ANALYTICAL CHEMISTRY
1862
Table 11. Determination of Added Zirconium in Various Steels and Alloys Composition of Steel or Alloy, hln C Cr
~
70
Si
S
0.29
0 020
0.009
0.75
0 40
0.38
0 019
0.014
0.65
0 07
0.58
0 015
0.008
1.44
0 08
17.62
0.42
0 015
0.012
0.51
1 01
16.00
...
0.20
......
0.79
0 16
0.015
0.76
0 36
0.7
1.73
0.29
......
0.79
0 019
0 012
1.79
0 07
17.41
10.14
..
Cb, 0 . 7 2
0.51
0 019
0.012
0.60
0 09
12.10
0.15
0.03
0.29
0 015
0.009
0.90
0 43
0.55
0.63
0.25
0.05
0 081
0,019
1.64
0 38
...
...
.....
..
0 027
0.018
0.27
0 04
...
...
.. ..
0.28
0 012
0.013
0.5:
0 10
1.23
3.30
0.15
......
0.19
P
...
0008
0 19
Ni
M O
0.97
0.02
0.23
......
17.41
8.90
0.13
9.21
..
Cu, 0 . 0 6 Se. 0 . 3 4 0 Ti, 0 . 5 9
15 07
0 05
Other
Zirconium Added, Gram
Cupferron phosphate 0,0028 0,0042 0.0028 0.0042 0.0028 0.0041 0.0028 0.0041 0.0027 0,0042 0.0028 0,0042 0.0029 0.0042 0.0028 0.0041 0.0027 0,0041 0,0028 0,0042 0.0028 0.0041 0.0028 0,0042
AI, 0 . 0 4 Sn. 0 006
...... ......
Co. 0 . 39 Fe. 8 . 0 3
75.35
cu. 0.09
0.68
0 018
0 013
1 63
0 12
16 29
25 60
Table 111. Determination of Zirconium Halomandelate by Direct Weighing Zirconium Determined, % Zr p-bromotetramandelate 0.096
n
ZTOl 0.094
n
09.5
0. 0Si
n94
0 OS0 0 081 0 054 0 054 0 074 0 101 0 096 0.135
0.081 0.055 0.056 0.076 0.104 0.098 0.136
watei and twice with 95% ethanol, dried in the oven for 15 minutes a t 100" C., cooled, and weighed. The amount of zirconium present u as calculated on the basis that the precipitate formed is zirconium tetra-p-bromomandelate. T o check the results, all precipitates were ignited to the oxide and v-eighed. Results are given in Table 111. DISCUSSIO-
p-Chloro- and p-bromomandelic acid were found to be equallv as accurate as mandelic acid in the determination of zirconium in steels and related alloys. -411 three reagents gave results u hich agreed satisfactorily with the generally accepted cupferron phosphate method ( I ) , and were superior to it in ease of manipulation and time required for analysis. Although mandelic acid is satis-
6.66
S. 0.192
0.0028
0.0028 0,0042
0.0042
Reagent _____ p-Bromomandelic acid
p-Chloromandelic acid
0,0027 0.0042 0.0028
0.0042
0.0028
0.0040 0.0027 0.0042
.... ....
.... .... .... ....
0.0027
....
0.0042
0,0027
....
0.0041
....
0 0043
0.0028 0.0029 0.0043 0,0028
....
....
0.0043
....
....
0.0042
....
0.0042 0,0027 0.0043 0,0028 0.0042
0.0027 0.0028
....
....
0.0041 0.0027
....
....
O'OOi2
....
0.0028
0.0041
....
factory as a reagent, the halo derivatives are believed to be superior because: 1. A larger amount of precipitate is obtained per given amount of zirconium present. This is particularly helpful a t the low concentration of zirconium present in steels. 2. Distilled water can be used as a wash solution. 3. Less time is needed for the format.ion of the zirconium halomandelate precipitate. 4. Direct weighing is possible, although in this present. work noadvantage over ignition to the oxide was observed. a. The increased cost of the halomandelic acid compounds is offset by the fact that only one tenth as much reagent is needed per analysis. p-Bromomandelic acid is preferred over p-chloromandelic acid as a reagent, although the difference between them is small. As far as is known, these reagents are not commercially available. Details of method preparation are available from the authors. LITERATURE CITED
-4m. SOC. Testing Materials, "Methods for Chemical Analysis of Metals," $STM Designation E 30-45 (1946). (2) Astanina, -4. A,, and Ostroumov, E. A , J . Anal. Chern., U.S.S.R.,
(1)
6 , 27-33 (1951).
Gavioli, G . , and Traldi, E., J.Iron Steel Inst., 167, 167 (1951). Hahn, R. B., ANAL.CHEM.,2 1 , 1579 (1949). (5) Kumins, C. A , , Ibid., 1 9 , 3 7 6 (1947). ( 6 ) Oesper, R. E., and Klingenberg, J. J., Ibid., 21, 1509 (1949). (3) (4)
RECEIVED for review July 25, 1952.
Accepted September 8, 1952.
New Spray Reagents for Paper Chromatography of Reducing Sugars LOUIS SATTLER, Brooklyn College, Brooklyn, N. Y . , AND F. W. ZERBAN, New York Sugar Trade Laboratory, New York, N. Y .
SUMBER of spray reagents are in use by workers in the
A field of paper chromatography of sugars.
Many of these reagents have such disadvantages as limited stability, production of fading spots, or a concomitant discoloration of the background. The authors find that a 0.3% ethyl alcohol solution of p-aminohippuric acid is very sensitive and stable, and when used a t 140' C. for 8 minutes, the spots which are produced do not fade and there is an almost imperceptible background discoloration. Under ultraviolet illumination the spots fluoresce strongly. The common hexoses and pentoses produce orange spots, and the sensitivity is 1 microgram with ultraviolet light on unirrigated paper. A spray reagent containing 3y0 phthalic acid reveals 0.25 microgram of glucose and 1 mirrogramof fructoseunder ultraviolet
illumination. I n ordinary light four to five times that amount of sugar is required to produce orange-red spots. This reagent also will detect reducing disaccharides such as maltose and lactose, and easily hydrolyzed nonreducing sugars such as sucrose and raffinose. Under similar conditions, 4-aminoantipyrene has a slightly lower sensitivity, and it must be used at 150" C. for 10 minutes. ACKNOWLEDGMENT
The writers express their thanks to John D. Nantz of the Sational Aniline Division of Allied Chemical & Dye Corp. for samples of the compounds. RECEIVED for review March 19, 1952.
Accepted September 3, 1952
