Journal of the Air Pollution Control Association

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

Acid Potassium Iodide Method for Determining

Atmospheric Oxidants

Samuel Deutsch

To cite this article: Samuel Deutsch (1968) Acid Potassium Iodide Method for Determining
Atmospheric Oxidants, Journal of the Air Pollution Control Association, 18:2, 78-83, DOI:
10.1080/00022470.1968.10469098

To link to this article: http://dx.doi.org/10.1080/00022470.1968.10469098

Published online: 16 Mar 2012.

Submit your article to this journal

Article views: 549

View related articles

Citing articles: 4 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=uawm16

Download by: [200.48.98.90] Date: 23 June 2017, At: 15:08

 SAMUEL DEUTSCH Acid Potassium Iodide Method for
Kaiser Steel Corporation
Determining Atmospheric Oxidants

This investigation used an acid medium for sampling atmospheric oxidants. The acid iodide oxidant pro-
cedure was unaffected by air or oxygen, temperature variance, and reducing gases (sulfur dioxide and hy-
drogen sulfide.) The method possessed good color stability. The method also agreed favorably with the
1 or 2 % neutral buffered iodide method when a chromium trioxide scrubber was required to remove the
reducing gases from the latter procedure.
The acid oxidant absorption solution of 1 3 ml in a midget impinger contained 10 ml of 1.5% potassium iodide
in a 0.1 N sodium hydroxide solution and 3 ml of acstic acid (1:5) which produced a solution of approxi-
mately 3.8 pH. Particulate matter was removed by a glass wool attachment to the midget impinger.
The air was sampled with a Gelman Sequential Sampler at the rate of 1.41 liters per minute. After the
oxidant sample was collected, the absorbing solution was transferred to a graduated cylinder and the vol-
ume was adjusted to 25 ml with distilled water. The absorbance was read at 355 millimicrons wavelength
by a spectrophotometer in a 1 cm cell. The acid oxidant method was effective between 1 to 70 pphm of

arious manual methods for
determining microquantities of oxidants
in the atmosphere are presented in the
literature. A review of all the oxidant
methods was not practical but a resume
of the potassium iodide oxidant methods
related to this paper was necessary for
background information.
The accepted procedure in the atmo-
spheric oxidantfieldhas been essentially
the 1% neutral buffered potassium io-
dide method of Byer and Saltzman1 and
Saltzman and Gilbert2 with modifica-
tions.6 The neutral buffer consists of
O.lilf potassium dihydrogen phosphate
and O.lilf disodium hydrogen phosphate.
The California State Department of
Public Health3 has another accepted
method which has recommended the use
of a 2% potassium iodide in the same
buffer adjusted to pH7. The literature4
states that both reagents gave compara-
ble results. The problem of negative re-
ducing gases, such as sulfur dioxide and
hydrogen sulfide in potassium iodide
oxidant procedures, was eliminated
when Wartburg and Saltzman6 intro-
duced an absorbing U-tube containing
glass fiber paper impregnated with
chromium trioxide. Although the com-
plexity of the neutral buffered oxidant
method was increased by the removal of
the reducing gases, the addition of
chromium trioxide scrubber to the ab-
sorption train improved the accuracy
and precision of the procedure.
Another oxidant method frequently
encountered in the literature was the
alkaline iodide oxidant method. Smith
and Diamond7 originally recommended
an absorbent reagent of 1% potassium
iodide in liV sodium hydroxide solution,
and after sampling it was treated with
1% hydrogen peroxide to remove sulfur
dioxide interference and finally acidified
with 36% phosphoric acid to release
iodine for spectrophotometeric measure-
ment. This method was subsequently
modified by other researchers. Byer
and Saltzman8 proposed the addition of
sulfamic acid to phosphoric acid which
reduced the interference of nitrogen di-
oxide. The chromium trioxide method
was substituted for hydrogen peroxide
to remove the sulfur dioxide.5 ASTM9
modified the alkaline potassium iodide
oxidant method by substituting 1:5
glacial acetic acid for 36% phosphoric
acid and also decreased alkaline concen-
trations from 1 to O.liV sodium hydrox-
ide. The change of acid was never ex-
plained in the publication but it seems
that the acidification by acetic acid
stabilized the iodine color. To improve
the accuracy and precision of the alka-
line oxidant method, Byer and Saltz-
man1 suggested a correction factor of
1.54 for the stoichiometry; however, it
has not effectively improved the reli-
ability of the alkaline method. It
seemed that the stoichiometry was not
necessarily the problem inherent with
the method because researchers10 had
found that the ozone stability decreased
as the alkaline concentration decreased.
The article stated that ozone half-life in
a liV sodium hydroxide solution at room
temperature was only two minutes.
Therefore, the above phenomenon ques-
tioned the value of the alkaline oxidant
method as an acceptable procedure for
determining atmospheric oxidant.
The author investigated the modified
neutral and alkaline oxidant methods.
The advantages and disadvantages will
be thoroughly examined. In addition, a
new method in the field of manual oxi-
dant sampling will be introduced and the
acid iodide oxidant procedure will be
compared with both of the above men-
tioned methods.
In the course of investigating the
alkaline oxidant method, it was ob-
served that the acidified standard potas-
sium iodate solutions were stable under
laboratory conditions. This observa-
tion initiated a further study of sampling
microquantities of oxidant in an acid
media. In the past Boelter, Putman,
and Lash11 and Birdsall, Jenkins, and
Spadinger12 had performed studies of
high ozone concentrations that were ab-
sorbed in an acid solution. Both teams
of researchers reported success in their
experiments, the Boelter group11 used
the potassium iodide buffered absorption
solution with pH values ranging from 2.3
to 12 while the Birdsall team12 employed

78 Journal of the Air Pollution Control Association


an acid unbuffered potassium iodide ab-
sorbent. There are, however, contrary
reports in the literature.
The acid ozone investigations ap-
peared inconclusive. Therefore, the
acid technique merited additional atten-
tion.
Apparatus
A. Gelman Sequential sampler (auto-
matic air sampler) B-12, Model 12.
B. Midget impingers. These should be
fitted with a small piece of poly-
ethylene tubing over the inlet. The
tubing is then filled with a small
amount of glass wool to remove
particulate matter.
C. Beckman, Model DU spectropho-
tometer, and 1 cm silica cells.
D. Ozone generator. Ozone was pro-
duced in a 5.1 by 7.6 by 33.0 cm
chamber containing a mercury vapor
ultraviolet lamp. Oxygen inlet was
controlled by a gas rotometer. The
excess ozone was discharged through
a sliding waste gate by a 1/so hp
centrifugal blower.
E. Pipet, 10 and 3 ml.
F. Cylinder, glass-stoppered, gradu-
ated, 25 ml.
G. Buret, micro, Koch, 5 ml.
Reagents
A. Sodium Hydroxide-potassium iodide
solution. Four grams of sodium hy-
droxide are dissolved in distilled
water. Fifteen grams of potassium
iodide are added, dissolved, and di-
luted to 1 liter with distilled water.
B. Acetic acid solution. Fifty mililiters
of glacial acetic acid are diluted to
300 ml with distilled water.
C. Standard potassium iodate stock solu-
tion. One gram of standard potas-
sium iodate is dissolved in distilled
water and diluted to one liter. One
milliliter of stock solution contained
1000 M of potassium iodate.
D. Standard potassium iodate working
solution. Ten mililiters of standard
stock solution is pipetted and diluted
to one liter with distilled water.
One milliliter of the working solution
contained 10 p of potassium iodate
and is equivalent to 35.36 ng of
iodine.
Preparation of Standard Curve
A series of standards is prepared by
measuring 0.07, 2.11, 3.51, 4.92 and 6.32
ml of the standard potassium iodate
working solution each into a 25-ml glass
stoppered graduated cylinder from a 5-
ml microburet. Each graduated cylin-
der contained the equivalent of 25, 75,
125, 175, 225 pg of iodine respectively.
Also, a zero microgram iodine solution is
prepared as the reference cell. Ten mil-
February 1968 / Volume 18, No. 2
U.3
0.8
liliters of the sodium hydroxide-potas- 0.7
sium iodide reagent is pipetted into each
graduated cylinder and it is followed by 0.6
3 ml of the acetic acid reagent. Each
cylinder is made up to 25 ml with dis- O.5
tilled water and thoroughly mixed. The
standards measured a pH value of ap- 0.4
proximately 3.8. The iodine absorbance
is read at 355 millimicrons wavelength O.3
by the spectrophotometer using a 1-cm
cell. After the standard curve was com- 0.2
pleted it is checked at a minimum of two
points whenever a set of unknown sam- 0.1 - /
ples is to be determined. By so check-
ing, the variables are closely controlled. / 1 1 1 1 I I I 1
25 50 75 1OO 125 150 175 200 225
Micrograms Iodine per 25 ml.
Procedure
Fig. 1. Standard curve. Absorbance of iodine
Ten milliliter of the sodium hydrox- standard solutions is plotted against the micro-
ide-potassium iodide reagent are grams of their respective iodine concentrations.
pipetted into a midget impinger. In
addition, 3 ml of the acetic acid reagent
are pipetted into the same midget im- One mole of iodine is liberated by 1
pinger. The above combination of solu- mole of ozone. Therefore 1 p.g of iodine
tions is called the acid oxidant absorp- is equivalent to 0.19 fxg of ozone.
tion solution. The oxidant concentration is ex-
A field reagent blank midget impinger pressed as pphm of ozone, calculated
is prepared as above and used in con- as follows:
junction with sampling atmospheric 1. First, from the standard curve, the
oxidant, however, no air is drawn corrected iodine concentration is multi-
through this impinger. The midget im- plied by 0.19 which equals the micro-
pingers are attached to a Gelman Se- grams of ozone in the sample.
quential sampler and each is sampled at 2. Empirically, the standard condi-
a flow rate of 84.6 liters per hour. The tions are set as 760 mm of mercury and
sampling period was normally 30 min. 25C. The volume correction for at-
However, if the oxidant concentration is mospheric pressure at the sampling loca-
anticipated to be higher than 40 pphm tion was insignificant; therefore it is
the sampling time was cut to 15 min. omitted.
The acid iodide oxidant solution should 3. To obtain the pphm oxidant, the
be shaded from direct sunlight. After following equation is used:
the atmospheric sampling is completed,
each acid oxidant absorption mixture , ., , S70, MO
pphm oxidant = X X
and the field reagent blank are quantita- 1/hr 7O3
tively transferred from the midget im-
pinger into a 25-ml graduated cylinder. (103) ^(Air) 10*
X
Then the volume is adjusted to 25 ml (MO3) 273A r(Std) t(h)
with distilled water and thoroughly
where
mixed. This solution measured the
same pH value as the standard curve S7O4 micrograms of ozone
solution. The absorbance of each solu- in sample
tion, including the field reagent blank, is 1/hr flow rate 84.6 1/hr
measured by the spectrophotometer us- MO 3 microgram of ozone in
ing the same procedure as in the determi- one mole or 48 X
nation of the standard curve. 106 micrograms of
ozone
Calculation (103)
= one mole of gas at
The absorbance of the iodine standard
standard conditions
solutions is plotted against the micro-
occupies a volume
grams of their respective iodine concen-
of 22.4 liters
trations. The resultant curve followed
T(air) air temperature at
Beer's Law (Fig. 1). The iodine con-
25C. = 298A
centration of the acid oxidant absorption
r(std) standard temperature
solution is read directly from the stan-
at 0C = 273A
dard curve. The absorbance of the field
reagent blank should be subtracted from 108 This factor is em-
ployed to read oxi-
the absorbance of the unknown sample.
dant concentration
The stoichiometry of the acid oxidant
pphm (parts per hun-
method is assumed to be as follows:
dred million.)
O3 + 2HI H2O + O2 sampling time in hour
79
Table IEffect of Purified Air Sam-
pling on Acid Absorbent Mixture
Reagent Blank Impingers
7I2/25 ml.
Run Unsampled Sampled
Table IIEffects of Purified Air
Sampling on Spiked Acid Absor-
bent Mixture
Iodine
Mid- Added
get to Iodine
Impin- Reagent Recov- Per Cent
ger Blank ered Iodine
No. T / 2 5 ml. T / 2 5 ml. Loss
1 25 12 52
2 50 22 56
3 75 30 60
After combining constants the equation
reads:
S7O3 X 0.600
pphm oxidant =
t containing acid oxidant absorption solu-
Results and Discussion
The Kruger automatic analyzer
Model 73 and the MAST, Model 724-2,
ozone meter and recorder were employed
as reference standards for this study.
The Kruger analyzer utilized 20% po-
tassium iodide in a neutral buffered solu-
tion. The MAST measures oxidant
coulombimetrically.
Air Effect
The problem of the effect of air or
oxygen on the acid iodide oxidant
method had to be examined since the
literature has published many reports
discouraging such a system. Diamond
and Smith7 reported that the oxidant
concentration, when measured by an
acid iodide solution, is increased by the
presence of oxygen. Conversely, Wald-
elin13 and Skare 14 published that an acid
iodide solution will volatilize part of the
liberated iodine when a large volume of
air is sampled. Although researchers
found that aeration affects the final re-
sults, the acid iodide oxidant method
under discussion did not experience
volatilization of iodine during regular
operating conditions.
When the incoming air was purified by
activated charcoal, the 13 ml acid ab-
sorbent mixture in a midget impinger
was practically unaffected by the clean
air or oxygen. The results are shown
in Table I. Unless otherwise specified,
all midget impinger solutions were
sampled for 30 min at 84.6 liters per
hour.
The data in Table I indicated little or
no positive interference due to aeration
80
.
Table IIIComparing Ambient Air Sampled by an Iodine Spiked and Un-
spiked Acid Oxidant Absorption Solution with Kruger Analyzer
7I1 added Kruger
Impinger per Oxidant
Run No. Impinger (pphm)
50 14
0 14.0
50 15
0 15.0
50 18
0 18.0
50 21
0 21.0
of the acid potassium iodide method.
Table II shows the effect of carbon
purified air bubbled through a known
quantity of iodine in a midget impinger
tion. Under these sampling conditions,
there is definitely a loss of iodine.
To further investigate the iodine
volatilization problem, ambient air was
sampled instead of activated carbon
purified air. Samples spiked with 50 ng
of iodine were sampled simultaneously
with samples containing only the acid
oxidant absorption solution. The re-
sults of this study were compared with
the Kruger oxidant analyzer and are
shown in Table III.
Table III shows that the unspiked
midget impinger compared favorably
with the Kruger oxidant analyzer but
again the spiked midget impingers re-
flected an appreciable loss of the total
oxidant. The comparison of the re-
sults in Tables II and III showed a
much greater loss of iodine when the
spiked midget impinger sampled filtered
air, than when the spiked midget im-
pinger sampled ambient air. It is as-
sumed that the loss of iodine is caused by
the reaction not being in chemical
equilibrium. The loss of iodine in the
spiked impingers, Table III, probably
occurs during the first part of the
sampling period, as the chemical equilib-
rium has not been reached. This
theory is supported by the values shown
in Table III. When lower concentra-
tions of atmospheric oxidant are present,
a smaller loss of iodine is observed in the
spiked impinger because it takes less
time to reach chemical equilibrium.
The opposite was true that as the ambi-
ent air oxidant concentration became
greater, the iodine loss increased.
In a normal acid iodide oxidant
Tot. Tot. Per Cent
Oxidant Oxidant Oxidant
Anticipated Recovered (Loss) Gain
26.5 22.1 (13.0)
15.5 11
26.4 22.3 (16)
14.5 (3.3)
29.4 24.1
17.6 (18)
32.4 25.8 (2.2)
20.7 (20)
(1.4)
midget impinger solution, the chemical
equilibrium is reached almost immedi-
ately as the reaction proceeds in the
proper direction. Therefore, the re-
sults of the unspiked midget impingers
compared favorably with the data from
the Kruger oxidant analyzer. The in-
vestigation demonstrated that the acid
iodide oxidant procedure contradicted
the position taken in the literature.7-13'14
The interference of air or oxygen with
the acid oxidant method is insignificant.
Ozone Study
An ozone generator, as described
under "Apparatus," using pure oxygen
was employed to establish the limita-
tions of the new acid oxidant procedure.
An aliquot of the ozone was withdrawn
for the acid oxidant procedure and the
remainder entered the Kruger Analyzer.
The acid oxidant absorption solution
consisting of 0.15 g potassium iodide
(10 ml of reagent "A") was found to be
best suited for atmospheric sampling
between 1 and 70 pphm ozone. More
iodide increased the reagent blank for
iodine excessively (11-15 ng of iodine
per impinger blank.) Less potassium io-
dide than 0.15 g produces an acceptable
blank; however, the capacity is limited
to atmospheres containing less than 30
pphm ozone.
The procedure as given produces a
5-8 ix of iodine blank and the results
agreed quite well with the Kruger oxi-
dant analyzer. Figure 2 shows the re-
sults of these simultaneous samples.
A further test of impinger efficiency
was made. When two midget im-
pingers were placed in series, the iodine
liberated from the second midget im-
pinger agreed very favorably with the
reagent blank. Therefore, the ozone
Journal of the Air Pollution Control Association
 Table V 2 % Neutral Buffered Po-
tassium Iodide Method with Chro-
mium Trioxide Absorption Tube
Compared with The Kruger Oxidant
Analyzer

2% Neutral Kruger
Table IVEffect of Increased Temperature on Acid Buffer Analyzer
Iodide Oxidant Method Run KI (pphm) (pphm)
1 14 14
Temp. Iodine Absorption Readings per 25 ml Sample 2 14 14
(F) 175y 3 18 20
4 17 19
75 0.094 0.295 0.495 0.699 5 20 20
80 0.093 0.292 0.493 0.698 6 17 18
90 0.093 0.290 0.492 0.696 7 26 27
95 0.092 0.291 0.492 0.695 8 25 26

sampling efficiency of the first midget
impinger was very good.
Temperature Effect
A study was necessary to determine
the effect of temperature variance on the
acid iodide oxidant method, if the
method is to be applicable as a manual
sampling procedure. A group of acid
iodide oxidant standards prepared as
those under Preparation of Standard
curve was placed in water at a constant
temperature for 15 min. The experi-
ment examined four controlled tempera-
ture settings which included room tem-
perature 75F, as the standard and 80,
90, and 95F. After the standards
were removed from the water bath they
were allowed to come to standard tem-
perature, 75F, and the absorbance
read. The reference cell solution re-
mained at the standard temperature
throughout the investigation. The tem-
perature effect experiment is shown in
Table IV.
The temperature effect on the acid
iodide oxidant standards showed that
10 20 30 40
Kruger Oxidant Analyzer, Cone, (p.p.h.m.)
Fig. 2. Acid iodide oxidant method vs. Kruger
oxidant analyzer.
the deviations of the absorption readings
were so small that they were insignifi-
cant for practical purposes. The field
tested acid iodide oxidant samples,
where the temperature ranged from 75
to 96F, agreed with the measurements
of MAST Model 724-2 recorder and the
Kruger oxidant analyzer. The tem-
perature of the samples tested in the
field are shown in Tables VI, VII, and
XL
Sulfur Dioxide Effect
The reducing gases, sulfur dioxide and
hydrogen sulfide, are responsible for
serious negative interference in iodo-
metric determination of atmospheric
oxidant as reported by Cholak, Schafee,
and Yeager.15 In the present study,
sulfur dioxide interference in the 1 or 2%
neutral buffered potassium iodide
method reduced the oxidant values as
much as three times the actual value
when compared with the Kruger an-
alyzer. When the chromium trioxide
sulfur dioxide absorber was employed to
remove the reducing gases from the
neutral buffer method, the atmospheric
oxidant concentrations then agreed with
the Kruger analyzer measurements.
This indicates the Kruger is unaffected
by sulfur dioxide at the 10 pphm level
studied. The manual procedure recom-
mended by the California State Depart-
ment of Public Health3 was followed to
determine the results of the 2% neutral
buffered iodide method. Data from
this experiment are shown in Table V.
A survey by Mueller, Terraglio, and
Tokiwa16 reported that when an oxidant
analyzer using 20% neutral buffered
potassium iodide solution was used, the
50 oxidant concentration was decreased by
about 27% of sulfur dioxide concentra-
tion. Agreement with this publication
has not been obtained. Therefore,
without any sulfur dioxide filtering de-
vice the Kruger analyzer was employed
as a reference standard so that the effect
of sulfur dioxide could be studied using
the acid iodide oxidant procedure.
To determine if the acid oxidant
method is affected negatively by sulfur
dioxide the study resulting in the data in
Table VI-A and VI-B was conducted.
It was found that the chromium trioxide
scrubber had to be conditioned with
outside ambient air for a minimum of 14
hr, and with an oxidant concentration of
at least 15 pphm. A shorter condition-
ing period gave very erratic results
when the filter was attached to the acid
iodide oxidant sampling train.
The data in Table VI-B showed that
the acid oxidant method can be sampled
from the ambient air without attaching
a chromium trioxide scrubber. Addi-
tional investigation compared the man-
ual acid procedure with a MAST oxidant
analyzer at less than 2 pphm sulfur
dioxide. The same operating proce-
dures were used as previously described
for the data in Table VI. The results
of this study are shown in Table VII-A
andVII-B.
The oxidant values for the MAST re-
corder are consistently lower. This
negative interference agreed with the in-
formation published by Cherniack and
Byran.17'6 When the 1 or 2% neutral
buffered potassium iodide method using
a chromium trioxide scrubber was
compared to the MAST recorder, addi-
tional evidence was provided that re-
ducing gases affected the oxidant value
of the MAST recorder. Therefore, the
modified neutral buffer method sub-
stantiated the sulfur dioxide inter-
ference of MAST recorder as found by
the acid oxidant method. Under at-
mospheric conditions prevalent in the
author's research area, the acid potas-

February 1968 / Volume 18, No. 2 81

 Table VISulfur Dioxide Interference Study
Table VIISulfur Dioxide Interference Study
\ Ml A t* If 1 m m

Vl-ASulfur LMoxme Kemovea rrom rne Acia loaiae Vll-ASulfur Dioxide Removed from the Acid Iodide
Oxidant Procedure with Chromium Trioxide Compared
withi the Kruger Oxidant Analyzer Oxidant Procedure by Chromium Trioxide Compared
with the Mast Oxidant Analyzer
SO2 Removed
From Acid SO2 Removed
Oxidant Kruger Temp. from Acid
Method Analyzer During Oxidant MAST Temp.
(pphm (pphm Sampling Method Analyzer During
Run No. Oxidant) Oxidant) F Run (pphm (pphm Sampling
1 15 14 89 Number Uxiuant) Oxidant) r
2 18 18 93 1A 22 19 88
3 21 21 93 2A 24 22 86
4 23 23 90 3A 24 21 82
5 14 15 96 4A 10 9 88
6 17 19 95 5A 8 8 86
R A O1 1n 00
DA Zl 19 06
\/l D C nc T#iklo VI A 1 /> v i n k c w% f\%
vi~D""~">ame iUS I H D I C VI~A\, UUI J U I I U I IS lUXIQc IS nOT
Removed from the Air Vll-BSame .as Table Vll-A but Sulfur Dioxide is not
A 1*
nCiMOVcu T rOifi /\ir
Ambient
Air-Acid Ambient Air-
Oxidant Kruger Temp. Acid
Method Analyzer Dviring Oxidant MAST Temp.
(pphm (pphm Sampling Run (pphm (pphm Sampling
Run No. Oxidant) Oxidant) ojp Number Oxidant) Oxidant) oF

10 14 13 93 10A 19 16 90
11 20 21 94 11A 18 15 86
12 17 17 93 12A 26 23 86
13 23 24 88 13A 6 5 83
14 10 11 95 14A 11 9 88
15 11 12 92 15A 12 11 85

sium iodide procedure for determining
atmospheric oxidant was unaffected by
reducing gases.
Since the negative interference of
sulfur dioxide was undetected in the acid
oxidant method, the chemical system
for this phenomenon is unknown. It is
assumed that one of the substances in
the chemical environment served as a
negative catalyst (inhibitor) which null-
ified the reducing potential of sulfur
dioxide. This theory received support
from Partington18 who reported that
negative catalysts suppress the oxida-
tion of sulfur dioxide. There are many
organic substances which can serve as a
negative catalyst; however, the specific
catalytic inhibitor which eliminated this
negative interference of sulfur dioxide
has not yet been isolated.
Color Stability
The acid oxidant procedure to be
practicable for field operation had to
possess color stability. This feature has
been repeatedly demonstrated. Practi-
cally all field samples pertaining to the
acid iodide oxidant method were an-
alyzed in the laboratory at the end of the
working day. Generally, midget im-
pingers were analyzed about five hours
after sampling was completed. Some
samples were spot-checked the following
morning. The time differential between
air sampling and completion of the
analyses did not affect the color stability
of the iodine. Thefieldreagent blanks
exposed for at least six hours had rela-
tively the same analysis as reagent
blanks exposed for shorter periods.
The blank reagent analysis ranged from
5 to 8 yug of iodine per sample.
To measure the color stability of the
acid oxidant method, groups of stan-
dard solutions were prepared and tested
over a period of time under different
conditions. Table VIII, Column I,
shows the relationship of reference con-
centrations to the same group four hours
later as presented in Column II. Fi-
nally, the same group, Column II, was
placed in darkness for seventeen hours
and the iodine concentration determined
as presented in Column III.
Each iodine standard solution group
was analyzed at different times and the
average of the four groups demonstrated
that the exposure for an additional 17 ta-
in darkness produced the largest amount
of color change. However, Table IX
showed that when the groups are placed
under refrigeration for the last 17 hr, the
iodine concentrations remained ex-
tremely stable. When samples were
collected in thefield,similar results were
obtained after these time exposures.
When the acid oxidant samples were
under refrigeration for 17 hr, the original
reference concentration was well within
the experimental error of manual oxidant
determinations as shown in Table IX.
No attempt was made to find the effect
on color stability over longer exposure
time than that reported.
Comparison of Methods
The various manual procedures in-
vestigated included the alkaline, the
neutral buffer, and the acidic iodide oxi-
dant methods.
The experiments performed on the
alkaline iodide oxidant procedure1'9
obtained very low results, as shown in
Table X.
In Table X, the same technique
previously employed in the discussion of
the ozone study was used to compare the
alkaline oxidant method with the
Kruger oxidant analyzer, the reference
standard. The nitrogen dioxide and
sulfur dioxide interferences did not pose
a problem as the ozone was produced
from oxygen gas. Therefore, the em-
ployment of the phosphoric and sulfanic
acid solution7 was not necessary to re-
duce the nitrogen dioxide interference.
Furthermore, the chromium trioxide
scrubber was not attached to the sam-
pling train. The calculation of the ozone
concentrations, Table X, included the
stoichiometric correction factor of 1.541
which did not significantly improve the
low results. A published report10 that
ozone was unstable at low alkaline con-
centrations seemed to verify the low re-
sults that are consistently obtained from
the alkaline iodide oxidant method.
The manual acid iodide oxidant pro-
cedure was used simultaneously with the
2% neutral buffered potassium iodide
procedure and the results of Kruger
analyzer were also recorded. The data
are presented in Table XI.
The acid iodide oxidant method fol-
lowed the pi'ocedure previously outlined.
The 2% neutral buffered iodide method
followed the outline recommended by
the California State Department of
Public Health.3 In Table XI, the oxi-
dant values are shown to be in good

82 Journal of the Air Pollution Control Association

Table VIIIColor Stability Test-Acid
Iodide Oxidant Standard Comparing
Stability vs. Time and Conditions

Column I Column III

Reference Column II Found After Table XIComparing the Acid Oxidant, the 2 % Neutral
Concen- Found 4 hr 17 hr in Buffer Iodide Method and Kruger Analyzer Simul-
tration later Darkness
(Avg. 4 (Avg. 4 (Avg. 4 taneously
Groups) Groups) Groups)
75 74.5 73 2% Neutral
125 125 126 Acid Buffered Kruger
175 176 184 Iodide Iodide Auto.
Oxidant Oxidant Oxidant Temp.
(pphm (pphm (pphm Sampling
No. Oxidant) Oxidant) Oxidant) oF

1 6 6 5 88
2 6 6 5 90
3 8 8 7 90
4 17 16 16 92
Table IXColor Stability Test Same 5 15 14 15 92
as Table VIII But Last 17 Hours Under 6 17 15 16 92
Refrigeration 7 34 33 35 90
8 31 29 31 91
9 24 22 22 92
Found After
Original Additional
Reference 17 hr under
Concentration Refrigeration Summary 7. Smith, R. G., and Diamond, P., (1952)
(Avg. 4 Groups) (Avg. 4 Groups) "The Microdetermination of Ozone,"
75 75.3 The acid potassium iodide oxidant Am. lnd. Hyg. Assoc. Quart. 13, 235-
125 126 method, as described in this paper, ef- 238.
175 177 fectively determines the oxidant con- 8. Byers, D. H., and Saltzman, B. E.,
"Ozone Chemistry and Technology
centration between 1 and 70 pphm Advances in Chemistry Series, No. 21,
ozone. The reducing gases, hydrogen 93-101, Am. Chem. Soc, Washington,
sulfide and sulfur dioxide, did not inter- D. C.(1959).
fere with this procedure. The method 9. "ASTM Standards on Methods of
Atmospheric Sampling and Analysis,"
was found to possess exceptional color 86-88, ASTM, Philadelphia (1959).
stability and withstands temperatures in 10. "Ozone is Stabilized by Strong Bases"
Table XThe Alkaline Iodide Oxi- the field between 75 and 96F. The C&EN, 42, 38-39 (1964).
dant Procedure Compared with the sampling efficiency of the acid oxidant 11. Boelter, E. D., Putman, G. L., and
Kruger Analyzer absorption solution in a midget impinger Lash E. I. (1950), "Iodometric Deter-
mination of Ozone in High Concentra-
obtained very good results. The com- tion," Anal. Chem., 22, 1533-1555.
Alkaline parison between the 2% neutral buffered 12. Birdsall, C. M., Jenkins, A. G., and
Oxidant Kruger Spadinger, E. (1952), "Iodometric De-
iodide method and the acid potassium
Method Analyzer termination of Ozone," ibid., 24, 662-
(pphm (pphm iodide oxidant method indicated the 664.
Run Oxidant) Oxidant) methods gave comparable results, how- 13. Wadelin, C , (1957), "Determination
1 5.4 11 ever, the latter method had greater of Ozone and Other Oxidants in Air,"
2 3.7 12 simplicity and color stability. Anal. Chem., 29, 4A1-A42.
3 3.7 12 14. Skare, I., (1965), "Generation and
4 3.4 10 Acknowledgment Determination of Ozone in Low Con-
5 18 30 centrations," Air and Water Poll., 9,
6 20 31 The author gratefully acknowledges 601-604.
7 20 32 the technical assistance of Gerald L. 15. Cholak, J., Schafer, L. J., and Yeager,
8 21 44 D. W., (1956) "The Concentration of
Rounds and the analytical assistance of Ozone in the Atmosphere of Certain
9 20 44
10 26 47 Paul R. King, Jr. American Cities," / . of APCA 5,
11 28 49 227-232.
12 26 43 References 16. Mueller,'P. K., Terraglio, F. P., and
1. Byers, D. H., and Saltzman, B. E., Tokiwa, Y., "Chemical Interferences
(1958) "Determination of Ozone in Air in Continuous Air Analysis," pre-
by Neutral and Alkali Iodide Proce- sented Seventh Conference on Meth-
agreement with one another and also dures," Am. Indust. Hyg. Assoc. J., ods in Air Poll. Studies, L. A. Calif.
251-257. (1965).
with the Kruger analyzer. Each neu- 17. Cherniack, I., and Bryan, R. J., (1965)
tral buffered sample was determined 2. Saltzman, B. E. and Gilbert, N., "A Comparison Study of Various
(1959) "Iodometric Microdetermina- Types of Ozone and Oxidant Detec-
within 60 min after sampling. The acid tion of Organic Oxidants and Ozone,"
oxidant samples were analyzed at the tors which are used for Atmospheric
Anal. Chem., 31, 1914-1920. Air Sampling," / . of APCA, 15, 351-
end of each working day. Where the 3. California State Department of Pub- 354.
neutral buffered procedure required a lic Health, "Recommended Methods 18. Partington, J. K., "A Text Book of
in Air Pollution Measurements," Inorganic Chemistry," 3rd Edition, p.
chromium trioxide scrubber to remove SDPH 1-20 (1960).
the reducing gases from the ambient air, 504 Macmillan and Co. Ltd., London
4. TJ. S. Department of Health, Educa- (1930).
the acid iodide method sampled the tion, and Welfare, Public Health Ser-
ambient air without negative inter- vice "Selected Methods for Measure-
ments of Air Pollutants," DI-D5
ferences. Undoubtedly, both proce- (August 1965).
dures seemed to be equivalent in ac- 5. Ibid, E1-E6. Mr. Samuel Deutsch, Chemist
6. Saltzman, B. E., and Wartburg, A. F., is in Air Control and Research at
curacy and precision, however, the acid Kaiser Steel Corp., Fontana Works,
iodide oxidant procedure has greater Jr., (1965) "Absorption Tube for Re- P.O. Box 217, Fontana, Calif.
moval of Interferring Sulfur Dioxide 92335.
simplicity and also greater color stabil- Analysis of Atmospheric Oxidant,"
ity. Anal. Chem., 37, 779-782.

February 1968 / Volume 18, No. 2 83