V O L U M E 2 2 , N O .

11, N O V E M B E R 1 9 5 0 1457

LI1'ER.ATURE CITED (9) ltossum, J. R., and Villarrus, P., Water and Sewage W o r k s , 96,
391 (1949).
(1) Am. Pub. Health Assoc., "Standard Methods for Examination
of lyater and sewage," 9th ed., xew york, Aqmerican public (10) Schwarzenbach, G., and hckernlann, H., Helo. C h i w Acta, 31,
Health Association, 1946. 1029-48 (1948).
(2) Beta, J. D., and Noll, C. A , , J . ~ m ate^. worksA ~ ~42,~49~ . (11)
, Schwarzenbach, G., and Biedermann, W., Ibid., 30, G78-87
(1947).
(1950).
(3) Bicdermami, W., and Schwarzenbach, G., Chitnia, 2, 56 (1948). (12) Schwarzenbach, G., Biedermann, W., and Bangerter, F., Ibid.,
29, 811-18 (1946).
(4) Cantina, E. C., Soil Sci., 5 , 361-8 (1946).
( 5 ) Canners, J. J., J . A m . Water Works Assoc., 42, 33 (1950). (13) Sheen, R. I., Kahler, H..L., and Ross, E. hl., IND.EN. CHFX.,
( 6 ) Diehl, H.. Goetz. C. A.. and Hach, C. C., Ibid., 42, 40 (1950).
ANAL.ED.,7, 262 (1935).
(7) Ingols, R. S., Filter Press, 4, S o . 8, 5 (1949). RECEIVEDJanuary 27, 1950. Presented before the hleeting-in-~liniature,
( 8 ) J. A m . Water Works Assoc., 42, 39 (1950). Georgia Section, AVERICASCHEMICAL SOCIETY,November 1919

Determination of Acetyl in Pectin

E. L. PIPPEN, H. JI. M C C R E A D Y , A N D II. S. OWENS, W e s t e r n K5gional Reseurch Laboratory, Albany, C a l q .

DURIKG a study of pectin acetates a t this laboratory, a sim-
method for the analysis acetyl in pectin was desired.
of
Although successful methods ( 3 , 4,6 ) have been described for the
determination of acetyl in pectin, the method presented here re-
quires few operations, is economical of materials, and is rapid and
accurate.
The method is a modification of Clark's ( 2 ) procedure, devised
to overcome the inconsistencies obtained when hot alkali is used
for the saponification. The authors' experience has agreed with
that of Liidtke and ~~l~~~( b ) ,who have shown that acids, other
than acetic, are formed whea pectin is heated in alkali.
APPARATUS
heating the distilling flask with a flame until the volume of liquid
in the distilling flask was about 15 to 20 ml. Steam was then per-
mitted to enter through the steam inlet tube by loosening the
Screw clamp. The rates of steam inlet and application of heat to
the distilling flask were adjusted so that the volume of liquid in
the distilling flask remained at about 15 t o 20 ml. (Keeping the
volume of liquid in the distilling flask low ensures a quantitative
recovery qf the acetic acid in a 100-ml. distillate volume.) Dis-
tillation thus carried out until a distillate of 100 ml. was c o ~ -
lected. which !vas titrated writh 0.05 N sodium hvdroxide to an
end point with phenol red as the indicator. A blink defermina-
tion was carried out by distilling, as described above, a mixture of
20 ml. of the magnesium sulfate-sulfuric acid solution and 20 ml.
of distilled water. Titration of the distillate from the blank run
usually requires 0.1 ml.

The apparatus is identical to that described by Clark ( 2 )except SCREW C L A M P 7 24/40 $ -7

for the distilling flask and condenser, which were modified

slightly (Figure 1).
MATERIALS

The pectin acetates analyzed were prepared by acetylation of

commercial citrus pectin by the procedure of Carson and Maclay
(1). Results for pectin are expressed on a moisture- and ash-free
basis. The purity of other substances analyzed was established
by their melting points, saponification equivalents, and specific 100 H L F L A S K

rotations, where applicable.

PROCEDURE Figtire 1. Diagram of Distilling Flask and C o n d e n s e r

An accurately weighed 0.5-gram sample of the pectin acetate
was placed in a 250-nd. Erlenmeyer flask and 25 ml. of 0.125 N Calculation. Net ml. of NaOH = (total ml. of XaOH re-
sodium hydroxide were added. The flask was stoppered and quired to titrate distillate) - (total ml. of NaOH required to ti-
the contents wcre stirred until all the pectin wasdissolved. The trate distillate of bla1:k run)
flask was then set aside at room temperature for at least 1 hour.
( A s a routine procedure, samples were permitted to stand in alkali (net ml. of NaOH) (normality of NaOH) X
overnight.) The contents of the flask were diluted to 50.0 ml. (0.043) (100)
and a 20.0-ml. aliquot was withdrawn and placed in the distilling % acetyl =
flask. This was followed by a 20-inl. aliquot of ('lark's ( 2 ) mag- weight of sample, grams, in 20.0-ml. diquat
rirsium sulfate-sulfuric acid solution and an ebullition tube. Af-
ter the steam inlet tube was set in place, the rubber tubing was RESULTS
closed with the screw clamp and distillation wa? carried out by
On duplicitte analyses on pectin, reproducibility of results
within 0.1ri or better was consistently obtained. Further cx-
Table I. Comparison of Authors' with Henglein and periments to dctcrmine the accuracy and scope of the method
Vollmert (4) Method were conduvted. Comparison with t8hemethod of IIenglein and
Acetyl Found, % Vollmert ( 4 ) (Table I ) shows that these two methods are in ex-
Method of cellrrit agrccmcnt, for the analyses of pectin acetates. When sub-
Henglein Modifiration of
Subbtance Analgzrd and Yollrnert Clark's method stances other than pectin acetates \?ere analyzed (Table II), re
Pectin acetate 13 2.5 2.56, 2.57 sults for glucosr: and galactosc pentaacetates were higher than the
Pectin acetate 12 2.9 3.01, 2.97
Citrus pectin 0.3 0.29, 0.30 theoretical acetyl values. \Vhile tk!e results of only two analyses
of galactose and glucose peritaacetates are presented, other analy-
Tahle 11. Acetyl i n Suhstances Other than Pectin ses of these compounds gave results which were consistently 1 to
Acetyl. % 2% higher than the theoretical values. I n the analysis of glucose,
Substance Analyzed Found Calculated as well as the acetates mentioned above, the apparent acetyl con-
Arabitol pentaacetate 59.3, 59 3 59.5 tent generally increased in direct proportion to the time of saponi-
Galactose pentaacetate 65.2, 56.4 55,l
Glucose pentaacetate 55,7,57.2 55.1 fication. Consequently, the method, as described in this paper,
is unsuitable for acetates of these sugars and presumably for ace-
1458
tates of other simple sugars. The high results obtained for these
compounds are probably due to the formation of acids, other than
acetic, which are sufficiently volatile to enable them to appear in
the distillate. On the other hand, consistent results were ob-
tained on duplicate analyses of pectin acetates, for which the
time of saponification was varied by as much as 1 to 20 hours.
Thus, if any acids, other than acetic, are formed under the condi-
tions specified, they are not sufficiently volatile to interfere with
the method herein described for the analysis of pectin acetates.
Arabitol pentaacetate served &s a suitable sthndard and the anal-
ysis of it gave consistent results which were close to, but never
exceeded, the theoretical acetyl value. Thus the method is suit-
able for arabitol and pectin acetates and would presumably be
Determination of Chloride in Water-Addendum
Preparation and Eflect of Mercuric Nitrate Reagent
FRANK E. CLARKE, U.S . Naml Engineering Experiment Station, Annapolis, M d .
IcuricNmethod
A previous article ( I ) , the author described an improved
for determining chloride ion by titration with mer-
nitrate solution in the presence of diphenylcarbazone-
bromophenol blue indicator and controlled pH. The instructions
for preparing reagents were given briefly, assuming that they
would be made in accordance with accepted laboratory practice.
This prescribes acidification of the mercuric nitrate solution to
prevent hydrolysis.
There has been some concern that acidification of the mercuric
nitrate might affect the accuracy of the chloride determination,
which is influenced by pH. This note provides more information
on the preparation of the mercuric nitrate reagent and shows that
its acidification does not affect accuracy significantly.
PREPARATION OF MERCURIC NITRATE SOLUTION
Mercuric nitrate does not dissolve readily in distilled water.
Even in preparing 0.025 N solution, a large proportion of the
crystals will remain undissolved and hydrolysis products may
precipitate. The solubility is affected somewhat by the degree of
hydration of the mercuric nitrate crystals.
It is common laboratory practice to dissolve the mercuric
nitrate residue by adding concentrated nitric acid slowly, while
stirring vigorously. This procedure usually consumes more
than the minimum effective quantity of acid. I t is better prac-
tice to dissolve the crystals directly in a small quantity of acidic
water, and then to dilute the solution to volume. The quantity
of mercuric nitrate required to make 1 liter of 0.1 N solution can
be dissolved in 100 ml. of water containing 1.0 to 1.5 ml. of con-
centrated nitric acid. The quantity requiredfor a 0.025 N solu-
tion can be dissolved in 25 to 50 m]. of water containing 0.25 to
0.40 ml. of concentrated nitric acid. When prepared in this
manner, either directly or by dilution from 0.1 N stock, the
0.025 N mercuric nitrate solution will have 6 pH of 2.25 to 2.50.
It will be clear and remain clear for long periods of storage. Sedi-
ment which forms in storage can be filtered off, but the solution
must be restandardized.
EFFECT OF MERCURIC NITRATE ACIDITY ON CHLORIDE
DETERMINATION
At the optimum pH, the mercury-diphenylcarbazone color
complex forms after all the chloride ion is combined as weakly
ionized mercuric chloride. I n weakly acid solutions the color
complex will form in the presence of a large exceea of chloride
ion. I n strongly acid solutions the tendency to form the complex
is reduced, 80 that a large exceas of mercuric ion is required to
develop the color. Between these two extremes there is a reaaon-
ANALYTICAL CHEMISTRY
useful for other o-acetyl compounds which are readily saponified
by dilute alkali near 20’ C. and do not give rise to acetic acid by
side reactions or to volatile acids other than acetic acid.
LITERATURE CITED
(1) Carson, J. F., and Maclay, W. D., J. A m . Chem. SOC.,68, 1016
(1946).
(2) Clark, E. P., “Semimicro Quantitative Organic Analysis,” p. 73,
New York, Academic Piess, 1943.
(3) Freudenberg, K.,and Harder, M., Ann., 433,230 (1923).
(4) Henglein, F. A., and Vollmert, B., Makromol. C h a . , 2,77 (1948).
(5) Liidtke, M.,and Felser, H., Ann., 549, 1 (1941).
(6) Nelson, E.K., J . Am. Chem. SOC.,48, 2945 (1928).
R E C E I V ~February
D 6, 1950.
ably wide p H region (3.0 to 3.5) in which excellent accuracy can
be obtained a t all chloride concentrations. It is most convenient
to establish the optimum p H by adding nitric acid to the chloride
solution before titrating it with mercuric nitrate (1). Because
the mercuric nitrate solution contains some nitric acid, there is a
slight increase in acidity of the chloride solution during the titra-
tion-for example, titration of 2 mg. of chloride ion in 100 ml. of
solution will require 2.26 ml. of 0.025 N mercuric nitrate and
reduce the p H from approximately 3.3 to 3.25. Titration of the
maximum quantity of chloride ion recommended in (1) will re-
quire 22.6 ml. of 0.025 N mercuric nitrate solution and reduce the
p H to approximately 3.05.
The acid error in milliliters of mercuric nitrate solution con-
sumed, and therewith milligrams of chloride, depends on the
deviation from the optimum pH. It is essentially independent of
the chloride concentration. The acid error aa percentage of chlo-
ride varies inversely with the total quantity of chloride present.
It therefore is most significant in low chloride concentration$.
Fortunately, these require small mercuric nitrate titrations, which
yield insignificant p H reductions. At higher chloride concentra-
tions, where larger quantities of mercuric nitrate yield greater p H
changes, the lower percentage errors balance out the effects and
maintain good accuracy. The pH-error graph in ( I ) was based
on a 20 p.p.m. solution of chloride ion (2 mg.), which is a con-
centration frequently encountered in water work. It would not
be applicable to chloride ranges far above or far below that con-
centration. The data in Table I11 (1) were obtained by first
adjusting the chloride solution in accordance with the recom-
mended procedure and then titrating with acidified mercuric
nitrate solution. No correction was made for the additional acid
introduced with that reagent. The data show that this procedure
is adequate for all normal. analytical work.
If extreme accuracy is desired, as in microanalysis, corrections
can be made for indicator sensitivity and for excew acid intro-
duced with the titrating solution. The indicator correction is
determined by making a blank titration on chloride-free water
containing the total quantities of indicator and acid which will
exist in the sample a t the end of its titration. The effect of e x c w
acid is overcome by neutralizing most of the excess before adding
the indicator. Slightly less than the required amount of mercuric
nitrate solution is run into the untreated chloride sample. The
diphenylcarbazone-bromophenol blue indicator is then added,
the P H of the solution is adjusted, and the titration is completed.
These refinements are not required for most analytical work.
I3TERATURE CXTED
(1) Clarke, F.E.,ANAL.CEDX.,22, 663-6 (1050).