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Journal of Liquid
Chromatography
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Determination of Benzoic
Acid, Chlorobenzoic Acids and
Chlorendic Acid in Water
a a a
E. A. Dietz , N. J. Cortellucci & K. F. Singley
a
Occidental Chemical Corporation Technology
Center , Grand Island, New York, 14072
Published online: 23 Sep 2006.
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JOURNAL OF LIQUID CHROMATOGRAPHY, 16(15), 3331-3347 (1993)
ABSTRACT
The title compounds were isolated from acidified (pH 1) water by extraction
with methyl t-butyl ether. Analytes were concentrated by back-extracting the
ether with 0.1 N sodium hydroxide which was separated and acidified. This
solution was analyzed by C,, reversed-phase HPLC with water/acetonitrile/
acetic acid eluent and UV detection at 222 nm. The method has detection
limits of 200 pg/L for chlorendic acid and 100 pLgn for benzoic acid and each
isomer of chlorobenzoic acid. Validation studies with water which was
fortified with the analytes at concentrations ranging from one to ten times
detection limits resulted in average recoveries of >95%.
INTRODUCTION
To characterize and conduct treatment studies of a landfill leachate an
analysis procedure was required to determine concentrations of benzoic acid,
the three isomers of chlorobenzoic acid and chlorendic acid (1-3). Without
derivatization, acids are not good candidates for GC analysis. Even with
derivatization, the chlorobenzoic acid isomers are poorly resolved (43);
therefore, an HPLC procedure was sought.
3331
EXPERIMENTAL
software, used a Hewlett Packard disc drive, and recorded data with a
Hewlett Packard 2225 Thinkjet printer. Analysis conditions were:
Column Waters Nova-Pak C , , (2 X 150 mm with
4 pm particle diameter)
Sample Vol. - 20p1
Temperature Column oven was set for 40 OC
Eluent Flow - 0.25 mL/min.
Eluent From 0 to 10 min. elution solvent was
composed of 11% acetonitrile/64%
waterf25% water which contained 2 mL/L
acetic acid; between 10 and 45 min.
composition changed linearly to 50%
acetonitrile/25% watert25% water with 2
mL/L acetic acid. This composition was
held for five min.
Run Time 50 min.
Post Time After run termination, a 15 min. hold time
was in effect to allow solvent equilibration
to initial composition.
Detector Set for 222 nm with a 10 nm window and
a reference wavelength of 550 nm with 80
nm window. A UV spectrum of each
3334 DETZ, CORTELLUCCI, AND SINGLEY
of stock solution were prepared in a similar way by diluting 7.5, 5.0, 2.5 and
1.0-mL aliquots of primary solutions.
Calibration Solutions
Aqueous calibration solutions were prepared by diluting 5.0 mL of
each stock solution to 10 mL with 0.02 N H2S04. For methanolic calibration
solutions, 5.0 mL of each stock solution was added to a 10-mL volumetric
flask along with 2 mL of 0.05 N H2S04 and 3 mL of methanol. Upon mixing
there was a small volume reduction which was corrected by adding a few
drops of methanol.
Sample Extraction
Samples were at room temperature and pH was adjusted to 1using a
0-2.5 pH strip to check acidity. A 100-mL aliquot then was added to an
extraction flask. To samples as well as any fortified solutions 11 mL of
MTBE was added and vigorously mixed to extract the water. After phase
separation only about 5 mL of MTBE phase resulted due to a 5% solubility
3336 DIETZ,CORTELLUCCI, A N D SINGLEY
loss of MTBE and solution volume reduction from phase mixing. Loss of
MTBE was a good indicator that extraction had been sufficiently vigorous.
Therefore, if noticeably more that 5 mL was recovered, extraction was
continued. The MTBE layer was withdrawn and placed in a centrifuge tube.
The extraction was repeated using 6 mL of MTBE. After phase separation,
the resulting 6 mL of MTBE was combined with that from the first
extraction. To the recovered MTBE 1.0 mL of 0.1 N NaOH was added and
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an extract matched a calibration solution made from the same stock solution
when 100% recovery was achieved. Therefore:
% Recovery = Area Response of Extract x 100
Area Response Cal. Soh.
TABLE 1
Solute I % Recovery* I
pH1 pH3 pH5 pH7 pH9 pH11 pH13
Benzoic Acid 75 75 49 38 19
o-Chlorobenzoic Acid 86 59 8 5 2
m-Chlorobenzoic Acid 92 92 75 68 44
~
p-Chlorobenzoic Acid 91 92 76 71 49
Chlorendic Acid 93 90 73 59 16
* A dash indicates no response greater than twice the background signal was observed.
BENZOIC, CHLOROBENZOIC, AND CHLORENDIC ACIDS 3339
TABLE 2
Effect of Extraction Vigor on Recovery
Benzoic Acid 96
1 o-Chlorobenzoic Acid I 95 I 74 I 81 I
m-Chlorobenzoic Acid 101 74 87
p-Chlorobenzoic Acid 100 74 87
Chlorendic Acid 95 58 72
back-extraction assures that only acidic compounds will be present in the final
extracts. Table 1 indicates that a pH>11 will completely retain analytes in
the aqueous phase. With 0.1 N NaOH (pH 13), total recovery is expected.
Even if traces of H,SO, are entrained in the ether from the MTBE
extraction, it is unlikely that this would cause the caustic pH to fall below 11.
As shown in Table 2, vigor of phase mixing during MTBE and NaOH
extractions is important. The data represents results from analyses of water
which contained each analyte at 1 ppm (2 ppm for chlorendic acid).
Significant recovery losses were evident when either extraction was not
sufficiently vigorous. Interestingly, recovered MTBE from the gentle
3340 DLETZ, CORTELLUCCI, AND SINGLEY
extraction was about 1 mL more than for the two more vigorous analyses. As
noted in the extraction process description, volume of MTBE collected after
extraction parallels extraction vigor.
The linal preparation step requires neutralization/acidification of the
caustic extract and its volume adjustment to 2.0 mL. For this, sufficiefit
H,SO, is added to produce a solution pH of 2. The extract pH is important
for providing good chromatographic behavior for o-chlorobenzoic acid.
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3A
I-CBA
p-CBA
3
aE 2100 0 ~
0-CBA 1
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0
0
J! I
10
m r ' r
20
I
Time (min.)
m * ' '
30
l ~ ~ "
40
I
w
TABLE 3 w
P
h)
Compound No I.C. N.S. PVDF PF PTFE Nylon PTFE (c) PTFE (d)
Filter
Benzoic Acid 1.00 0.89 0.99 0.95 0.95 0.99 0.86 1.oo 1.01
o-Chlorobenzoic Acid 1.00 0.94 1.00 0.94 0.96 0.99 0.81 0.99 1.00
m-Chlorobenzoic Acid 1.00 0.73 0.97 0.87 0.88 1.00 0.57 1.00 1.00
p-Chlorobenzoic Acid 1.00 0.74 0.97 0.89 0.88 0.99 0.60 1.oo 1.00
Chlorendic Acid 1.00 0.92 0.86 0.86 0.76 0.99 0.0 0.99 0.99
i.
16 66 201 26 6 - I M d (zo) 01'0
26 201 01 26 56 - I W d ( 2 0 ) 01'0
L8 96 S6 98 06 -Iar/%d(5'0) szo
t6 901 M)T L6 86 - I w m (0'1) 05'0
56 001 TOT P6 96 - I m m (s.1) SL'O
L6 01 01 66 66 F / % d(0.z) 0 1
E L e a - (q)k a A m 9 X %
56 86 86 Z6 26 -Iru8d (Z'O) 01'0
06 66 86 26 6 (S'O) szo
6 66 66 6 6 -IoI/%d (01) oso
26 L6 L6 16 26 - I W d (S'T) SL'O
66 sot SOT 001 001 1 m m (5'1) SL'O
P6 001 101 56 96 1 w m (0.2) 0 1
z Lea - (q)L a m a 8 %
L6 L6 L6 M1 56 - I m m (Z'O) 01'0
06 101 101 6 56 - I w m (5.0) szo
26 L6 L6 6 6 l @ d (0.1) 05'0
P6 86 66 L6 96 -I"/%d (5.t) SL'O
L6 96 L6 6 26 - I W d (O'z) 0 1
S6 66 86 56 P6 -I@d ( 0 z ) 0 1
V3 VE3-d V83-" VE3-0 V8 ( s ) uo!iequmuq ay!dS
1Lea - (q)OaAooaX %
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w
w
P
P
TABLE 5
injection solution is a stronger elution solvent than that of the initial HPLC
conditions. Peak shape and resolution are not affected. A disadvantage to
having analytes in acidified methanol is formation of chlorendic acid
monomethyl ester. This was shown when two-day old calibration solutions
were reanalyzed after being maintained at room temperature. A new
response was observed after the chlorendic acid peak; its area was about 1-2%
of the chlorendic acid peak. By day four, it had become 5% and after a week
had grown to 8%. A two-week old solution exhibited a peak with 17% the
area of chlorendic acid. Due to unwanted esterification of chlorendic acid,
the optional procedure should be used only when needed and sample extracts
should be chromatographed within a few days after preparation.
Recovery results which were obtained at five concentrations on three
separate days using Milli-Q water spikes are given in Table 4. Each day a
duplicate sample also was analyzed. Spiked samples containing 1ppm of p-
chlorobenzoic acid had to be analyzed using the optional methanolic
procedure. To obtain comparable data for the other spiking levels, calibration
soluitons and all extracts were prepared with methanol. Two field samples,
each spiked at two concentrations, were included with this study. One set was
analyzed using aqueous extracts while the other used methanol addition to
extracts. These recovery data are presented in Table 5. The mean recovery
of all the Milli-Q water spikes is 96.3% with a relative standard deviation of
4.1% These results and > 98% average recovery average for actual field
samples validate the sample extraction and HPLC procedures presented in
this paper.
3346 DIETZ,CORTELLUCCI, A N D SINGLEY
REFERENCES
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(1986)
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11. Standard Methods for the Examination of Water and Wastewater, 17th
Ed., American Public Health Association, Washington, D.C., Method
6640 (1989)
13. B. Patel, J.H. Purnell, C.A. Wellington, HRC CC, J. High Resolut.
Chromatogr. Chromatogr. Commun., 375-381 (1984)
19. Het@ Acid for Paints, Coatings and Other Applications, Bulletin No. 40-
A, Hooker Chemical Corp., Niagara Falls, N.Y. (1960)
20. The Merck Index, 9th Ed., Merck & Co., Inc., Rahway, N.J. (1976)