Journal of Analytical Chemistry, Vol. 60, No. 7, 2005, pp. 629–632. Translated from Zhurnal Analiticheskoi Khimii, Vol.

60, No. 7, 2005, pp. 707–710.

Original Russian Text Copyright © 2005 by Ivanov, Figurovskaya, Barbalat, Ershova.

ARTICLES

Chromaticity Characteristics of NH2Hg2I3 and I2:

Molecular Iodine As a Test Form Alternative
to Nessler’s Reagent
V. M. Ivanov, V. N. Figurovskaya, Yu. A. Barbalat, and N. I. Ershova
Department of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119992 Russia
Received October 22, 2004; in final form, November 15, 2004

Abstract—The chromaticity characteristics were studied for the product of the reaction of Nessler’s reagent
with ammonium ions and for solutions of molecular iodine. These characteristics were used for the determina-
tion of the concentration variation step in the construction of the calibration plot in test methods. It was dem-
onstrated that chromaticity measurements can be used for improving the sensitivity of the determination, and
iodine solutions can be used in test methods for the construction of the scale simulating NH2Hg2I3 .

Nessler’s reagent is the most widespread and popu- methods. In addition, the chromaticity approach to the
lar reagent for the detection and photometric determi- construction of the calibration plot is optimum, because
nation of ammonia and ammonium ions [1, 2]. This is the series involves solutions with concentrations that
favored by the high sensitivity and selectivity of the form the geometric progression characteristic of the
reaction: the sensitivity of the reaction is 3 µg of NH3 human eye rather than the arithmetic progression,
in a drop with a volume of 0.02 mL, and only Ag, which is used in photometry. In hue and yellowness, the
Hg(II), Pb, and S2– ions interfere with the determination reaction product of ammonium and Nessler’s reagent
[1]. The selectivity and sensitivity are increased by con- (NH2Hg2I3) is similar to molecular iodine; therefore,
ducting the reaction in a chamber with the detection on iodine solutions can be used for the construction of a
paper impregnated with Nessler’s reagent. Photometry mimic scale for ammonium ions. In closed vessels in
is performed at 400–425 nm (<0.2 mg of NH3) and diffused light, test scales do not fade within 6 months.
550–580 nm (~1 mg of NH3; a precipitate is rapidly On exposure to sunlight, the color intensity can
formed in this case). increase because of the oxidation of iodide ions, which
are used for preparing Nessler’s reagent, in the alkaline
The maximum permissible concentration (MPC) of solution to molecular iodine.
ammonium ions in potable water is 1.5 mg/L (2 mg/L
nitrogen according to Sanitary Regulations SanPin The aim of this work was to determine the chroma-
2.1.4.1074-01), which corresponds to 0.045 µg per ticity characteristics of NH2Hg2I3 and molecular iodine
drop of a solution with a volume of 0.03 mL. However, and to construct a visual mimic test scale.
often larger amounts should be determined, e.g., in melt
waters from pastures and fields and sewage waters from EXPERIMENTAL
animal farms. Test strips for ammonium with Nessler’s
reagent allow the determination of 10–400 mg/L NH3 Reagents. A stock solution of ammonium was pre-
[2, p. 163]. The scale is of insufficient contrast in the pared by the corresponding dilution of a standard solu-
test version. A disadvantage of NH2Hg2I3 as the analyt- tion of an ammonium salt (GSO 7786-2000,
+
ical form is its rather low solubility in water. Therefore, 1.0 mg/mL NH 4 ). Nessler’s reagent was prepared
colloid solutions for the construction of the calibration according to the recommendations from [1, p. 86] and
plot in the photometric determination grow turbid with stored in a dark bottle. An I2 solution (0.025 M) was
time. For the same reason, test scales with the concen- prepared from a commercial volumetric standard and
tration of ammonium even at a level of 1–2 MPC are then diluted by exactly five times with water to the
unsuitable; they should be freshly prepared each week. mark in a volumetric flask.
The test determination of ammonium at a level of a Instruments. The absorbance and chromaticity
fraction of MPC presents the greatest difficulty because characteristics were measured on a KFK-2 concentra-
Nessler’s reagent itself is yellow colored and masks the tion photometer–colorimeter (l = 1 cm) and a Spectro-
color of the reaction product of ammonium and ton colorimeter (Khimavtomatika Chirchik Experimen-
Nessler’s reagent. tal Design Bureau of Automatic Equipment, Tashkent,
Previously, we demonstrated [3] that chromaticity Uzbekistan; l = 0.5 cm), respectively. The following
measurements are more sensitive than other optical chromaticity functions were used: chromaticity coordi-

1061-9348/05/6007-0629 © 2005 Pleiades Publishing, Inc.

630 IVANOV et al.

Table 1. Optical characteristics of NH2Hg2I3 and I2 solutions (KFK-2, l = 1 cm)

+
+
c( NH 4 ), c( NH 4 ), ε × 10–3 V(I2), mL
A400 ∆A400 A(I2)400 ε × 10–3 (I2)
µg/25 mL M × 105 (NH2Hg2I3) 0.005 M

18.75 4.15 0.418 0.088 2.12 0.5 0.208 2.08

37.50 8.30 0.500 0.170 2.05 1.0 0.440 2.20
75.0 16.6 0.690 0.360 2.17 1.5 0.676 2.26
112.5 24.9 0.88 0.55 2.21 2.0 0.915 2.28
150.0 33.2 1.05 0.68 2.05 2.5 1.15 2.30
187.5 41.5 1.25 0.92 2.22
Average 2.14 2.22

nates X, Y, and Z in the XYZ system; chromaticity coor- metric flasks and diluted with water to the mark. In the
dinates L, A, and B in the CIELAB system; lightness L; test determination of ammonium by a mimic scale, 1 ×
color saturation S; hue T; whiteness W; yellowness G; 10–4–6 × 10–4 M iodine solutions for the construction of
and color difference E. The symbol ∆ before the char- the calibration plot were transferred into colorimetric
acteristic denotes its measurement with respect to the test tubes tightly closed with glass stoppers, and stored
analogous characteristic of a reference sample. in diffused light or in the dark.
Procedure. Ammonium (18.75–187.5 µg) was Calculations were performed by the Origin 6.0 pro-
introduced into 25-mL volumetric flasks and diluted gram.
with water to 10 mL, Nessler’s reagent (1 mL) and
water (to the mark) were added, the mixture was stirred, RESULTS AND DISCUSSION
and the absorbance or chromaticity characteristic were
measured. For preparing a mimic scale, 0.5–2.5 mL of The optimum conditions of the interaction between
a 0.005 M iodine solution were placed in 25-mL volu- Nessler’s reagent and ammonium ions were described

Table 2. Chromaticity characteristics of NH2Hg2I3 at differ- Table 3. Chromaticity characteristics of iodine solutions
ent concentrations of ammonium (µg per 25 mL)
Function* 0.5 1.0 1.5 2.0 2.5 3.0
Func-
18.75 37.5 75.0 112.5 150.0 187.5
tion* c(I2) × 104, M 1 2 3 4 5 6
R400 0.203 0.171 0.123 0.082 0.061 0.042 R 0.455 0.272 0.137 0.074 0.040 0.023
R440 0.702 0.641 0.523 0.419 0.344 0.280 X 84.38 83.16 81.04 78.30 77.77 76.23
X 82.83 82.01 78.72 76.30 72.69 71.47 Y 88.78 87.91 86.77 85.85 84.86 83.68
Y 86.27 85.79 82.61 80.35 76.58 74.93 Z 86.23 82.34 72.23 64.03 58.19 52.36
Z 86.36 80.64 68.46 57.78 49.35 42.36
L 95.70 95.12 94.64 94.20 93.82 93.31
L 94.43 94.22 92.84 91.84 90.13 89.36
A –3.14 –5.65 –7.65 –9.80
A –3.28 –3.98 –4.42 –4.89 –4.92 –4.15
B 10.21 13.91 20.89 28.33 33.46 39.56 B 11.40 14.24 20.99 26.40 31.39 35.97
S 10.72 14.47 21.36 28.75 33.82 39.78 S 11.82 15.32 22.34 28.16 33.11 37.74
T 107.8 106.0 101.9 99.84 98.41 96.02 ∆L 0.898 1.394 1.876 2.317 2.695 3.203
∆L 0.109 0.318 1.695 2.699 4.410 5.171 ∆S 10.21 15.06 22.09 27.90 32.85 37.48
∆S 9.616 13.36 20.25 27.64 32.71 38.66 ∆T –0.57 –0.81 –1.04 –1.15 –1.34 –1.51
∆T –0.23 –0.38 –0.83 –1.17 –1.40 –1.82
∆E 10.53 15.15 22.19 28.05 32.99 37.65
∆E 9.620 13.37 20.33 27.79 33.03 39.05
W 87.18 83.92 77.02 71.18 66.31 61.67
W 87.91 84.41 77.47 70.11 64.76 58.82
G 16.77 22.71 34.11 45.31 53.18 62.15 G 17.0 23.7 31.30 38.03 44.61 50.27
* The concentration of ammonium ions (µg per 25 mL of the solu- * The volume of a 0.005 M iodine solution (mL per 25 mL of the
tion) is given in the first row. solution) is given in the first row.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 60 No. 7 2005

 CHROMATICITY CHARACTERISTICS 631

Table 4. Equations of the calibration plots for the determina- Table 5. Equations of the calibration plots for iodine solu-
tion of ammonium with Nessler’s reagent (c = 18.75– tions (c = 1 × 10–4–6 × 10–4 M; n = 5, P = 0.95)
187.5 µg/25 mL) (n = 5, P = 0.95)
Chroma-
Chromaticity

Molar coeffi- ticity Equations of the calibration plots RSD, %

cients of chro- RSD, functions
functions

Equations of calibration plots

maticity func- % G (10.6 ± 0.6) + (6.8 ± 0.1) × 104c 2
tions × 10–4
Z (94.2 ± 1.5) – (7.2 ± 0.4) × 104c 5
G (13 ± 1) + (0.27 ± 0.01)c 12.1 4 ∆E (4.9 ± 0.7) – (5.6 ± 0.1) × 104c 3
Z (90 ± 2) – (0.26 ± 0.01)c 11.9 5 W (93.2 ± 0.8) – (5.4 ± 0.2) × 104c 4
∆E (6.9 ± 0.6) + (0.175 ± 0.005)c 7.8 3 B (5.9 ± 0.8) + (5.2 ± 0.2) × 104c 4
W (90.7 ± 0.5) – (0.173 ± 0.004)c 7.8 4 ∆S (4.7 ± 0.7) + (5.6 ± 0.2) × 104c 3
Y (89.9 ± 0.1) – (1.0 ± 0.1) × 104c 2
B (7.5 ± 0.6) + (0.174 ± 0.005)c 7.8 5
X (86.1 ± 0.5) – (1.7 ± 0.1) × 104c 8
∆S (7.0 ± 0.6) + (0.172 ± 0.005)c 7.7 3
∆L (0.47 ± 0.04) + (4.5 ± 0.1) × 103c 2
Y (88.0 ± 0.4) – (0.071 ± 0.003)c 3.2 5
∆T (–0.43 ± 0.04) – (1.8 ± 0.1) × 103c 5
X (84.2 ± 0.4) – (0.072 ± 0.004)c 3.2 6
R (0.46 ± 0.06) – (8.4 ± 1.6) × 102c 19
∆L (–0.7 ± 0.2) + (0.031 ± 0.002)c 1.4 5 L (96.09 ± 0.06) – (4.5 ± 0.1) × 103c 3
∆T (–0.07 ± 0.04) – (0.009 ± 0.0004)c 0.4 4 A (–1.6 ± 0.3) – (0.97 ± 0.04) × 104c 4
R440 (0.73 ± 0.02) – (2.5 ± 0.2)c 0.1 6 S (5.9 ± 0.8) + (5.6 ± 0.2) × 104c 4

in the literature for the photometric procedure and ful- It is seen that the calibration plot with Nessler’s
filled in this work. The calibration plot was constructed reagent begins not at the origin of coordinates, unlike
+
in the range 18.75–187.5 µg of NH 4 in a volume of the plot for iodine, and the molar absorptivities are
nearly identical (Table 1) but do not coincide with the
25 mL or 1 × 10–4–6 × 10–4 M in the case of iodine, data reported in the literature, where ε ~ 106. This
which corresponds to the concentration of ammonium increased value of molar absorptivity in the literature
at a level of 0.5–5 MPC. The selection of wavelengths can be attributed to colloid formation, whereas the
of 400 and 440 nm for the measurement of absorbance, results obtained in this work and their reproducibility
on the one hand, was caused by the instrument and, on indicate that true solutions are formed in the studied
the other hand, does not contradict the recommenda- concentration range. From the data in Tables 1–5, it is
tions [1, p. 85] for the amount of ammonia of 0.2 mg seen that the plots of the dependences of all chromatic-
(400–425 nm). ity functions for the reaction product with Nessler’s
Table 1 presents optical characteristics determined reagent and for solutions of molecular iodine are linear
in this work, Tables 2 and 3 present chromaticity char- in the same range as diffuse reflection coefficients.
acteristics, and Tables 4 and 5 present the equations of However, the molar coefficients of all chromaticity
calibration plots for these functions and molar coeffi- functions are larger than the molar absorbances of the
cients of chromaticity functions. The calibration plots analytical forms. The orders of decrease of molar coef-
for diffuse reflection coefficients at 400 and 440 nm are ficients nearly coincide for the two forms. Because the
linear in the studied concentration range of ammonium solutions are colored yellow or yellow–brown, the yel-
ions with the use of Nessler’s reagent (Eqs. (1) and (2)) lowness molar coefficient is larger than the analogous
and a solution of molecular iodine (Eq. (3)); the equa- whiteness coefficient and is maximum among all stud-
tions of calibration plots for diffuse reflection coeffi- ied chromaticity functions. Finally, it is important that
cients are presented below: the calibration plot for iodine solutions begins at zero,
which is adequate to the problem in hand, and allows
R400 = (0.21 ± 0.11) – (9.5 ± 1.1)c, (1) the use of iodine solutions for the construction of a
mimic scale for ammonium ions. The volumes of a
∆R440 = (0.73 ± 0.02) – (2.5 ± 0.2)c, (2) 0.005 M iodine solution equivalent to the above
amounts of ammonium ions (µg per 25 mL) are given
R400 = (0.46 ± 0.06) – (8.4 ± 1.6) × 102c, (3) below:
where R400 and ∆R440 are diffuse reflection coefficients
+
at the given wavelengths with reference to water and a c( NH 4 ), µg/25 mL 18.75 37.50 75.0 112.5 150.0 187.5
reagent solution, c is the amount of ammonium ions
(µg) in 25 mL (Eqs. (1) and (2)) or iodine (Eq. (3)). V(I2), mL 0.005 å 0.20 0.41 0.82 1.20 1.45 2.00

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 60 No. 7 2005

632 IVANOV et al.

Thus, we demonstrated that coinciding orders of the ACKNOWLEDGMENTS

variation of chromaticity functions and the correlation
of optical characteristics allow the replacement of a The work was supported by the Russian Foundation
scale with Nessler’s reagent, which is unstable in stor- for Basic Research, project no. 05-03-32337.
age, with a mimic scale with a molecular iodine solu-
tion, which is stable for 6 months, in the construction of
the calibration plot. The determination with Nessler’s REFERENCES
reagent is descried in the experimental section. For the
1. Volynets, V.F. and Volynets, M.P., Analiticheskaya
construction of the mimic scale, 0.20, 0.41, 0.82, 1.20, khimiya azota (Analytical Chemistry of Nitrogen), Mos-
1.45, and 2.00 mL of a 0.005 M iodine solution, which cow: Nauka, 1977.
is prepared by the 10-fold dilution of a solution of a
commercial volumetric standard, are introduced into 2. Zolotov, Yu.A., Ivanov, V.M., and Amelin, V.G.,
25-mL volumetric flasks. The scale is suitable for both Khimicheskie test-metody analiza (Chemical Test Meth-
the test determination and the quantitative determina- ods of Analysis), Moscow: Editorial URSS, 2002.
tion of ammonium ions with the use of a KFK-2 pho- 3. Ivanov, V.M. and Kuznetsova, O.V., Usp. Khim., 2001,
tometer. vol. 70, no. 5, p. 411.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 60 No. 7 2005