Determination of Zirconium in Steels Using p-Bromo- or p-Chloromandelic Acid JOSEPH J . KLINGENBERG 4ND ROLAXD A. P.IPUCCI' Xavier I-nirersity, Cincinnati, Ohio
washed well and the combined precipitates are ignited. The silicon is determined in the usual way. The remaining oxides are fused with potassium acid sulfate, dissolved in hydrochloric acid (1 to l), and united with the original solution. The combined solutions are made up to 250 ml., and 125 ml. is used to determine chromium, manganese, nickel, molybdenum (if under 0.5%), and iron. The remaining 125 ml. is used to determine zirconium as described. The presence of selenium causes the mandelate precipitate to appear somewhat brown but does not impair the final result.
4NDELATE method was found to be superior to the cupfer-
ylA ron phosphate method for the direct determination of zir-
conium in alloy steels. p-Bromo- and p-chloromandelic acids are somewhat more convenient to use than mandelic acid. Since Kumins ( 5 )introduced mandelic acid in 1947 as a reagent for precipitating zirconium in the presence of titanium, iron, aluminum, chromium, vanadium, thorium, cerium, tin, barium, calcium, copper, bismuth, antimony, and cadmium, the applicability and scope of the method have been considerably enlarged. Hahn ( 4 ) showed that the mandelate method p-as superior to thr phosphate method in the determination of small amounti: of zirconium. Successful separations from cobalt, magnesium, manganese, mercury, nickel, uranium, and zinc n-ere also achieved. Gavioli and Traldi (3) recommended the use of mandelic acid in the determination of zirconium in steels containing 0 . X to 3.65% of this element. S o interference was experienced from manganese, nickel, titanium, vanadium, molybdenum, cohalt, iron( II), magnesium, chromium, and copper. Astanina and Ostroumov ( 2 ) also found mandelic acid to be a highly selective and sensitive reagent for zirconium. Oesper and Klingeriberg (6) showed that p-chloro- and pbromomandelic acids also precipitate zirconium quantitdtively. These reagents possess certain advantages over mandelic acid, notably that a larger amount of precipitate results from the same amount of zirconium and that distilled water may be used as wash solution. The present work deals n-ith the application of these reagents to the determination of zirconium in steels containing a wide variety of alloying elements.
Table I gives the results on steels of the following composition: Element
Per Cent
Element
Silicon Manganese Chromium Zirconium Sulfur
0 , 6 0 4 ) . 90
Phosphorus Total carbon Sickel Molybdenum Copper
0.504.65 0.054.15 0.040 max.
max. max. mar. max. max.
The procedure outlined for determining zirconium was also tried on a wider variety of steels and alloys described in Table 11. Since samples of steel of these compositions containing zirconium were not available, a standard zirconium solution was added to the dissolved samples. Direct Weighing of Zirconium p-Bromomandelate. The possibility of weighing the zirconium halomandelate precipitate directly was also investigated. The same precipitation procedure was followed. However, the zirconium p-bromomandelate was filtered by means of a previously rreighed Selas rrucible. The precipitate n-as wished approximately ten times with distilled
PROCEDURE
Table I.
Rapid Determination of Zirconium in Steel. Three grams of the steel sample in a 150-nil. beaker is dissolved in 40 to 50 ml. of hydrochloric acid (1 to 3). (If the zirconium content is greater than 0.25%, the weight of sample may be correspondingly less.) The cooled solution is filtered on No. 31 Whatmaii filter paper to remove silica and any carbides which failed to dissolve. (Carbides could be destroyed by addition of 1 to 1 nitric acid and boiling the solution for some minutes. This has not been found to be necessary with the steels analyzed.) Twenty-five milliliters of a solution of 0.1 ,Zf p-bromo- or pchloromandelic arid is added with constant stirring, to give a total volume of around 100 ml. The mixture is digested for 20 minutes a t 80" to 85" C., cooled to room temperature, and filtered on a No. 40 Whatman filter paper. The precipitate of zirconium halomandelate is r5 ashed about ten times with distilled water. The paper and precipitate are charred slowly and ignited in a platinum crucible a t approximately 1000" C. The zirconium oxide is then transferred to a tared ryeighing dish and weighed.
Determination of Zirconium i n Steels Using \'arious Reagents
Steel Sample 1 2 3
p-Bromomandelic acid
0,056 0 056
... ...
? 6 7 8 9 10 11
12 13 14 15
FoZr = n-eight ZrOl X 0.74030 X 100 weight of sample
16
0'0i9 0.062 0.074 0,076 0 : 076 0.081 0.092 0.092 0.093 0.094 0.094 0.094 0.094 0.094
n. 094
For samples high in siliron, it is desirable first to remove the silica by dehydration in the usual manner. The residue from the eilira determination is fused ivith potassium acid sulfate, dissolved in hydrochloric acid ( 1 to l ) , and combined with the original filtrate.
17
18 19
Alternate Method for Chrome Steels If a Complete Analysis Is Desired. One gram of the sample in a 150-ml. beaker is dissolved in 15 ml. of perchloric acid (70%) containing one drop each of concentrated nitric and hydrochloric acids. The contents are heated until white fumes of perchloric acid form and red crystalline particles appear on the sides of the beaker. The beaker and contents are cooled, 10 ml. of water added, tlip contents digested for about 10 minutes to remove chlorine, cooled, and diluted to about 100 ml. The precipitate is then fijtered on a No. 31 Whatman filter paper to remove the silicon, zirconium, and any columbium present. The precipitate is
20
21 22 23 24 25 5
1
0.504.75
Per Cent 0,040 0.15 0.15 0.10 0.15
Present address, Broeman Chemical Co., Cincinnati, Ohio.
1861
Method ( 1 ) .
0 0 0 0 0 0 0 0 0
n
094 096 096 096 096 096 096 098 096
nqfi
0.098 0.104 0.104 0.104 0 104 0.104 0.104 0.107 0.108 0.108 0.116 0.116 0.116 0.136
Zirconium Determined, % Reagent p-ChioroMandelic Cupferron mandelic acid phosphatea acid 0.052 ... 0.055
... ... ... ...
... ...
0:076
...
0:0s1 0,092 0.092 0.093 0,094 0.094 0.094 0.094 0.094 0,092 0,092 0.094 0.094 0 096 0.098 ,.. ,..
0 : 099 0,099 0,099 0.104 0.104 0.104 0.104 0 104 0.104 0 : io8 0 108
0.113 0.116 0.113 0.136
0.056 0.058 0.061 0,061 0.062 0.067 0.074 0.074 0.078 0.076 0.081 0.091 0.092 0.093 0.096 0.094 0.094 0.092 0.094 0,094 0.094 0.096 0.096 0.096 0.096 0.092 0.104 0.096 0.096 0.096 0,099 0.104 0.104 0.104 0.102 0.104 0.104 0.104 0.108 0.108 0.116 0.116 0.113 0.136
0.055 0.057 0.061 0.061 0.061 0.065
0 : 077 0.076 0:0s1
...
0: 092
...
... 0:093
... .
.
I
...
... ... ... 0:093 0.093
0.094 0.095
...
0 : io3
... , . .
.,. ... . , ,
...
...
o:ii4
...
0' li4
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
