Volumetric Determination of Nickel in Steel

WILLIA3.I F. HARRIS AND THO31.4S R . SWEET

Ohio State Kniuersity, Columbus, Ohio

HE gravimetric determination, in which nickel is separated standardization agreed with each other to Rithin one part per
Tand weighed as nickel dimethylglyoxime, was proposed by thousand. A more readily recognizable end point was obtained
Brunck (3) and is widely used a t the present time for accurate in the standardization against the nickel solution.
Determination. The sample (2 grams for a 1% nickel steel)
analyses. Instead of being weighed, the nickel dimethylglyoxime was dissolved in 30 ml. of 1 to 1 hydrochloric acid. The iron
precipitate may be dissolved and the nickel determined volumetri- was oxidized with nitric acid, citric acid was added, and the
cally. A number of such methods have been proposed. Pomer- nickel was precipitated in the usual manner. A 1% solution of
anta ( 7 ) suggested the cyanide method, in which the nickel pre- the disodium salt of diniethylglyoxime was used as reagent.
However, a large quantity (40 ml.) of the reagent was added.
cipitate is decomposed with acid and the nickel is titrated with a The solution was not filtered before the precipitation of the
standard cyanide solution. Tougarinoff (10) dissolved the nickel nickel diniethylglyoxime.
dimethylglyoxime in acid, hydrolyzed the liberated dimethyl- The nickel precipitate \\as collected by filtration on an S. and
glyoxime to hydroxylamine, oxidized this with a ferric salt, and 8. black ribbon filter paper. After being washed, the recipitate
was dissolved by passing about 30 ml. of 9 S hydroc&oric acid
titrated the ferrous ion formed with potassium permanganate. through the filter. This was followed by washing the filter paper
Furman and Flagg ( 5 ) reported results obtained by a bromate well with hot water. The filtrate containing the nickel was
osidation of the hydroxylamine obtained from the nickel dimethyl eva orated almost to dryness (to 2 or 3 ml.) and was dissolved
glyoxime. Arsenite p a s added to react with the excess bromate. witlin a short time in 50 ml. of water. Sufficient ammonia was
added to produce the blue color of the nickel complex. A 0.2-
The excess arsenite u as then titrated with bromate. gram portion of the indicator was added. If the solution turned
Schwarzenbach has published a series of articles on the forma- red-orange a t this point, it was evaporated again to near dryness.
tion of organic complexes with metal ions. In his paper with Otherwise, an indefinite end point was obtained. The standard
Biedermann and Bangerter, he showed that calcium may be ti- Versenate solution was added t o the clear yellow solution until
the purple end point appeared. About 0.5 nil. before the end
trated with disodium dihydrogen ethylenediamine tetraacetate point the solution became red-violet. The end point was reached
(T’ersenate) using murexide as the indicator (8). He also pointed when a drop of the reagent produced the last visible color change.
out that in addition to calcium, murexide may be
used as an indicator for a large number of other
metal ions, including nickel (9). The method of
Table I. Analytical Results
titration of metals with Versenate, using a dye to Max.
indicate the end point, has been successfully ap- Dev. Q/ Ni
Sample So. Range of from F&d,
plied to the determination of hardness in water Weight. of Values, h l e a n , Mean KBS
and is being widely used for this purpose ( 1 , 2, 4 ) . Sample Material G. Detns. % Ni % Xi Value Value
S B S 82 Ni-Cr cast iron 2-2.4 3 0.998-1.000 0.001 0 , 9 9 9 1.00 ’
In the present procedure the nickel that has NBS 3 2 ~ N ~ - c ~ 2 3 1.17-1.21 0.02 1.19 1.19
been separated by the dimethylglyoxime precip- NBS 32C Xi-Cr steel 1 3 1.19-1.22 0.0‘2 1.20 1.20
NBS l l l B Ni-Mo steel 1-1.3 3 1.83-1.84 0.01 1.84 1.810
itat,ion is titrated with a st’andard solution of NBS 33C Ni steel 0.4 3 3.28-3.29 0.01 3.28 3.28
NBS 160 Cr-Mo-Ni steel 0.2-0.3 4 8.89-8.91 0.01 8.90 8.91
F’ersenate in the presence of the dye murexide.
a Provisional Bureau of Standards value.
The nickel dye complex has a yellow color, whereas
the dye is purple
- - in color when uncombined with
nickel. At the end point all the nickel has com-
INTERFERENCES
plexed with the Versenate and the color of the solution changes
from yellow to purple. A large amount of ammonium salts in the solution at the time
RE4GENTS of titration produced an indistinct end point. This interference
Dimethylglyoxime Solution. -4 1-gram sample of the disodium was eliminated in the procedure by evaporating the solution to
salt of dimethylglyoxinie was dissolved in 100 ml. of water. near dryness after the precipitate was dissolved in acid.
Indicator. A 0.2-gram quantity of murexide was well mixed Metals such as copper, cobalt, manganese, chromium, or iron
with 100 grams of finely ground sodium chloride, as suggested do not interfere when present in the usual quantities found in
by Betz and Sol1 in their procedure for the determination of
calcium in water samples (1). The murexide was prepared from steels or cast irons. The separation of the nickel from these
alloxantin by the method of Hartley (6). constituents by the dimethylglyoxime precipitation is complete
Versenate Solution. A 5-gram sample of disodium dihydrogen enough to eliminate interference. Furthermore, it was found that
ethylenediamine tetraacetate dihydrate was dissolved in water if 10 mg. of cupric, cobaltous, manganous, chromic, or ferric ions
and diluted to 1 liter.
Standard Calcium Solution. A 0.5-gram quantity of calcium were added to a known pure nickel solution, the volume of stand-
carbonate (99.97y0 pure) was dissolved in a minimum amount of ard Versenate required for its titration was not appreciably
3 S hydrochloric acid and diluted with water to 500 ml. affected, even though a dimethylglyoxime separation was not
Standard Sickel Solution. To 0.6 gram of nickel metal, 15 ml. made. Some difficulty xvm experienced in observing the end
of dilute nitric acid (1 part by volume of concentrated nitric
acid to 2 parts of water) was added. This was heated on a hot point with the manganese, chromium, or iron, because of the
plate until all the nickel dissolved. The solution was evaporated precipitates formed. If titration was delayed when the manganese
to less than 10 ml. and diluted to 1 liter with water. was present, the end point appeared too soon, probably because of
PROCEDURE adsorption of nickel ions on the manganese precipitate. How-
Standardization. The Versenate solution was standardized ever, this quantity of impurity is more than would ordinarily
against the standard calcium solution. Five milliliters of 1 to 1 be expected to contaminate the nickel dimethylglyoxime precip
ammonium hydroxide and 0.2 gram of the indicator were added itate.
to a 50-ml. aliquot of the calcium solution. Versenate wa8 added CONCLU SION s
from a buret until the color changed from pink t o purple. The
standardization was cheched with the standard nickel solution. The method given has certain advantages over the classical
To a 50-ml. aliquot of the nickel solution 5 ml. of 1 t o 1 ammo- gravimetric procedure and other existing volumetric procedures.
nium hydroxide and 0.2 gram of the indicator were added. This
solution was titrated with T’ersenate until the color changed It is not necessary to filter the solution before the dimethyl-
from yellow to deep purple. The results of the two methods of glyoxime precipitation if insoluble matter is present. This is
1062
V O L U M E 2 4 , NO. 6, J U N E 1 9 5 2 1063

particularly convenieiit, when analyzing samples coiitainiiig :ipyre- LITER4TLRE CITED

ciable carbon such as iron ores. In t'he present method, the carbon
is collected on the filter paper along with the nickel dimet,hyl-
glyoxime. This carbon is left' on the filter when the preripitate
is dissolved with hydrochloric acid.
The addition of an excess of dimethylglyosime reagent up to
seven times the theoretical amount required had no unfavorable
effect on the results. No harm is done if the reagent contami-
nates the precipitat'e. Therefore much less care need be exercised
in the addition of the proper volume of reagent than in most
other methods. In addit,ion,a much larger excess of the reagent
than is ordinarily permissible has the effect of slightly reducing
the solubility of the nickel precipitate.
The standard Versenate solution is easilj- prepared and is stable.
It, does not require rest,andardization a t frequent intervals, as
does the standard solution used in the cyanide method.
(1) Beta, J. D.,and Noll, C. -4,, J A m . W a t e r Works 9 s s o c . 42,
49 (1950).
(2) Biedermann, W., and Schwaizenbach, G., Chirnia (Suck ), 2,
56 (1948).
(3) Brunok, O.,2. angew. C h e m , 20, S34,1844 (1907\.
(4) Diehl, H.,Goetz, C. A., and Hach, C. C., J. Am. Water Works
Assoc., 42, 40 (1950).
( 5 ) Furman, N. H., and Flagg, 3. F., IND. ENG.CHEM.,A N ~ LED..
12, 738 (1940).
(6) Hartley, W. N., J . Chem. Soc., 87, 1791 (1905).
(7) Pomerantz, I. I., Zavodskaya Lab.,4, 966 (1935).
(8) Schwarsenbach, G., Biedermann, W., and Bangerter, I-., H e l i .
Chzm. Acta, 29, 812 (1946).
(9) Schwaizenbach, G., and Gysling, H., Ibid., 32, 1314 (1940).
(10) Tougarinoff, 11. B.,4nn. m c . BCZ. Bruxelles, 54B,314 (1934).
RIGEI\E D for rex iew Januarj 2 , 1 9 2 . -4ccepted February 14, 10.52.

Modified Signer Molecular Weight Apparatus

LAWRESCE RI. WHITE AND RICHdRD T. MORRIS
F'estern Regional Research Laboratory, .ilbany, Calif.

r IIE Signer inethod for the determination of molecular weights 3. The shape of the cover elioultl pcniiit the well to be coni-
r h a s been shon-n to be accurate and applicable to many types of pletely filled without forming air pockets. If the filling tube is off
center (toward t'he back in the vien- s h o m in Figure l), it facili-
organic compounds ( 1 , 2 ) . The method is based on the principle tates the removal of the mercury with a capillary suction tube
that, when tJvo isothermally insulated solutions are placed with after the determinat'ion is complete.
their vapors in contact, distillation take? place until the solutions 4. illthough ideally calibrated tubes for making the mcasuriiig
have the same vapor pressure. .kt the isopiestic point the solu- arms are not conimerrially available, satisfactory arms ran be
made from 2 X 0.1 nil. serological DiDets x-ith the t i m sealed.
tions are equimolar. -The graduation numbers should
The apparatus used for the determination consists essentially of he changed to read from the tip
two bulbs connected by a vapor bridge. Ope bulb holds the u p instead of from the top down.
reference solution and the other holds the unknown solution. 5 . The concentric-sleeve stop-
cock is made by drilling a 1-nim.
Provisions are made for introducing the solutes and solvent,, for hole perpendicular to the asis of
evacuating the apparatus before it is sealed, and for measuring the an assembled 7/15 joint and seal-
volumcs of the solutions. ing the small end of the outer 7/16
The chief deterrents to the use of this excellent method are that joint. The stopcock is turned
nith a wrench made from a short
the apparatus must be returned to the glass blower after each lengt,h of aluminum alloy tub-
second or third determination to have new filling tubes sealed on ing, 0.5 inch in outside diameter
and t h a t the filling tubes must be sealed off with a torch after the with '/,s-inch wall, that fit,s the
apparatus is evacuated. The sealing of the filling tubes must take q u a r e shoulder.
Tl-eighed samples of t'tie refer-
place in such a manner that no moisture is introduced into the ence and unknown compounds,
apparatus and that neither of the solutes nor the solvent is de- sufficient of each to make 0.05
composed in any degree by the heat of sealing. The sealing of t.he to 0.1 molal solutions a t equilib-
evacuated apparatus is a difficult manipulation for an inexperi- rium, are placed in their respec-
t.i\-e bulbs with micro weighing
enced glass blower and is potentially ha.zardous when the solvent tubes. One to 1.5 ml. of solrent
is flammable. This operation can be avoided through the use of is added to each bulb. The inner
the apparatus described herewith. sleeve is seated in the stopper
n-ith tjhe drilled holes in align-
APPARATUS AND PROCEDURE ment and the assembly is placed
in the base. The handles are used
The apparatus, shown drawn to scale in Figure 1, is similar to :o hold t,he stopper in position.
the one previously described ( I ) , except that the filling tubes that -%vacuumline (a good water as-
had to be sealed off for each determination have been replaced by pirator is adequate) terminating
in an outer 5 / 6 joint is inserted
a re-usable closure consisting of a spherical joint and a concen- through the wrench and attached
tric-sleeve stopcock. As these joints cannot be lubricated, they TO the 5 / e joint on the sleeve.
are placed within a mercury well to effect a completely airtight Immediately after the vacuum
seal. connection is made, mercury is
Figure 1. Sketch of poured into the well until the
The details of construction and the function of each part are Apparatus ioint is covered. Evacuation is
evident from the figure and the description of the filling of the A . Base ;,ontimed until about 0.25 1111.
apparatus. Although the dimensions are not critical, five details B . Stopper ni solvent has distilled from each
C. Inner sleeve nulb, then bhe sleeve is turned
should be kept in mind n-hile construct,ing the equipment. D . Cap
E . Steel spring about 90". Thevacuumconnec-
1. The angle of the two arms of the vapor bridge, Figure 1 , A , F . Cover iion and the wrench are removed,
6. Filling tube (offcenter) h e cap is placed on the open
should permit, the introduction of micro weighing tubes and H . Square shoulder
pipets directly into the bulbs. J . Handle end of the sleeve, and the spring
2. The volume of mercury in the well, the upper part of A , K . Serological pipet is placed over the cap. The
should be kept a t a minimum to provide better stability and to Standard taper and spheri- i'orer, with the joint lubricated,
decrease the weight of the apparatus. For this reason the joints cal joint sizes are shown on is seated in the base, so that the
right. Numbers in paren- tension of the spring will hold
a t the tops of the mercury well and inner sleeve were made from theses show. original joint
sawed-off joints of t.he sizes indicated in the figure. sizes The cap in position. Springs or