alkaline impurity (as K2C03)is applied to the oxygen values, the difference between neutron activation and amalgamation

method mean oxygen values is reduced by a factor of about 2. When, in addition, a n estimated correction for environmental contamination is applied to the Series I11 potassium, the difference in fully adjusted mean oxygen values becomes vanishing small. (A comparable contamination correction could not be applied to the alkaline impurity-adjusted oxygen values of the Series IV potnssium for lack of d a t a on atmospheric contamination pick-up in the inert gas environment.)
LITERATURE CITED

(2) Champeix, L., Darras, R., Duflo, J., J . i\TucI. Mater. 1, 113 (1959). (3) Dupraw, W. A., Graab, J. W., Gahn, R. F., ANAL. CHEM. 36,430 (1964). (4) Epstein, L. F., Nut. Aeron. Space Admin. Tech. Xemo. X-884 (1963). (5) Gahn, R. F., Rosenblum, L., Zbid., Tech. .\ote D-3239 (1966). (6) Goldberg, G., Conference on An-

No. 91, U. S. Government Printing Office. ~ ~ - 1963. (12)Peak, R. D., U. S. At.. Energy
->

alytical Chemistry and Applied Spectroscopy, Pittsburgh, March 2-6, 1964. (7) Humphreys, J. R., Jr., Nuclear Engineering and Science Congress, Cleveland, Dec. 12-16, 1955. (8) Kuivinen, D. E., Nut. Aeron. Space

Comm. Rept. ORNL-CF-57-4-11 5 (1957). (13) Pepkowitz, L. P., Judd, c., ANAL: CHEM. 1283 (1950): 22, (14) Steele, E. L., Lukens, H. R., Guinn, V. P., General Dynamics Corp. Rept. GA-5982 (1964).

w.

nger, V. A., Anders, 0. U., Van Kramer, iem. Co.

( 1 ) Anders, 0. U., Briden, D. W., ANAL. CHEM. 530 (1965). 37,

Admin. Tech. Pre. 6-63 (19631. (9) Litman, A. P., U . S. At. Energy Comm. Rept. ORNL-3751 (1965). (10) Malikova, Y. D., Turovtaeva, Z. X., Analzz Gazov V Metalakh Bkah. iVauk SSSR (English Transl. FTD-TT-621338, 1962.(11) Natrella, XI. G., Experimental

Statistics, Xat. Bur. Stds. Handbook

(16) White, J. C., U . S. Energy Comm. At. Rept. ORNL-CF-56-4-31 (1956). (17) Williams, D. D., Miller, R. R., ANAL. CHEM. 1865 (1950). 23, (18) Winer, B. J., Statistical Principles in Experimental Design, McGrawHill, New York, 1962. (19) Zellers, G. R., iVat. Aeron. Space Admin. Tech. Memo. X-1085 (1965). RECEIVED review December 27, 1965. for Accepted May 5, 1966.

2-Chloro-5-Cyano-3,6-Dihydroxybenzoquinone, a New Analytical Reagent for the Spectrophotometric Determination of CaIciurn(l1)

R. E. REHWOLDT, 8. L. CHASEN, and J. 6. LI
Vassar College, Poughkeepsie,

N.Y .

The synthesis of a new analytical reagent, 2- chloro 5 cyano 3,6dihydroxybenzoquinone (HDDQ), is described. Its structure is similar to that of the chloranilic acid, and it promises to b e a versatile analytical reagent. Micro amounts of Ca + 2 have been determined spectrophotometrically by complexing with HDDQ. By using an excess of the reagent, the Ca+2 complex was removed as a precipitate, and the absorbance of the colored supernatant was measured at 490 mp. This method may b e used in the presence of BafZ.

- -

chloranilic acid as a complexing and colorimetric reagent (1). Chloranilic acid, however, is not highly selective for Ca+2 alone, and is hindered by interfering ions ( 7 ) . During the investigation of the molecular complexes of 2,3-dichloro-5, 6-dicyanobenzoquinone(I), DDQ, in this laboratory ( 5 ) , it was observed that water caused the decomposition of DDQ as had been noted previously (6). The isolated decomposition product has now been identified as 2-chloro-5-cyano-3,Bdihydroxybenzoquinone(II), HDDQ. The similarity of HDDQ to chloranilic acid, 2,5-dichloro-3,6-dihydroxybenzoquinone(III), suggested that HDDQ might also be a good complesing agent

have been described in the literature for the determination of calcium ion. However, certain drawbacks exist in these reported methods. The calcium oxalate procedure is long and cumbersome, and it is difficult to obtain a complete precipitation when certain organic materials are present. The use of the reagent EDTA is dependent upon a colorimetric procedure involving the indicator, murexide. Although murexide is sensitive to 0-1.2 p.p.m. Ca+2, it can tolerate only trace amounts of alkaline earths, making prior separation of these interfering ions necessary for accurate determination ( 8 ) . More recent procedures involve the use of
ARIOUS REAGENTS

(4).
C I O CN HOI O CH HO C1I C N C l O N CH Q
0 0 I1
EXPERIMENTAL

IC1
0 I11

Apparatus. A Beckman D B recording spectrophotometer was used to obtain t h e absorption spectra of the various solutions. Quantitative absorption measurements were performed with a Beckman D U spectrophotometer. Matched Corex cells of

1 cm. were used. A Perkin-Elmer 237 spectrophotometer was used for the infrared spectrum. Reagents. P R E P A R A T I O N OF H D D Q . The disodium salt of H D D Q was prepared from D D Q (obtained from Arapahoe Chemicals). Five grams of D D Q were added to 120 ml. of hot water and stirred until the yellow solid dissolved and produced a red solution. Thirty ml. of 6 3 KaOH were added with stirring. The volume of water was reduced to initiate crystallization. Crystals were filtered off and washed with acetone before recrystallization from hot water. The hydrated crystals are brown to red in color and needle-like. The structure was determined by elemental analysis and the infrared spectrum (Figure 1). The anhydrous free acid was obtained with difficulty from an ethanol-water hydrolysis; decomposition 247-249 C., with sublimation. REAGESTSOLUTIOK.. 0.1% soluA tion of disodium HDDQ was made in distilled water. The solution appeared to be stable indefinitely. STANDARD CALCIUM SOLUTION. A standard 0.035X calcium solution was prepared from Ca(l\Oa)2. INTERFERING IONS. Solutions (0.01M) of interfering ions were prepared from their nitrates.
PROCEDURES AND RESULTS

Nature of the Disodium H D D Q Solution and Complexes. As can be

seen in Figure 2, the salt has a n

1018

ANALYTICAL CHEMISTRY

0.8

3 z 0.6

2 5

w
I I
1

s
I I

0*4
0.9.

I
12.0

0.0

3.0

4.0

5.0

6.0

1.0

8.0

9.0

10.0

11.0

400

WAVELENGTH, m r

450 500 550 WAVELENGTH, mr

600

Figure 1. The infrared spectrum of the hydrated disodium salt of 2-chloro-5-cyano-3,6-dihydroxybenroquinone pellet) (KBr

Figure 2. The visible absorption spectra of the disodium salt of HDDQ in acidic and basic aqueous media, 1 6 X .
1 0 - 3 ~

absorption maximum a t 490 mp in basic solution and one at 465 mp in acidic solution. Dilutions of the solutions follow Beers law. Precipitates of this coniplexing reagent vary in color and in crystalline structure, depending on the cation being complexed. Colors range from brownish-red to purple. Stoichiometry of the Calcium Complex. A constant molar method was employed to determine the composition of the Ca complex. The solutions were allowed to stand, with occasional shaking, for 48 hours, and the absorbance of each supernatant was then measured. The mole fraction ( r )of Ca+2 was calculated for each solution and A - (z/lO)A ( A is absorbance a t 490 nip) mas plotted against 2. As can be seen from Figure 3, there is a n intersection point at 0.5 mole fraction, corresponding to a 1:1 complex. Calibration Curve for the HDDQ Supernatant Solutions of the Ca Complex. A series of solutions were prepared using the stock so!utions of disodium HDDQ and Ca(XO&. Fortyfive-ml. portions of disodium HDDQ were added to 50-ml. volumetric flasks. Appropriate amounts of Ca(nO& and distilled water were added to bring the solutions up to volume. The solutions were allowed to stand overnight, and the absorbance of the supernatant of each was found. A linear plot was obtained. Effect of pH. pH study indicated t h a t the sensitivity of this determination decreased when the pH was less than 4, undoubtedly due to the formation of free acid. The optimum range for complexing is between pH 4-8 * Interfering Ions. Table I shows the effect of interfering cations upon the complesing of Ca+*. This was measured by the change in absorbance of solutions containing cations, as compared to a control. As can be seen from Table I, the prior removal of heavy metal ions is necessary in this Cai2 determination. Although other alka-

0.1

- - - Acidic soh. -Basic soh.

0.6

0.5

4 i 0.4 ;

5
v

I 0.3
4
0.2

Table 1. Influence of Interfering Ions on 5.50 mg. of Ca+2 in a Volume of 50 ml. Allowable concentration Interfering (p.p.m.) for % Relative &2% rel. to Ca+2 ion
A1+a

Ba +2

c o +2

0.1

0 0

0.2 0.4 0.6 0.8 M O L E FRACTION Ca +Yx)

1.0

c u +2 Fe +a Mg +2 Mn +2 Ni +2
Pb +* Sr +2

Figure 3. Constant molar method to determine the Ca complex composition; A - (x/lO)A plotted against x ( A is absorbance at 490 mp, x is mole fraction)
line earth ions do complex with HDDQ (S), they do not interfere under these experimental conditions. Application of Method. Spectrophotometric analyses were performed on several aquaria water samples. Five ml. of sample were added directly to 45 ml. of 0.1% H D D Q solution and allowed to stand overnight. The results of this analyses are presented in Table 11, as well as the results of a n EDTA titration method (2). The relative precision for HDDQ determinations has been found to be f1-20/,.
ACKNOWLEDGMENT

Zn +2

5 110 5 5 <5 110 10 5 15 110 20

4.55 100 4.55 4.55 100 9.10 3.54 13.6 100 18.2

...

Table It. Analysis of Aquaria Water Samples (5-ml. samples) EDTA IlDDQ method titration mg. Ca+* mg. Ca+2
0.763 0.323 0.032 0.777 0.859 0.766 0.323 0.033 0.777 0.859

of Quantitative Analysis, The Ronald Press Co., New York, 1956. (3) Li, J. B., unpublished thesis, 1966. (4) Organic Chemical Bulletin, Eastman

Organic Chemicals, Division of Eastman Kodak Company, Vol. 33, NO. 3

The authors thank V. B. Fish of Lehigh University for the elemental analyses.
LITERATURE CITED

(1961). (5) Rehwoldt, R. E., Boynton, E., J. Chem. Educ. 42, 648 (1065). (6) Thiele, J., Giinther, F., Ann. 349, 45 (1906). (7) Tyner, E. I., AN.~L.CHEM.20, 76 (1948). (8) Williams, M. B., Moser, J. H., ANAL. 25, CHEM. 1414 (1953).

(1) Baretto, A., Rev. quim. ind. (Rio de Janeiro) 14, No. 163, 18 (1945). (2) Benedetti-Pichler, A. A., Essentials

RECEIVED review February 24, 1966. for Accepted May 16, 1966.
VOL. 38, NO. 8, JULY 1966

1019