
Indirect titration using bromate-arsenic (III) biamperometric
titration.
749. Stock, J. T., "Electro-Chemical Methods of Micro-Analysis," in Methods
of Quantitative Micro-Analysis, R. F. Milton, Ed., 2nd Ed., pp. 495-
497, Edward Arnold (Publishers), Ltd., London (1955).
Amperometric titration.
750. Button, F., A Systematic Handbook of Volumetric Analysis or The Quanti-
tative Determination of Chemical Substances by Measure, Applied to
Liquids, Solids, and Gases, J. Grant, Ed., pp. 261, 438-442, 575,
Butterworths Scientific Publications, London (1955).
Conductometric; chromate titration; potentiometric; amperometric;
benzidine; BaCl2 precipitation; gravimetric.
751. Tamamushi, R., "Application of Polarography and Related Electrochemical
Methods to the Study of Labile Complexes in Solution," in Progress in
Polarography, P. Zuman, Ed., Vol. Ill, pp. 35-36, 40-41, Wiley-Inter-
Science, New York (1972).
Stability constants of SO^ complexes.
752. Tblg, G., "Elemental Analysis with Minute Samples," in Wilson and Wilson's
Comprehensive Analytical Chemistry, G. Svehla, Ed., Vol. Ill, pp. 101,
103, Elsevier Scientific Publishing Company, Amsterdam (1975).
Spectrophotometric; fluorimetric.
753. Tyrrell, H. J. V., Thermometric Titrimetry. pp. 95-96, 131, Chapman and
and Hall, Ltd., London (1968).
BaCl2 titration.
126
-------
754. Vogel, A. I., A Text-Book of Quantitative Inorganic Analysis Including
Elementary Instrumental Analysis. 3rd Ed., pp. 276, 446-448, 462-468,
573, 806-807, 850-851, 958-959, 996-997, 1040-1041, Chaucer Press,
Great Britain (1966).
Various S04= methods (BaS04: EDTA titration; PbSC>4: EDTA titration;
Ba chloranilate: colorimetric; BaSO^: nephelometric; potentiometric
titration; high-frequency titration; amperometric titration).
755. Wagner, W., Advanced Analytical Chemistry, pp. 8, 206-207, Reinhold Pub-
lishing Corporation, New York (1956).
Volumetrically (benzidine, chromate, rhodizonic acid, tetrahydroxy-
quinone); gravimetric (benzidine, BaSC<4, hexamminocobalt (III) bro-
midesulfate); nephelometric.
756. Walden Research Corporation, Improved Methods for Sampling and Analysis
of Gaseous Pollutants from the Combustion of Fossil Fuels. Vol. I.
Sulfur Oxides. EPA Contract No. CPA-22-69-95 (1971).
General sampling and analysis procedures.
757. Walton, H. F., Principles and Methods of Chemical Analysis, pp. 106, 352,
391, 400, Prentice-Hall, Inc., New York (1952).
Volumetric (sodium rhodizonate, tetrahydroxyquinone); conductometric;
amperometric.
758. Walton, H. F., Principles and Methods of Chemical Analysis, 2nd Ed., pp.
151, 177, Prentice-Hall, Inc., Englewood Cliffs, New Jersey (1964).
Ion-exchange (gravimetric or titrimetric); S reduction.
759. West, P. W., "Spot Test Procedures," in Comprehensive Analytical Chem-
istry, C. L. Wilson, Ed., Vol. IA, p. 387, Elsevier Publishing Company,
Amsterdam (1959).
Spot test (Hg[N03]2).
760. White, C. E., Fluorescene Analysis, p. 99, Marcel Dekker, Inc., New York,
(1970). .
Determination of S04= by excess thorium determination using morin.
127
-------
SAMPLING
761. Adams, D. F., "Analysis of Sulfur Containing Gases in Ambient Air Using
Selective Prefilter and a Micro Goulometric Detector," APCA, 18(3):145
(1968).
Sampling; not specific for S0^=.
762. Barton, S. C., "Preparation of Glass Fiber Filters for Sulfuric Acid
Aerosol Collection," Environ. Sci« Technol., 4:769-770 (1970).
Extracted filters with H SO prior to sampling.
763. Barton, S. C., "A Specific Method for the Automatic Determination of Am-
bient H2S04 Aerosol," Proceedings of the 2nd International Clean Air
Congress, pp. 379-382, Academic Press, New York (1970).
Extracted filters with isopropyl alcohol to selectively remove H SO,•
764. Cadle, R. D., "Determination of the Composition of Air-Borne Particulate
Material," Anal. Chem.. 23:196-198 (1951).
Particulate collected by impaction on microscope slides covered with
mineral oil film and treated with various reagents; Bad test for SO =.
765. Colucci, J. M., "Polynuclear Aromatic Hydrocarbons and Other Pollutants
in Los Angeles Air," Proc. Int. Clear Air Cong., 2nd., 1970, pp. 28-35
(1971).
Measured aromatics, CO, Pb, THC, V, NO , and SO = using classical methods.
X H~
766. Commins, B. T., "Determination of Particulate Acid in Town Air," Analyst,
88:364-367 (1963).
Sample collected on 4.25 cm Whatman No. 1 filters in Perspex holder;
up to 30 liter/min and up to 6 hr.
767. Corn, M., "Particulate Sulfates in Pittsburg Air," APCA, 15X0:26-30
(1965).
Cascade Impactor sampling. BaSO, analysis.
768. Corn, M., "Sulfate Particulates - Size Distribution in Pittsburg Air,"
Science, 143(3608):803-804 (1964).
S04= may be better indicator of atmospheric pollution than S02*
769. Dubois, L., "Determination of Sulfate in Air," Int. J. Environ. Anal. Chem.,
-------
770» Forrest, J», "Ambient Air Monitoring for Sulfur Compounds* A Critical
Review," J. Air Poll. Contr. Assoc.. 23/9):761-768 (1973).
Review of sampling and analysis methods*
771. Gelman, C., "Estimation of Water-Soluble Chlorides, Sulfates, and
Nitrates in Suspended Atmospheric Dusts," J. Air Poll. Contr. Assoc.,
7(3):216-219 (1957).
Sampling on Whatman 41H filter paper; turbidimetric method for SO/=;
advantage of cellulose filter paper.
772. Green, W. D., "Identification of Chemical Constituents in Single Aerosol
Particles," Amer. Chem. Soc., Div. Water, Air Waste Chem., Reprints,
7(2):83-90 (1967).
Samples collected on glycerin-gelatin films containing a soluble
Ba salt.
773. Hall, S. K., "Sulfur Compounds in the Atmosphere," Chemistry, 45(3):
. 16-18 (1972).
Discussion of health effects.
774. Higgins, F. B., Jr., "Sampling of Gases and Vapors," Source Samp. Atmos.
Contam., Symp. Proc., 1971, pp. 47-62.
Review of sampling trains, procedures, and analytical methods.
775. Huey, N. A., "Determination of Sulfate in Atmospheric Suspended
Particulates; Turbidimetric Barium Sulfate Method," U.S. Public
Health Service Publ., 999-AP-ll, I-1-I-4 (1965).
High volume collection on glass fiber. Water extraction-BaSO^ method.
776. Jacobs, B., "Air Pollution and Atmospheric Analysis," Encycl. Ind. Chem.
Anal.. 1:99-121 (1966).
Review of sampling and analysis of air contaminants.
777. Junge, C. E., "The Concentration of Chloride, Sodium, Potassium, Calcium,
and Sulfate in Rain Water Over the United States," J. of Meterology,
l£(5):417-425 (1958).
A geographic survey.
778. Kiyoura, R., "Review of Direct Measurement Method of Sulfuric Acid Mist
in Atmosphere," Preprint, Japan Chemical Society, Paper, 3406, Jap. Chem.
Soc. Ann. Mtg., 24th, Tokyo (1971).
Discussion of sampling techniques.
129
-------
779, Leaky, D., "The Separation and Characterization of Sulfate Aerosol,"
Atmos. Environ., £:219-229 (1975).
Studies pyrolytic and selective extraction for separation of sulfates.
Also investigated filters.
780. Lee, R. E., "A Sampling Anomaly in the Determination of Atmospheric
Sulfate Concentrations," Amer. Indus. Hyg. Assoc., J., 27:266-271
(1966).
S02 oxidized to S0^= on filter elevates S0^= readings for short term
samples; solution to problem given.
781. Ludlam, F. H., "Atmospheric Aerosol," Sci. Progr., 42(165):65-75 (1954).
Sample deposited on slides behind two slits that divided > 0.9 u and
0.1 to 0.9 u particle radius.
782. Maddalone, R. F., "Radiochemical Evaluation of the Separation of Sul-
phuric Acid Aerosol by Micro-Diffusion from Various Filter Media,"
Mikrochim. Acta.. 3:391-402 (1974).
Dubois work explained; glass-fibre poor, PTFE or graphite filters
good.
783. Matsumura, Y., "Evaluation of Chemical Analysis Method of Sulfuric Acid
Mist for Air Pollution," Rodo Eisei Kenkyusho Nenpo, pp. 48-49 (1971).
Discussion of analysis and sampling equipment and procedures.
784. Miller, J. M., "Rate of Sulfate Formation in Water Droplets in the
Atmosphere with Different Partial Pressures of Sulfur Dioxide,"
Proc. Int. Clean Air Cong., 2nd, 1970, pp. 375-378 (1971).
Theoretical calculation of reaction rates.
785. Nakaoka, A., "Preparation of Standard Gas Containing Sulfuric Acid
Aerosol. (Determination of Microamounts of Sulfur Trioxide in
Atmosphere, Part I)," Tokyo Chuo Kenyusho Gijutsu Daiichi Kenkyusho
Hokoku. (71044): 1-19 (1971). '
Discussion of filters and collection.
786. Nucciotti, F., "improvements in Sampling Techniques and in the Methods
for Determining Acid Gases in the Atmosphere," Riv. Ing., (5):353-356
(1969).
General sampling and analysis.
787. Quitmann, E., "Chemical Analysis of Mist Nuclei in the Atmosphere,"
Z. anal. Chem.. 116:81-91 (1939).
Nuclei of moisture with radii of 10" to 10~ cm condensed on chilled
*
surface and examined (S0/-=included).
130
-------
788. Rauh, W., "Die Bestimmung von Freier Schwefelsaure in der Atmospharischen
Luft," Z. gesammte Hygiene Ihre Grenzgebiete, Ij3:8-12 (1972).
Collected by impingement on copper foil*
789. Richards, L. W., "A New Technique to Measure Sulfuric Acid in the Atmosphere,"
Abstracts, 165th Natl. Meeting of the Amer. Chenu Soc., Dallas, Texas,
April 1973, No. WaTR047.
Instrument: collects on filter, volatizes and measures with FPD.
790. Roesler, J., "Size Distribution of Sulfate Aerosols in the Ambient Air,"
APCA, 15^(12):576-579 (1965).
Sampling with Anderson Impactor.
791. Scaringelli, F. P., "Dynamic Calibration of an Acid Aerosol Analyzer,"
JAPGA, 1£(6):310 (1966).
792. Scaringelli, F. P., "Determination of Atmospheric Concentration of
Sulfuric Acid Aerosol by Spectrophotometry, Coulometry, and Flame
Photometry," Anal. Chem., 41(6);707-713 (1969).
I^SO^ separated from SO and other sulphates. SOo in N£ converted to
362 with hot Cu. SO. determined by FPD. Method can measure 112804 in
presence of 100 times as much S02 and other sulphates.
793. Wagman, J., "Influence of Some Atmospheric Variables on the Concentration
and Particle Size Distribution of Sulfate in Urban Air," Atmos. Environ.,
Isi479-489 (1967).
Discussion.
794. West, P. W., "Evaluation of Sulfur and Selenium Compounds as Air Pollu-
tants," Proc., Int. Symp. on Ident. and Meas. of Environ. Pollutants,
Ottawa, Ontario, Canada, 14-17 June 1971, pp. 38-43.(1971).
Discussion.
131
-------
ADDENDUM
The following references were located after the report was submitted for
approval •
795. Brosset, C., "Particle-Borne Acid: Occurrence, Effects and Determination
Methods," Presented Before the Division of Water, Air and Waste Chemistry,
Amer. Chem. Soc., August 1972*
796. Grennfelt, P., "Determination of Filter-Collected Airborne Matter by
X-Ray Fluorescences Atmos. Environ., 5:1-6 (1971).
797. Huygen, C., "A Simple Photometric Determination of Sulphuric Acid Aerosol,"
Atmos. Environ «, 9:315-319 (1975).
Reacted with diethylamine and determined excess DEA photometrically.
798» Lukin, A. M., "Spectrophotometric Determination of Microamounts of Sulfates
Using Chlorophosphonazo III." Zavod. Lab.. 4£(l):22-23 (1974).
Ba complex of chlorophosphonazo III reacted with S0^~ to release com-
plexant. Decrease in absorbance of complex measured at 645 nm at pH 2.
799. West, P. W., "The Determination of Sulfuric Acid Aerosols," Analyt. Chim.
Octa., 69^:111-116 (1974).
Ring oven method. Not specific.
800. Zenki, M., "Titrimetric Method for Sulfate with Bisazochromotropic Acid
Analogs as the Indicator." Bunseki Kagaku. 22^(8): 1013-1017 (1973).
Titrate with Ba (ClO^) at pH 3. Sulfonazo III one of the best studied.
A number of cations and anions interfere.
132
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO
EPA-600/4-76-008
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
MEASUREMENT OF ATMOSPHERIC SULFATES:
SEARCH AND METHODS SELECTION
LITERATURE
5. REPORT DATE
mm* 2,
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO,
Fred J. Bergman
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
1HD621
11. CONTRACT/GRANT NO.
68-02-1728
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park. North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A thorough literature search for methods of sulfate analysis has been com-
pleted. The results of the search with a very brief abstract of each method are
attached as an appendix. The analytical methods have been reviewed for strengths
and weaknesses, and the two most promising methods have been selected. Based on
this review, the two recommended methods are the methyl thymol blue method
described by A. L. Lazrus and the barium chloranilate method modified by H. N. S.
Schafer and developed by R. J. Bertolacini and J. E. Barney, II. The results of
this phase of the investigation have been submitted to EPA. Acceptance of the
two recommended methods and approval to complete the investigation were received
October 15, 1975.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Bibliographies
Methodology
Sulfate Analysis
Methyl Thymol Blue
Barium Chloranilate
Literature Search
13B
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassi fi ad
21. NO. OF PAGES
140
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
133
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