Volumetric Determination of Nitrate Ion
Simultaneous Determination of Nitrite
OTTO RICHARD GOTTLIEB and MAURO TAVEIRA MAGALHAES
lnstituto de Qdrnica Agrkola, Minisi6rio da Agricultura, Rio de Janeiro, Brazil
,The reaction between sulfamic acid
and nitric acid is used in the deter-
mination of nitrate ion by titration of
the excess sulfamic acid with standard
sodium nitrite solution, using an ex-
ternal indicator such as starch-iodide
to detect the end point. Quantities
of potassium nitrate between 5 and
100 mg. were determined with a
deviation from the correct value oscillat-
ing between &0.6% and an average
error of less than 0.1%. The method
is sufficiently selective. Nitrites and
ammonium salts do not interfere.
The procedure does not call for any
special apparatus, and it is rapid
and well suited for routine work.
A METHOD Iyas needed for the deter-
mination of nitrate nitrogen which
did not rely on special equipment, rea-
gents, or techniques.
Berglund (3) discovered that sulfamic
acid is decomposed with effervescence,
even a t room temperature, by nitric
acid or by a mixture of sulfuric acid
and a nitrate. He identified the gas
as nitrous oxide. Baumgarten '(2)found
that at room temperature the reaction
occurs only with concentrated nitric
acid, proceeding quantitatively accord-
ing to the equation:
HNO' + HzN*SOsH + NzO + HzsOt
+ Hz0
Previous work on gasometric titration
(8) showed that this reaction can be
used for the determination of nitrate ion.
The acids are freed from a mixture of
nitrate and a known quantity of sulfa-
mate, by adding concentrated sulfuric
acid a t room temperature. After this
rapid reaction is completed, the excess
sulfamic acid is titrated with a standard
solution of sodium nitrite.
REAGENTS
SODIUM NITRITE. Crystallize rea-
gent grade material three times from
water. Dry the crystals to constant
weight in a desiccator under vacuum.
Dissolve a 5.5206-gram sample in dis-
tilled water and dilute t o 1 liter. This
0.08M solution can be used as a primary
standard (9) for 90 days (6).
SULFAMIC ACID. Dissolve about 7.77
grams of sulfamic acid (reagent grade,
G. Frederick Smith Chemical Co.,
Columbus, Ohio) in distilled water.
Dilute to 1 liter, to prepare an approxi-
mately 0.08M solution.
Starch, 3% aqueous solution.
Potassium iodide, free from iodine,
20% aqueous solution.
PROCEDURE
Prepare a neutral sample solution
containing 0.4 to 0.6 gram of nitrate
ion per 100 ml.
Preliminary Test. If one drop of
the sample solution after acidification
with dilute sulfuric acid, 10% by vol-
ume, gives a feeble or negative starch-
iodide test (absence of nitrite), use
25.00-ml. portions of 0.08iM sulfamic
acid solution in the procedure below. If
a strong blue color appears in the test,
treat 2 ml. of 0.086f sulfamic acid with 1
ml. of 10% sulfuric acid and titrate the
solution rapidly with the sample solution
to an approximate starch-iodide end
point. If 4 ml. of sample solution have
been used up and the end point has not
been reached (presence of only small
quantities of nitrite), follow the pro-
cedure as described with 25.00-ml.
portions of 0.08M sulfamic acid solu-
tion. If, however, between 4 and 0.5
ml. of sample solution are required to
reach the end point (presence of signifi-
cant quantities of nitrite), increase
the portions of 0.08M sulfamic acid solu-
tion in the procedure. It is best to use
portions in the vicinity of (25.00 + (about 2 to 3 ml. per minute), stopping
20.00:~)ml., z representing the volume
of sample solution consumed in the
titration above. If less than 0.5 ml. is
sufficient to reach the end point (pres-
ence of very great quantities of nitrite),
dilute the sample solution until a t
least 0.5 ml. is needed to react with 2
ml. of the sulfamic acid solution.
Determination of Nitrate. Transfer
t o each of two 250-ml. beakers
marked I and 11, equal volumes,
25.00 ml. or more (see Preliminary
Test) of 0.08M sulfamic acid solu-
tion. Add t o each 0.5 ml. of 10%
sulfuric acid. Run into each slowly
10.00 ml. of sample solution with
stirring. Continue t o stir for 3
minutes. Add one drop of 0.1% phenol-
phthalein indicator and then dilute so-
dium hydroxide solution to slight alka-
linity. Evaporate the contents of both
beakers t o dryness on the steam bath.
Heating should be discontinued a t the
moment the residue completely solidi-
fies; if heating is prolonged beyond this
point, it will be less easily attacked by
Table 1. Effect of Procedure Condi-
tions on Stability of Sulfamate
0.08M
Sulfamic
Bcid
solution 0.08M Sodium Nitrite
Taken, Solution, Used M1.
Ml., 1. 2b
25,00 25.05 25.05
25.00 25.03 25.04
25.00 25.05 25.03
0 The sulfamic acid solution, after addi-
tion of sulfuric acid, was titrated with
sodium nitrite solution.
* The sulfamic acid solution mas sub-
jected to the conditions of the procedure
and then titrated with sodium nitrite solu-
tion.
sulfuric acid. Cool the residue to room
temperature. To beaker I, add 2 ml. of
concentrated sulfuric acid and make the
mixture homogeneous. After the gas
ceases to evolve (a few minutes), dilute
n-ith distilled water to approximately SO
ml. To beaker 11, add 80 ml. of dis-
tilled water and then 2 ml. of concen-
trated sulfuric acid.
Titrate the excess sulfamic acid in
both beakers with standard 0.OSM
sodium nitrite solution, using a starch-
iodide solution as an external indicator.
Stir the contents of the beaker con-
stantly. Add the nitrite solution slowly
for 1 minute after each 5-ml. addition.
To verify the end point of the titration,
perform two spot tests, the first 1minute
and the second 3 minutes after adding
each drop of nitrite solution. The
equivalence point is considered reached,
when the indicator shows a slight blue
color within 15 seconds in both tests.
Perform these spot tests by adding a t
the moment of their execution, in the
cavity of a plate, one drop of starch
solution and one drop of potassium
iodide solution and touching this mis-
ture with the tip of a glass rod which
has been immersed in the titrated solu-
tion.
Determination of Nitrate and Ni-
trite. To beaker 111, add the same
volume of 0.08M sulfamic acid solu-
tion used in beakers I and I1 and
proceed as outlined for beaker 11,
omitting the sample solution.
CALCULATION
The per cent nitrate (or nitrate nitro-
VOL. 30, NO. 5, MAY 1958 * 995
gen) and nitrite (or nitrite nitrogen) in sulfamic acid to compensate for the (4) or even the more sensitive sulfanil-
the sample may be calculated, respec- reagent used up by the nitrite ion. amide-1-naphthylamine (Y), are not
tively, through the expressions: If the sample does not contain nitrite satisfactory \\-hen solutions of nitrite
Q (c - b ) M ion, the order of addition of sulfamic and sulfamate ions more dilute than
-
P (a - a) M
lo.p
and -
lo.p acid solution and sample is irrelevant, 0.0lM are titrated. This establishes a
and treatment of the sulfamic acid solu- lower limit of about 5 mg. for the quan-
where P is the molecular weight of the tion by sulfuric acid and slow addition tity of nitrate ion which can be deter-
nitrate (or the atomic weight of nitro- mined by the procedure described. Pre-
gen), Q is the molecular weight of the of sample solution are also unnecessary.
nitrite (or the atomic weight of nitro- Only very concentrated aqueous solu- liminary experiments showed the possi-
gen), p is the weight in grams of the tions of nitric acid react with sulfamic bility of performing the titration by
sample in the aliquot taken for analysis, acid ( 2 ); hence reaction betxeen the electrometry. The amperometric titra-
11f is the molarity of the standard nitrite two substances is prevented by dilution. tion of sulfamates with nitrite, as de-
solution, and a, b, and c are the volumes By performing tIvo parallel operations- scribed by Hirozawa and Brasted (@, in
in milliliters of standard nitrite solution Le., reacting nitrate with sulfamic acid combination with the method here out-
consumed, respectively, in the titration in beaker I and preventing the reaction lined, might reduce the lower limit of
of the content of beakers I, 11, and 111. in beaker 11-problems pertinent to the nitrate ion determination.
stability of the sulfamic acid solution Slow reaction near the equivalence
DISCUSSION point is responsible for the wait before
are excluded. The data of Table I
Because large amounts of nitrite may show that the sulfamic ion is not appre- proceeding with the verification and the
use up significant quantities of sulfamic ciably altered under the conditions of confirmation of the end point.
acid, it is necessary to make a prelimi- the analysis. Quantities of concentrated
nary check for nitrite and, if this is sulfuric acid larger than 2 ml. make the RESULTS
present, to add a sufficient excess of starch-iodide end point rather difficult Some results of the application of this
to observe. Quantities smaller than 0.5 method to an analytical sample of po-
ml. make a thorough suspension of the tassium nitrate are presented in Table
evaporation residue difficult and de- 11. Table I11 illustrates results which
Table II. Determination of Pure Potas- crease the velocity of the reaction be-
sium Nitrate can be obtained in the determination of
tween the nitrite and sulfamate ions. mixtures of nitrite and nitrate.
Mg. Mg. Error, The optimum quantity of sulfamic
Present Found 7% acid to be titrated with the 0.08V ni- INTERFERENCES
80.92"** 80.60 -0.40 trite solution was established from data
80.75 -0.21 given by Bowler and Arnold (4). Ex- Chloride ion causes loss of nitrate
80.87 -0.06 when the residue is treated with sul-
80.87 -0.06 ternal indicators, such as starch-iodide
80.90 -0.02 furic acid. This interference can be
80.92 0.00 eliminated by transforming the chloride
80.95 +0.04 ion to silver chloride with a slight ex-
80.98 +0.07 Table IV. Determination of Nitrate cess of silver sulfate. The determina-
80.98 $0.07 Nitrogen in Commercial Products tion of nitrate in a fertilizer (Table IV)
81.03 $0.14
81.11 $0.23 Nitrate Nitrogen was performed in this manner.
81.17 $0.31 Found, yo Although nitrite ion reacts with sul-
81.17 +0.31 AOAC famic acid, the double titration pro-
81.42 $0.62 method Proposed
(1) procedure cedure eliminates its influence on the
Av. 80.98 i0.15 f 0 . 0 7 nitrate determination. By an addi-
Fertilizer" 4.6 4.67
8.09"*c 8.02 -0.87 4.70 tional titration, using the same solu-
8.10 +o. 12 4.70 tions and technique as in the nitrate
8.10 $0.12 determination, nitrite can be deter-
8.15 +0.74 Calcium nitrateb 14.1 14.14
Av. 8.09 =t0.04 $0.03 14.11 mined simultaneously. The interfer-
14.13 ence of other substances capable of re-
a Quantity contained in 10.00 ml. of
eolution. 4 Organic nitrogen, 1.7y0 as N; chloride, acting with sulfamic acid in aqueous
* 25.00 ml. of 0.08M sulfamic acid solu- 4,5% as C1; phosphorus soluble in 2% solution is also eliminated by the double
tion added. Titration performed with citnc acid, 11.7y0 as PzO5; total phos- titration. However, substances which,
0.08M sodium nitrite solution. phorus, 12.2y0 as Pp06; potassium soluble like nitrate ion, react with sulfamic acid
c 20.00 ml. of 0.016M sulfamic acid in water, 5.1% aa KIO.
solution added. Titration performed with * Product, which contained 1.6% am- only when treated with concentrated
0.016M sodium nitrite solution. monium nitrogen, was labeled 15.5% N. sulfuric acid cannot be present.
Phosphates, sulfates, carbonates, and
many cations, including ammonium, do
not interfere. Cobalt(I1) ion is trans-
formed by nitrite to the cobalt(II1) com-
Table 111. Simultaneous Determination of Nitrate and Nitrite plex, [Co(NO&]---, which is stable
hlg. Present pvlg. Found toward sulfamic acid (6). Hence co-
Samde KNO, NaKOS KNOI NaNOl balt(I1) interferes with the nitrite de-
1 80.92 11.07 80.95 10.81 termination. The introduction of salts
80.78 10.98 into the aliquot, as through some pre-
80.71 11.18
treatment of the sample, must be prac-
2 80.92 55.36 80.71 55.53 ticed with caution. Relatively large
80.87 55.36
81.03 55.24 quantities of solids in the mivture with
the nitrate make a thorough suspension
3 32.37 166.08 32.20 166.63
32.45 166.30 of the residue in concentrated sulfuric
33.01 165.91 acid difficult. This condition may cause
In samples 1, 2, and 3, respectively, 25, 35, and 50 ml. of 0.08M sulfamic acid solution
low results.
were used, Titration was performed with 0.08M sodium nitrite solution. Organic substances which are easily
oxidized under the conditions of the

996 ANALYTICAL CHEMISTRY

method can be destroyed with per-
oxide (IO), which, in turn, must be
eliminated before nitrate can be deter-
mined. Organic substances which are
reasonably stable under the conditions
of the method do not interfere consid-
erably, even if they are nitrogenated.
Preliminary experiments showed that
satisfactory, although somewhat low,
results can be obtained for nitrate in
the presence of equal quantities of gela-
tin or urea.
ACKNOWLEDGMENT
The authors wish to express their ap-
preciation to Kalter B. Mors for his
interest in this work and t o Mary Ne-
bel, Wayne State University, Detroit,
hIich., for revision of the English manu-
script.
LITERATURE CITED
(1) Assoc. Offic. Agr. Chemists, “Official
hlethods of Analysis,” 8th ed.,
p. 13, 1955.
(2) Baumgarten, P., Bey. deut. chem.
Ges. 71, 80 (1938).
(3) Berglund, E., Bull. S O C . chim. [2],
29, 422 (1878).
(4) Bowler, W. W., Arnold, E. A.,
ANAL.CHEN.19, 336 (1943).
(5) Brasted, R. C., Zbid., 23, 980 (1951).
( 6 ) Zbid., 24, 1111 (1952).
(7) Cumming, W.M., Alexander, W. A.,
Analust 68, 273 (1943).
(8) Gottlieb, 0. R., “Titrimetria Gaso-
mbtrica,” Bol. 42, p. 47, Tnstituto
de Quimica Agricola, Ministbrio da
Agricultura, Rio de Janeiro (1955);
Anal. Chim. Acta 13, 531 (1955).
(9) Hirozawa, S. T., Brasted, R. C.,
ANAL.CHEM.25. 221 (19531.
(10) Johnson, C . M., blrich, A,; Zbid.,
22, 1526 (1950).
RECEIVEDfor review May 9, 1957.
Accepted December 5, 1957. Work sup-
ported by Conselho Nacional de Pesquisas,
Brazil.

Basic Behavior of Molecules and Ions in Acetjc Anhydride

C. A. STREULI
Analytical Research laborafory, American Cyanamid Co., Stamford, Conn.

,Titration of neutral and anionic
bases in acetic anhydride has shown
that a linear relationship exists be-
tween pK,(H20) values and half neu-
tralization potentials in acetic anhy-
dride. The relationship is, however,
different for the neutral bases than
for ions. Anions are stronger bases in
acetic anhydride than in water relative
to the neutral compounds. It is also
possible to titrate halide salts directly
in the solvent. Chlorides and iodides
may be resolved, but this is not possible
for chlorides and bromides or bromides
and iodides. Anions which form weak
acids in water solution are leveled in
basic strength in acetic anhydride.
this restricted the choice to tertiary PROCEDURE
amines and heterocyclics. Weigh out 1 mmole of the sample to
Two assumptions must be made in be tested, dissolve it in acetic anhy-
viewing qualitatively acid-base behavior dride, and dilute to 100.0 ml. in a
in acetic anhydride: Hydrogen acids volumetric flask. Pipet 25.0 nil. of
behave (and bases react with hydrogen this solution into a EO-ml. beaker, add
acids) in much the same manner as they 75 ml. of anhydride, and titrRte with
do in a protonated solvent, such as
acetic acid; and liquid junction poten-
tials, while unknown, are constant and
do not distort the titration curves.
REAGENTS AND APPARATUS
Reagents. The acetic anhydride
used as solvent was Baker and Adam-
son reagent made. which was not fur-

T HE utility of acetic anhydride as a

titration medium, either alone or in
conjunction with another solvent, has
been noted by Gremillion (4), Fritz (S),
and Usanovich ( I S ) . A number of
compounds which do not exhibit basic
properties in water, acetic acid, or ace-
tonitrile may be quantitatively titrated
in the anhydride. The principal draw-
back of this solvent is its reactivity with
some solutes to produce new products,
usually weaker bases.
The work described was initiated to
determine if weak anionic bases might
be titrated in this solvent, to give a more
detailed picture of acid-base behavior in
the anhydride, and to establish, if pos-
sible, a relationship between pK,(H20)
and half neutralization potential (HNP)
of weak bases in acetic anhydride.
The substances used as standards
were chosen to give as large a range of
pK, values as possible, but were limited
to those substances which showed a
minimum chance of being acetylated by
the solvent. In the case of the amines,
ther purifiedu.
PERCHLORIC
‘
ACIDSOLUTION, 0.05N.
This was prepared by diluting 4.2 ml.
of 72% acid with about 500 ml. of acetic
acid and then diluting this to 1 liter with
acetic anhydride. The solution became
highly cofored on standing, but color
formation did not affect the normality.
The acid was standardized against po-
tassium hydrogen phthalate (11).
Xost of the organic compounds mere
Eastman Kodak White Label. Quater-
nary ammonium salts were obtained
from the southwestern Chemical Co. ‘
0 ll-ullJ
P 40 80 80 100 120
Other salts were reagent grade.
Apparatus. All titrations were per- % Neutralization
formed using a Precision-Dom Recordo-
matic titrator. Solutions were agitated Figure 1 . Titration of neutral nitro-
with a magnetic stirrer during the gen bases in acetic anhydride
titration. The electrodes mere a a. Acetanilide
conventional glass electrode and a b. Acetamide
silver-silver chloride reference cell. c. Caffeine
The latter was made from the shell of d. Urea
e. Methylurea
a Leeds & Northrup calomel electrode, f. N,N-Dimethylaniline
and contained a coiled silver wire, elec- g. Quinoline
trically coated with silver chloride, im-
h. Pyridine
mersed in acetic anhydride which had 1. N,N-Diethylanlline
been saturated with silver and lithium k. N,N-Dimethylbenzylamine
chlorides. I. Tri-n-butylamine

VOL. 30, NO. 5, MAY 1958 997