were comparatively small in practice.

ACKNOWLEDGMENT
Deviations from a standard dilution The authors gratefully acknowledge
curve prepared with the sample chamber
technical and other assistance from
empty were usually not significant. Beckman Instruments, Inc., the (Cali-
These sets of curves were always used
fornia) Citrus Industry Committee
to determine net fiberboard desorption on Fungistats, and the (California) Cit-
m. rus Industry Research Advisory Com-
The second much larger system pre- mittee.
sented different problems. For ex-
ample, the fruit or vegetable sample
could not be introduced into a pre- LITERATURE CITED

stabilized atmosphere, and the volume (1) Gunther, F. A., Barkley, J. H., Kol-
of the system compared to the over-all bezen, M. J., Blinn, R. C., Staggs,
throughput of air-ammonia mixture us- E. A., Anal. Chem. 28, 1985-9
(1956).
Effect of diluting air-
ually represented a ratio of about 6 to 1. (2) Gunther, F. A., Blinn, R. C., Kol-
Figure 10. Dilution of the ammonia stream with air
ammonia mixture with air or of diluting bezen, M. J., Barkley, J. H., Staggs,
at the start of each cycle was therefore a E. A., Conkin, R. A., Wilson, C.
air with ammonia in a light-bulb filled W., J. Agr. Food Chem., in press.
chamber vs. an empty chamber large factor; deviations of this factor
from one run to another were "often sig- (3) Klotz, L. J., personal communication.
Dilution of air-ammonia with air (4) Klotz, L. J., unpublished data for
nificant and required compensation (2), Project 808, University of Cali-
•— Chamber with light bulbs
as shown in Figure 9. Similar consid- fornia, Riverside, Calif.
Dilution of air with ammonia
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

O— Chamber empty erations applied to desorption cycles. (5) Rideal, S., “Disinfection and Preser-
Downloaded via KTH ROYAL INST OF TECHNOLOGY on June 10, 2024 at 08:01:36 (UTC).

In general, first-hour sorption and de- vation of Food,” p. 246, Wiley, New
X---Chamber with light bulbs
York, 1903.
sorption data required correction for (6) Roistacher, C. N., Eaks, I. L., Klotz,
With fiberboard, significant dilution of this dilution factor, but after the first L. J., U.S. Dept. Agr. Plant Disease
the air-ammonia stream at the start of a hour corrections for both dilution and Reptr. 39, 202 (1955).
sorption run was avoided by charging variation among chambers were negli- (7) Roistacher, C. N., Klotz, L. J., Eaks,
I. L., Hilgardia, in press.
the sample into the chamber with mini- gible. Detailed scrutiny of the desorp-
mum disturbance of the previously es- tion cycle in chambers filled with par-
tablished internal atmosphere. Contam- affined light bulbs indicated that dilu- Received for review June 20, 1957.
ination of the stripping air stream with Accepted January 13, 1958. Division of
tion of the air-ammonia mixtures with Analytical Chemistry, 131st Meeting,
residual air-ammonia mixture during a air, or of air with ammonia, was at sub- ACS, Miami, Fla., April 1957. Paper
desorption cycle could not be avoided, stantially the same rate as for com- No. 993, University of California Citrus
but the volume of the sample and the pletely empty chambers, as shown in Experiment Station, Riverside, Calif.
Contribution to the University of Cali-
total volume of the system relative to zones C and F in Figure 9 and analyzed fornia College of Agriculture Project No.
the rate of introduction of gas mixture graphically in Figure 10. 808, under the guidance of L. J. Klotz.

Potentiometric Titration of Free Amine and Amine

Carbonate in Carbonated Monoethanolamine Solutions
YI-CHUNG CHANG
Low-Temperature Tar Laboratory, Bureau of Mines,
U. S. Department of the Interior, Morgantown, W. Va.

Determination of free amine and process, numerous determinations of percentage conversion to amine car-
amine carbonate in carbonated mono- the amine and carbon dioxide contents bonate (1). Wagner and Lew made
ethanolamine solutions by means of a were necessary and a rapid, accurate amine carbonate react with excess so-
double end point titration seems to method was sought to facilitate the dium hydroxide and back-titrated the
have great simplicity. Results of work. excess base in 75% ethyl alcohol solu-
potentiometric titrations for mixtures of A number of papers have been pub- tion (7). Mason and Dodge reported
monoethanolamine and its carbonate lished on methods for determining free a double indicator titration procedure
are presented. End points are found amine and amine carbonate. A pro- but did not get reliable results (4).
to occur at pH 7 and 4. Using a sample cedure widely used for this analysis However, the double end point ap-
of 0.5 to 1
gram of amine and to 1 consists of determining the total amount proach based on the following reactions
2N hydrochloric acid, a titration can of amine in solution by titrating with seemed to be the simplest, the question
be performed within 15 minutes. strong acid, using either methyl orange of reliability depending on the con-
Titrated values agree within 2% of the or methyl red as an indicator, and de- ditions of titration and the method of
calculated percentage compositions for termining the carbon dioxide content by locating the end points:
synthetic mixtures, indicating an ac- liberating the carbon dioxide with acid, For the first end point:
curacy adequate for routine control followed by either measuring the volume
purposes. of the gas or absorbing it in Ascarite HOCH2—CH2NH2 + HC1 -*
HOCH2—CH2NH8C1 (1)
or baryta (1, 2, 4~6). Cryder and
a the regeneration
study on Maloney determined the carbon di- (HOCH2—CH2NH3)2C03 + HC1 ->

During of carbonated monoethanolamine oxide content of an amine solution from hoch2—ch2nh5hco3 +

solutions used in a phenol extraction a chart prepared by plotting pH vs. HOCH2—CH2NH3C1 (2)

VOL. 30, NO. 6, JUNE 1958 · 1095

 For the second end point: help of anarchitect’s scale (l/j scale), The free amine and amine carbonate
it was able to read to the nearest contents of each solution can be de-
HOCH2— CH2NH3HC03 + HC1
inch. Thus, the accuracy of these termined by means of the following
HOCH2—CH2NH3C1 + H2C03 (3) measured values was to ±0.02 inch. formulas:
This paper presents the results of To check the reliability of the end
2F2A" number of meq. of amine
points obtained in this manner, three
-

potentiometric titrations of such mix- combined as carbonate

tures. mixtures of the stock solutions were (4)
made and titrated under the same con- number of meq. of
(Vi —

T'2)A =

ditions (Table I). Titration curves

APPARATUS AND REAGENTS amine in free form (5)
for mixtures 1 and 2 are given in Figure
A titrator equipped with automatic 2 and for mixture 3 in Figure 3 (curve where
delivery and mixing devices and a self- A). All three curves show that the
recording potentiometer, as described Ty 5 X 0.413
= ml. of hydro- =

first end point occurred at pH 7 and chloric acid used to the first end
by Katz and Glenn (S), was used with a the second at pH 4. Thus the relia-
glass electrode as the indicator electrode point
and a calomel electrode as the refer- bility of the pH levels of the end points Vi S2 X 0.413
=
ml. of hydro- =

was established. chloric acid used from the first end

ence.
To simulate the actual amine carbon- point to the second end point
ate samples encountered in the regenera- AT normality of hydrochloric acid
=

tion study, two stock solutions were pre-

pared. Stock solution 1 was made by RESULTS AND DISCUSSION
mixing approximately 70% by weight
of monoethanolamine and 30% of dis- Inasmuch as percentage composition
tilled water; stock solution 2 was of the amine solution was of primary
made by bubbling carbon dioxide gas interest in the regeneration study, the
through a part of stock solution 1 experimental compositions are com-
at room temperature and under atmos-
pheric pressure, resulting in a mixture pared in Table I with the calculated
of free amine and amine carbonate. values based on the composition of the
Mixtures of these two stock solutions stock solutions. The carbonate con-
were used in this study. tent of the stock solution containing
carbonate was checked by evolving the
carbon dioxide from the solution with
PROCEDURE
mineral acid. The liberated carbon
The stock solutions prepared were too dioxide was absorbed in Ascarite and
viscous for convenient measuring with a weighed. When calculating the per-
pipet and consequently were diluted 50 centages of free amine and amine car-
times with distilled water, so that a
bonate, the distances of chart travel
volume of 20 to 30 ml. of solution could
be measured accurately for titration. (as indicated in the respective figures)
For the titration, exactly 25 ml. of the were used instead of the volumes of
diluted stock solution was introduced titrant, to save time and also to increase
into the titration vessel and enough dis- accuracy by avoiding the rounding off
tilled water (approximately 50 ml.) was of figures.
added to the vessel so that the ends of By comparing the results, it is seen
the electrodes, and also the stirrer, were Figure 1. Titration curves for stock that the difference between the ex-
sufficiently covered to ensure proper solutions
functioning of the titrator.
The titrant, 2.182 7 hydrochloric acid,
was delivered at a rate of 0.2065 ml. per
minute. The chart of the recorder was
regulated to travel 0.5 inch per minute;
thus, 1 inch of chart travel corresponded
to 0.413 ml. of titrant. The time
required for this titration was about 12
minutes.
The titration curves for stock solu-
tions 1 and 2 are shown in Figure 1 as
curves A and B, respectively. Curve
B indicates two end points, one at pH
7 corresponding to Equations 1 and 2,
and the other at pH 4 corresponding to
Equation 3.
From these titration curves, the
volume of the titrant used in titration
was obtained by measuring the distance
from the starting point to the respective
end point on the chart and multiplying
the distance in inches by the conversion
factor 0.413. The measured distances,
designated as Si for the distance from
the start to the first end point and S2
for the distance from the first end point DISTANCE OF CHART TRAVEL , INCHES DISTANCE OF CHART TRAVEL, INCHES
to the second end point, are indicated
in these figures. The scale of the chart Figure 2. Titration curves for mix- Figure 3. Titration curves for mix·
was one inch to each pH unit; with the tures 1 and 2 tures 3 and 4 and an actual sample

1096 · ANALYTICAL CHEMISTRY

perimental percentage composition and
the calculated values varies from 0.4 Table I. Resultsof Titration
to 2.2%. This agreement is satisfactory Calculated Values, Titration Values, Difference,
for routine control purposes. __%_ % %
As the amine solutions used in the Free Amine Free Amine Free Amine
regeneration study contained some amine carbonate amine carbonate amine carbonate
phenol, a test was made to determine Stock solu- 100.0 0 100.0 0 0 0
the effect of small amounts of phenol tion 1
on the end point by adding 0.5 gram of Stock solu- 29.8 70.2“ 30.2 69.8 +0.4 -0.4
tion 2
phenol to 25 ml. of mixture 3. The Mixture l6 47.5 52.5= 46.9 53.1 -0.6 +0.6
titration curve for this case, mixture 4 Mixture 2J 65.0 35.0= 65.8 34.2 +0.8 -0.8
in Table I, is shown as curve B in Mixture 3= 82.6 17.4= 83.3 16.7 + 0.7 -0.7
Mixture 4Z 82.6 17.4= 84.8 15.2 + 2.2 -2.2
Figure 3. By comparing curves A and Actual 23.5 76.5
B, it is evident that the effect of a sample
small amount of phenol on the accuracy “
Based on carbon dioxide as determined by evolution method.
of the titration is rather small. 6
75 vol. % stock 2+25 vol. % stock 1.
To determine whether or not other =
Based on compositions of stock solutions.
* 50 vol. % stock 2+50 vol. % stock 1.
acidic materials, such as carboxylic
‘
25 vol. % stock 2+75 vol. % stock 1.
acids, generally present in coal-tar 1 25 vol. % stock 2 + 75 vol. % stock 1 + 0.5 gram phenol.
distillates, would interfere with this
determination, a carbonated amine solu-
tion actually used in a tar acid ex-
traction experiment was titrated to using ethanolamine as absorbent, is LITERATURE CITED

determine the amine and the carbon expected to cause trouble. However, (1) Cryder, D. 8., Maloney, J. O., Trans-
dioxide contents. Curve C of Figure 3 the procedure as outlined was developed Am. Inst. Chem. Éngrs. 37, 827
shows the titration curve. Examina- specifically for a tar acid-amine-carbon (1941).
dioxide system in which these constitu- (2) Girdler Corp., Louisville,Ky., “Oper-
tion of this curve reveals no interference. ating Instructions, Synthesis Gas
This method was therefore adopted in ents are not generally present. There- Purification Pilot Plant,” Bureau of
the study of the regeneration of the fore, judgment must be exercised in Mines, Morgantown, W. Va., 1949.
carbonated amine solution used in using this procedure for analyzing (3) Katz, M., Glenn, R. A., Anal.
Chem. 24, 1157 (1952).
the phenol extraction process. samples containing appreciable amounts
(4) Mason, J. W., Dodge, B. F., Trans.
of interfering materials. Am. Inst. Chem. Engrs. 32, 27
In general, while the presence of
acids weaker than carbonic acid, such (1936).
(5) Reed, R. M., Wood, W. R., Ibid., 37,
as phenols, will not interfere with de- ACKNOWLEDGMENT 363 (1941).
termination of the end points of titra- (6) Shneerson, A. L., Leibush, A. G., J.
tion, the presence of sulfur dioxide, The author washes to thank J. R.
Appl. Chem. (U.S.S.R.) 19, 869
(1946).
carbonyl sulfide, and acids such as Comberiati, Robert C. Johannsen, and (7) Wagner, P. T., Lew', M., Anal.
hydrogen sulfide, acetic acid, etc., Patricia A. James of the Low-Tem- Chem. 26, 575 (1954).
as usually encountered in commercial perature Tar Laboratory for technical Received for review July 10, 1957.
synthesis gas purification processes help. Accepted January 28, 1958.

Estimation of Serum Phospholipide and Total

Phosphorus Using Chloric Acid
JESSE F.GOODWIN, ROGER THIBERT, DAISY McCANN, and A. J. BOYLE

Department of Chemistry, Wayne State University, Detroit, Mich.

Chloric acid is a most suitable ponents of serum rapidly and requires potassium chlorate into a 3-liter beaker,
reagent for the digestion of serum and very little attention during the process. add 900 ml. of distilled water, and heat
serum extracts in the colorimetric The phosphorus content following on a hot plate until solution is effected.
estimation of phosphorus. A sensitive chloric acid digestion of serum was Remove from the hot plate and add
and uncomplicated method for phos- determined using the heteropoly blue slowly with constant stirring 375 ml. of
72% perchloric acid which precipitates
phorus is obtained in combining chloric color reaction of Boltz and Mellon (2),
acid digestion with the heteropoly potassium as the perchlorate. Cool and
which employs hydrazine sulfate as a place the covered beaker in a refriger-
blue color formed by hydrazine sulfate reducing agent. The color produced is ator for 12 to 24 hours. Filter on a
reduction of the molybdiphosphate not only more stable than that produced Büchner funnel with suction through a
complex. using l-amino-2-naphthol-4-sulfonic acid Whatman 41H paper. The filtrate _

(S) in the reduction of the phospho- is approximately 28% chloric acid.

acid has been used success- molybdic acid complex but also far more Standard Phosphorus Stock Solu-
tion. Dissolve exactly 0.351 gram of
Chloric
fully for serum protein destruc- sensitive.
pure, dry monopotassium phosphate in
tion in the estimation of protein-bound distilled water and transfer quantita-
REAGENTS
iodine (S). This reagent has the tively to a 1-liter volumetric flask.
property of destroying the organic com- Chloric Acid. Weigh 500 grams of Add 10 ml. of 10AT sulfuric acid, dilute

VOL. 30, NO. 6, JUNE 1958 · 1097