Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/uawm16

A Rapid Method for the Determination of Sulfur in

Fuel Oil by the Schoniger Oxygen Flask Method
D. A. Levaggi & M. Feldstein
To cite this article: D. A. Levaggi & M. Feldstein (1963) A Rapid Method for the Determination
of Sulfur in Fuel Oil by the Schoniger Oxygen Flask Method, Journal of the Air Pollution Control
Association, 13:8, 380-387, DOI: 10.1080/00022470.1963.10468195
To link to this article: http://dx.doi.org/10.1080/00022470.1963.10468195

Published online: 19 Mar 2012.

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Date: 12 September 2016, At: 04:59

A Rapid METHOD for the DETERMINATION of SULFUR in FUEL

OIL by the SCHONIGER OXYGEN FLASK METHOD*
D. A. LEVAGGI, Chemist, and M. FELDSTEIN, Laboratory Director,
Bay Area Air Pollution Control District, San Francisco, California

Vlassic methods for the determination of sulfur in organic compounds

generally involve combustion of the
material and subsequent estimation of
the sulfate formed. Most of the standard procedures require the use of complicated apparatus, considerable skill,
and are generally time consuming.1-2
ASTM methods for sulfur3- 4-5-G are
based on classic techniques requiring
special apparatus and skills, and are
also time consuming.
Schoniger7 introduced the oxygen
combustion flask which has been used for
the determination of a number of elements in organic compounds; a comprehensive review of the method and bibliography has been published.8- 9
This study was undertaken to determine the applicability of the Schoniger
technique to the determination of sulfur
in fuel oil.

paper dropwise from a capillary pipet.

The flask is flushed with oxygen, and
combustion of the filter paper carrier
and sample is carried out in the Schoniger flask in the usual fashion.
After combustion is complete, the flask
is shaken several times and allowed to
stand for 10 to 15 min to permit complete absorption of sulfate. The contents of the flask are quantitatively
transferred to a 125 ml Erlenmeyer
flask with the aid of 40 ml isopropyl
alcohol. Three drops of one to four
perchloric acid are added followed by
one drop of 0.2% Thorin. The solution
is then titrated with 0.01 M BaCL 2 to a
salmon-pink end point.10
A blank
paper is combusted in a similar fashion
and carried along as a procedure blank.
(The blank should contain a known
amount of added sulfate in order to
obtain the proper end point.)

Equipment and Reagents

Standardization of BaCI?

(1)
(2)
(3)
(4)
(5)
(6)

Schoniger Oxygen Flask

Filter paper carrier
Oxygen
Isopropyl alcohol
30% H2O2
Perchloric acid, 72%, diluted 1 to
4 with H2O
(7) Thorin solution, 0.2%, aqueous
(8) BaCL2, 0.01 M in 80% isopropyl
alcohol, adjusted to a pH of three
using perchloric acid
(9) H2SO4, 0.0200 normal

* Presented at the 55th Annual Meeting

of APCA, Sheraton-Chicago Hotel, May
20-24, 1962, Chicago, Illinois.
380

Analysis of Fuel Oil Samples

A series of fuel oil samples whose
sulfur content was known by analysis
according to ASTM D1552-58 was
analyzed by the above procedure. In
addition, a series of mixtures of sample
No. 5 (9.56% S) and transformer oil
(0%
sulfur) was formulated with
varying sulfur content and these were
analyzed by the above procedure. The
results are shown in Table I.
Discussion and Conclusions
The data indicate that repeatability
and reproducibility are well within
ASTM requirements. The proposed
procedure is extremely simple and
requires no complex equipment. A
complete analysis can be performed in
about 10 to 15 min, with only four to
five minutes of actual working time.

The BaCl2 is standardized against

0.0200 N H2SO4. An aliquot is pipetted
into a 125 ml Erlenmeyer flask and
diluted to 50 ml with water and isopropyl alcohol to a final concentration
of 80% alcohol. After the addition of
four drops of 30% H2O2 and one drop of
Thorin, the solution is titrated with the
0.01 M BaCl2 as described above. The
sulfur equivalence of the BaCl2 solution
is then calculated.
Calculation of sulfur content of fuel

Acknowledgment
The authors wish to thank the Tidewater Oil Company for generously
supplying the fuel oil samples and the
ASTM D1552-58T analyses.
REFERENCES

1. W. W. Scott, "Standard Methods of

Chemical Analysis," 5th Edition, 2:
(Continued on p. 887)

Table IAnalysis of Fuel Oil Samples

Procedure
Place 10 ml water and four drops of
30%
H2O2 in the Schoniger flask.
Weigh a sample of the oil directly onto
the filter paper carrier. The weight of
the sample required depends on the sulfur
content of the oil. We have found that
the following amounts are adequate: 5 to
10% sulfur10 to 15 mg sample; 2 to
5% sulfur15 to 25 mg sample; 0 to
2% sulfur25 to 40 mg sample. The
sample is conveniently added to the

oil: (ml BaCl2 usedml BaCl2 for blank)

X sulfur equivalence = mg sulfur in
weight of sample taken.

Sample
1
2
3
4
5

Mixture
Mixture
Mixture
Mixture
Mixture

1
2
3
4
5

Sulfur
by ASTM
D1552
1.48
1.43
2.51
2.08
9.56
3.87
1.58
0.71
4.41
2.66

Percent Sulfur by
Proposed Me1-Vinrl
jnoci
No.

DeterAverage
Average minations Deviation
0.023
1.54
7
4
1.48
0.020
5
2.62
0.028
4
2.15
0.015
4
9.66
0.043
4
3.84
0.020
3
1.57
0.035
3
0.71
0.012
4
4.42
0.052
2
2.68
0.000

Deviation
from ASTM
Value

+0.06
+0.05
+0.11
+0.07
+0.10
-0.03
-0.01
0.0

+0.01
+0.02

Deviation
from
ASTM
Value
4.0
3.5
4.3
3.4
1.1
0.8
0.6
0.0
0.2
0.8

Journal of the Air Pollution Control Association

100

UP-TO-DATE WITH APCA

Reports

The 1962 Annual Report of the City

of Chicago is now available.
The 1962 Annual Report of Cleveland's Division of Air and Stream
Pollution, Department of Urban Renewal and Housing is also ready for
distribution.
Brochures
0

10 20 30 40 50 60 70 80 +
AGE (JJP.)

Fig. 6. The above diagram accompanied a

letter to the Lancet (December 22, 1 962) from
three general practitioners, on the effects of the
smog on patients to a general practice in the
Beckenham area. One of the writers, Dr. John
Fry, published a similar survey in the Lancet
after Ihe 1952 episode, and the diagram compares the two. In 1952 the patients were
treated for acute chest infections at a rate of
95 per 1000. In 1962 the rate was 24. In
1 952 there were two deaths; in 1 962 none.

Fig. 5.
The tower at the Royal Military College
showing through the fog. (Photo courtesy of
the Daily Express.)

recorded the highest smoke concentrations and one of them, Crumpsall, recorded the highest sulphur dioxide measurement, but tied with the City Centre
forfirstplace.
There was no significant change in
mortality rates and no records are available regarding respiratory disease morbidity. Significantly, for the first time,
the general public became aware of the
distinction between smoke and its effects and sulphur dioxide and its effects
and realized that smoke control did not
mean the automatic elimination of sulphur dioxide from the atmosphere.
In Leeds the fog was particularly
dense on December 4 and 5. Records
of smoke and sulphur dioxide concentration were taken at nine points in the
city and marked increases were noted.
The cold weather preceding the fog had
resulted in householders using their
domestic open fires for long periods.
The highest recorded level of pollution
occurred in an industrial area situated
in the lowest part of the city. Deaths
rose a little, the figures for respiratory
diseases being the highest yet recorded
this winter.
August 1963 / Volume 13, No. 8

Glasgow reported a typical smog on

one day only, December 5. That week
the city recorded increases in deaths
from pneumonia and bronchitis, a
large proportion being elderly people.
The main characteristic of the fog
in Salford was an increase of nearly
400% above the normal December
average in smoke pollution measurement on the second day of the incident.
Visibility was down to ten yards. The
increase in sulphur dioxide pollution
was over 300% above the December
average. No great change was noted
in the mortality figures.

SULFUR DETERMINATION
(Continued from, p. 380)
1756, D. Van Nostrand Company,
New York (1939).
2. J. B. Niederel and V. Niederel, "Micromethods of Quantitative Organic
Analysis," 2nd Edition, p. 182, Wiley,
New York (1942).
3. ASTM D129, "Sulfur in Petroleum
Products and Lubricants by the Bomb
Method."
4. ASTM D1551, "Sulfur in Petroleum
Oils by Quartz Tube Combustion
Method."
5. ASTM D1552, "Sulfur in Petroleum
Products by the Rapid, High Temperature Combustion Method."
6. ASTM D1226, "Sulfur in Petroleum
Products Including Liquefied Petroleum Gas by Lamp Combustion."
7. W. Schoniger, "A Micromethod for
the Determination of Halogen and
Sulfur Compounds," Microchem. Ada,
123(1955).
8. W. Schoniger, "The Oxygen Flask
Method," Facts and Methods, 1:
2, 1, F & M Scientific Corporation,
1202 Arnold Avenue, Air Base, Newcastle, Delaware (1960).
9. "Directions for Use of ThomasSchoniger Combustion Apparatus,"
A. H. Thomas Company, Philadelphia,
Pennsylvania (1958).
10. J. S. Fritz, S. S. Yamamura, "Rapid
-. Microtitration of Sulfate," Anal.
Chem., 27:9, 1461 (1955).

A brochure entitled "Air Pollution

Selected 16 mm Films" may be obtained
through the U. S. Department of
Health, Education, and Welfare, Public
Health Service, Division of Air Pollution, Washington 25, D. C. This
brochure describes motion pictures on
air pollution which are available from
the Division.

AUTOMOBILE EXHAUST
7.
8.

9.
10.

11.

12.

13.

14.

(Continued from p. 367)

521-4(1960).
N. A. Renzetti and George J. Doyle,
Int. J. Air Poll, 2 : 327-345 (I960).
George J. Doyle, "Model Aerosols for
Atmospheric Smog," presented at the
3rd Air Pollution Medical Research
Conference of the California State
Department of Public Health (December 9, 1959).
George J. Doyle, "Self-Nucleation in
the Sulfuric Acid-Water System," / .
Chem. Phys., 35: 795-799 (1961).
G. J. Doyle, N. Endow, and J. L.
Jones, "Sulfur Dioxide Role in Eye
Irritation," Arch. Environ. Health, 3 :
657-667(1961).
C. W. Labelle, J. E. Long, and E. E.
Christofano, "Synergistic Effects of
Aerosols," Arch, of Indus. Health, 11:
297(1955).
L. Dautreband, R. Capps, and E. Weaver, "Studies on Aerosol-Enhancement
of Irritating Effects of Various Substances on the Eye, Nose, and Throat
by Particulate Matter and Liquid
Aerosols in Connection with Pollution
of the Atmosphere," Arch. Internal
Pharmacodynamics, 82: 505 (1950).
Stanford Research Institute, "The
Smog Problem in Los Angeles County,
Summary Report," published by
Western Oil & Gas Association, Los
Angeles, California (1954).
N. Endow, G. J. Doyle, and J. L.
Jones, "The Nature of Some Model
Photochemical Aerosols," / . Air Poll.
Control Assoc, 13: 5 (May 1963).

CINCINNATI SMOG
(Continued from p. 383)

not frequent in southern Ohio, may be

expected periodically. These conditions can lead to excessively high
pollution levels if the sources of contaminants remain at their present
number or increase in quantity.
REFERENCE

J. Korshover, "Synoptic Climatology of

Stagnating Anticyclones (East of the
Rocky Mountains in the United States
for the Period 1936-56)," R. A. Taft
Sanitary Engineering Center, Technical
Report A60-7 (1960).
387