Colorimetric Determination of Nickel in Steel
G. R. MAKEPEACE AND C. H. CRAFT
Metallurgical Laboratory, Menasco Manufacturing Company, Burbank, Calif.
The method of Murray and Ashley for the colorimetric determina-
tion of nickel in steel is outlined and criticized. Experimental data
are presented on the stability under various conditions of the red
color of oxidized nickel dimethylglyoxime. A modification of the
method is described which gives a highly stable and readily repro-
M I-RRAl- and Ashley ( 1 ) have presented a method for dc-
veloping quantitatively the red color of oxidized nickel
dimet hylglyoxime.
The sample is dissolved in dilute nitric acid (in the case of diffi-
cwltly soluble chromium-nickel steels, a mixture of nitric and
hydrochloric acids is used). To a n aliquot of suitable size the
following additions are made: citric acid to prevent' iron prc-
cipitation a t the final pH, bromine water to oxidize nickel, am-
monium hydroxide in sufficient quantity to bring the pH to 8-9,
and dimethylglyoxime in the form of 1% solution in alcohol to
develop the red nickel color. The solution is diluted to known
volume and the color is compared. A wave length that has bcen
recommended for spectrophotometric reading is 530 mp.
Although t,he method of Murray and Ashley has been wed with
some succcss in this laboratory and elsen here, it has certain un-
desirable characteristics. The color developed in the nickel solu-
tion shows continuous change from the instant, of addition of di-
methylglyoxirne, tending for the first few minutes to become more
int'ense, then to fade. Murray and Ashley note the phenomenon
of the color intensity cliange a t 530 mp with time, and present a
.*et of curves illustrating its characteristics. At no time is there
:t period of constant t,ransmittance in the transmittance 1's. time
cwve of sufficient duration to give a time margin for truly repro-
ducible reading.
Bot,h the slope and the time of the minimum of the traiismit-
t m c c PY. time curve appear to be changed by c-hanges in the
nickel concentration of the solution used for making the curve.
Small differences in p H a t t,he time of adding dimethylglyoxime
to otherwiqe similar. solutions were found to have pronounced
effects on the shzipe of the transmitt,ancae 1's. time curve, altering
bot,h thc 4ope : i d tht, position of the minimum to :I marked dc-
grce.
If 807; of the recommended amount of ammonium hydroxide
ih used, no color a t all develops (pH 6.8). (All pH measurements
were made with a k e d s & Northrup potentiometric pH meter
using a standard glass electrode and a calomel-saturated potas-
sium chloride reference electrode.) With 90% of the amount re-
quired (pH 8.1), the rate of color development is slow and rate
of fading is high. If the concentration of ammonium hydroxide
is high, the rate of color development is high and the rate of fading
slow, solutions retaining substantially all their color for several
hours. If as milch as four times the recommended amount of
ammonium hydroxide is used, the color is completely developed
in about 30 seconds. A second effect enters, however-a rapidly
increasing interfcwnce of the iron in the solution. Ultimately
iron hydroxide is precipitated under these conditions. Critical
examination of the pH range within which the Murray-.Miley
method is ~rorkableshows it t,o be less than 1 pH unit, pH 8.2 to
8.7. I t waa found that the amounts of tartaric acid, bromine
water, and dimcthylplyoxime solut'iori were not' critical above
a minimum value if sufficient extra ammonium hydroxidc was
added to neutralize increases in the acid content.
I t \va- concluded that the unmodified method of Mui~rayand
Ashley, while suitable for many purposes, is not sufficiently re-
producible (at least without elaborate precautions) to meet the
need3 of this laboratory. I t does, however, have the virtue of
being rapid. I t was in a n effort to reta.in its speed while improv-
ing its accuracy that this research was undertaken. The original
method recommends dissolving thc sample in 1 to 1 nitric acid,
375
ducible red color, and i s particularly suitable for routine work be-
cause of its rapidity and manipulative simplicity. Copper and cobalt
interfere only slightly; the other elements ordinarily found in steel
d o not interfere. The accuracy of the method is comparable to that
of routine gravimetric procedures.
except difficultly soluble rhromium-nickel steels for which a mix-
ture of equal parts of nitric and hydrochloric acids is suggested.
Since many of the st,eelsanalyzed in this laboratory contain about
17; chromium and do not dirsolve completely in nitric acid or
rapidly in hydrochloric acid, a method was tried of decomposing
first in an "acid mixture" (133 ml. of 1.82 sp. gr. sulfuric acid and
167 ml. of 8575 phosphoric acid per liter of solution) and then
completing dissolution by adding 1 to 1 nitric acid. For 170
rhromium steels the method was more rapid than decomposing
with hydrochloric acid and more nearly complete tha,n dissolving
in nitric acid. S o effect, on the development of the nickel color
was observed.
I n the effort to produce a nickel color that would be quickly
formed, stable, and reproducible without elaborate control of the
ctonditions of development, various other basic substances were
tried in place of ammonium hydroxide. Among them were so-
dium carbonate, sodium tetraborate, sodium orthophosphate,
potassium pyrophosphate, and sodium hydroxide, all in the con-
centrations required to produce the proper pH range for color
development. S o n e proved satisfactory. Other oxidizing
agents such as sodium perborate, potassium chlorate, potassium
iodate, and hydrogen peroxide were tried in place of the bromine.
Only ammonium peroxydisulfate in the presence of silver ion
showed promise, but the desired degree of color stability was not
achieved with ita The effects of solution temperature on color
development were studied, but no worthwhile modification utiI-
izing temperature control was found. Color development a t high
ammonium hydroxide concentration followed by reduction of t h e
.solution pH to 8.5 to prevent iron precipitation proved unwork-
able.
It was realized at thi.; point t'hat tartaric acid will hold iron in
solution at a considerably higher pH than will citric acid. Ac-
cordingly, the citric acid n-as replaced by tartaric. Upon experi-
ment it was discovered that, while iron will develop an interfering
color in tartrate solutions made basic with ammonium hydroxide
nearly as quickly as in citrate solutions under the same conditions,
the interference and any precipitate that may form can be cleared
up rapidly by increasing the pH still further with sodium hydrox-
ide. This is not true of citrate solutions. While the nickel color
develops ,slowly and incompletely in very dilute sodium hydroxide
solutions of pH 8 to 9 and not a t all in more concentrated solu-
tions, the color, once developed, remains stable over long periods
of time even in rather strongly basic sodium hydroxide solutions.
In view of these fact?, the folloning approach wax tried:
The sample n-as treated with tartaric acid and bromine and
made strongly ammoniacal. Then the dimethylglyoxime solu-
tion was added. 17nder these conditions the rolor developed
rapidly. hfter 1 minute, sodium hydroxide was added. .%iter
2 to 3 minutes the increase in iron interference which had taken
place in ammoniacal solution cleared up completely and the color
hecame stalile. S o furthvr change in color and conrequently in
transmittanc-e at ,530mp ~vaqobserved. The reading a t 24 hours
was identical n-ith the reading 5 minutc3 after adding dimethg-l-
glyoxime.
PROCEDURE
Since these results seemed very encouraging, a procedure was
devised to make use of them and was used in all the studies here-
after reported. High-purity reagents must be used. Particular
376 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 16, No. 6

attention should be paid to the witability of the tartaric acid and

of the dimethylglyoxime.
Decompose a 0.25-gram sample in 20 ml. of an acid mixture
(133 ml. of 1.82 sp. gr. sulfuric acid and 167 ml. of 85% ortho-
phosphoric acid per liter of solution). Steels containing little
chromium may be dissolved directly in 8 N nitric acid. Stainless-
type steels may require the use of hydrochloric acid. Cautiously
add 10 mi. of 8 N nitric acid and boil to expel oxides of nitrogen.
Transfer the solution to a volumetric flask of suitable size and
dilute to the mark. Transfer by pipet to a 100-ml. volumetric
flask an aliquot of the diluted solution containing between
0.05 and 0.3 mg. of nickel. Add to it, mixing after each addi-
tion, 5 ml. of a 20% tartaric acid solution, 5 ml. of saturated
bromine water, 10 ml. of 0.90 sp. gr. ammonium hydroxide, and
5 ml. of a 1% solution of dimethylglyoxime in methyl alcohol.
(Occasional difficulties in development of color and in fading upon
addition of sodium hydroxide have been traced to impure or
partially decomposed tartaric acid and dimethylglyoxime. C . P .
reagents are not uniformly satisfactory in this respect. Impure
tartaric acid interferes with development of color upon addition
of dimethylglyoxime, in extreme cases preventing any color
formation a t all. Impure dimethylglyoxime results in a fading of
the color upon addition of sodium hydroxide. The fading may
take place very rapidly or slowly, depending on the degree of
impurity. Both difficulties can be overcome by special treat-
ment. Addition of a second 5-ml. portion of bromine water after
introduction of the dimethylglyoxime ensures complete color de-
velopment. Difficulties with the dimethylglyoxime reagent can
be overcome by acidifying the alcohol solution with dilute sulfuric
acid and adding enough bromine water to color it yellow. This I I I I I I
should be done 15 to 30 minutes before it is used. Occasional 350 400 450 500 550 600 6.50
small further additions of bromine water are necessary to keep
the solution yellow. The treated reagent is usable for only a few Wovdenyth /k m p
hours.)
After 1 minute add 10 ml. of 6 N sodium hydroxide solution Figure 1. Per Cent Transmittance vs. Wave Length
and dilute to the mark. After 5 minutes, transfer the solution Curves lor Beuemer steel blank and C.P. nickel nltratc solution as read on
to the optical cell and compare the transmittance a t 530 mp with Colenlan Universal spectrophotometer (35 mp band .widlh)
that of pure water.
Two transmittance us. wave-length curves were prepared, one They were prepared according to the method previously out-
from National Bureau of Standards Bessemer steel 10d contain- lined, and the points so obtained were plotted on semilog paper
with the per cent transmittance of the sample compared with
ing substantially no nickel, and one from a nickel solution made water a t 530 mp as the ordinate and the per cent of nickel in the
from C.P. nickel nitrate. They are shown in Figure 1as read on a steel as the abscissa. I n this fashion three transmittance us.
Coleman Universal spectrophotometer. A B c k m a n spectro- concentration curves were obtained, for 0 to 1%, 1 to 2.5%, and
photometer, with a much narrower wave band than the Coleman, 2.5 to 5.5% nickel steels. A total of 27 concentrations was used
in obtaining the three curves.
gave a similar curve for the nickel solution; the positions of the
maxima and minima were identical. Appreciable interference of The color was found t o follow the Beer-Lambert law very ex-
the blank (Bessemer steel), however, did not occur on the Beck- actly when read a t 530 mp; therefore the transmittance US. con-
man instrument until wave lengths as short as 470 mp were centration curves, when plotted as described, were straight lines
reached. over the entire range utilized.
From a study of these curves it was decided that the most satis- No one of the 27 points determined from the National Bureau
factory wave length for reading the transmittance of the nickel of Standards samples deviated from the transmittance us. con-
color in steel on a Coleman Universal spectrophotometer, which centration curves plotted from them by more than 2% of the total
has a wave band width of 35 mp, is 530 mp, the wave length origi- nickel present in the steel in the case of steels containing more
nally suggested for the method of Murray and Ashley. This se- than 1% nickel. No one of the points deviated from the trans-
lection was made on a basis of minimum interference of the blank mittance US. concentration curve by more than 0.02% nickel (2
and maximum interference of the nickel color. For instruments “points”) based on the total analysis of the steel in the case of
with a wave band much narrower than 35 mp, such as the Beck- steels containing less than 1% nickel. These points were estab-
man photoelectric spectrophotometer, a lower setting such as 480 lished by single determinations, not by averages of groups of de-
or 490 mp seems to be preferable, since the lower value is closer terminations. The differences between the high and the low
to a minimum of the nickel curve and since iron interference is values on the National Bureau of Standards reports sent with
small in this range with such an instrument. Presumably, it each steel are as great as 1.77, of the total nickel present in the
would be possible to use for both spectrophotometers a wave- steel in the case of steels containing more than 1% nickel. Dif-
length setting a t the 470 mp minimum of the nickel curve, if a ferences of as much as 0.021?4 of nickel (2 “points”) based on the
blank prepared from a steel free of nickel were used as the ref- total analysis of the steel are listed in the case of steels containing
erence solution, thus canceling the effect of iron interference. less than 1%nickel.
For colorimeters using filters one probably would do best to se- Reproducibility was checked by making five complete deter-
lect a filter with a rather sharp cutoff a t about 450 mp, passing no minations by the authors’ method on National Bureau of Stand-
light of shorter wave length. This selection is indicated to elim- ards nickel steel 33b containing 3.48% nickel. Using the trans-
inate interference due to the color of the iron present. Increased mittance US. concentration curve established for steels containing
sensitivity can be obtained by further restriction of the wave 2.5 to 5.5% nickel, the average value of the five determinations
length of light used for comparison to the range of maximum in- was 3.48% nickel. The maximum deviation from the average
terference of the nickel color. value was -0.05% nickel. High and low values on the National
Bureau of Standards report are 3.51 and 3.46% nickel, respec-
Samples were taken from a series of National Bureau of Stand-
ards nickel-containing steels and mixtures of these steels t o cover tively. The method appears to be capable of the high order of
in small steps a series of nickel percentages from 0.002 to 5.12. reproducibility neressary for precise steel analysis.
June, 1944 ANALYTICAL EDITION
SENSITIVITY
Tests were made to determine the sensitivity of the method to
small variations in procedure. It was found that the tartaric
acid, bromine water, and dimethylglyoxime added could be
decreased 25y0 or increased 100% without affecting the re-
sults. The ammonium hydroxide may be decreased 20% or in-
creased 507, without effect. Approximately the same range of
values holds for the sodium hydroxide. It was determined that
the time elapsed between adding the dimethylglyoxime and the
sodium hydroxide i. not ciitical SO long ar it exceedq 1 minute-
Le., color development iq complete in less than 1minute.
Three identical samples equivalent to a standard steel contain-
ing 0.60% nickel were prepared, using for each sample 0.125 gram
of National Bureau of Standards Bessemer steel 10d and 0.125
gram of nickel-chromium stee1.32~. To sample 1 the sodium hy-
droxide, which arrests color development as well as preventing
iron precipitation, was added 30 seconds after adding di-
methylglyoxime; to sample 2,jminutesafter adding the dimethyl-
glyoxime; and to sample 3, 10 minutes after adding the di-
methylglyoxime. In each case the solution was diluted to the
volumetric mark and mixed immediately after adding the sodium
hydroxide. Transmittance readings in each case were taken 10
minutes after adding the sodium hydroxide. The results, ex-
pressed in terms of the analysis of the steel as read from the 0 to
l.y0nickel curve, averaged 0.599% nickel with a maximum devia-
tion from the average value of 0.0057, nickel.
INTERFERENCES
The method wab tested for interference by copper, cobalt, tung-
sten, molybdenum, chromium, and vanadium. The small
amounts of copper (less than 0.2%) present in the usual steels did
not interfere. Copper, when present to the extent of 0.50(7, in
the steel, caused a positive nickel error of 0.027,. Cobalt, tvhen
added to thr sample equivalent to 2.57, in the steel, caused a posi-
tive error of 0.037, nickel. Both elements were tested for inter-
ference on a <ample of +el containing 0.6Ovp nickel. The inter-
Identification OF Nornicotine in Tobacco
C. V. BOWEN AND W. F. BARTHEL
U. S. Department of Agriculture, Bureau of Entomology and Plant Quarantine, Beltsville, Md.
THE4, rather common occurrence of nornicotine in tobacco
(3, 6, 7 ) indicates the need of a reliable qualitative means
of identifying this alkaloid when present with nicotine.
Shrnuk (8) identified nornicotine in such a mixture after
extracting the ether-soluble material from alkalized plant ma-
terial, by forming the alkaloid picrates, recrystallizing from hot
water, and methylating the mixture of picrates. He attributed
the resulting elevation in melting point of the picrate to the
conversion of nornicotine to nicotine.
This procedure has several serious drawbacks. The ether
extract of the alkalized plant material will contain pyridine and
other amines, not all of which are removed by “blowing”. These
compounds as well as the alkaloids form picrates. The re-
crystallizations that occur before and during methylation will
tend to remove these amine picrates but a t the same time to
eliminate the picrate of the minor alkaloid. If the minor al-
kaloid is present in small amount, it may be lost in the recrystal-
lization of the original picrate. Since the mixed picrates before
methylation have a melting point lower than that of nicotirie
picrate, and, being solid, require the addition of liquid for the
methylation, it is possible for a fractional crystallization to occur
with the formation of new picrate crystals richer in nicotine
content and consequently having a higher melting point. Such
a rise in melting point could easily be misinterpreted as being
due to methylation of nornicotine, while in fact the alkaloid
377
Table I. Analysis of Steels
Sample 50a Sample 132
Bureau of Aut,horr‘ Bureau of Authors’
Standards method Standards method
I “/r 70 %
Tungsten 18.25 6.29
Chromium 3.52 4.09 ..
Vanadium 0.970 1.64
Nickel 0.045 0:Oi 0.095 o:i3
Molybdenum .. .. 7.08 ..
ference of the other elements mentioned was determined by wing
the method without modification of any sort to analyze for nickel
in two Bureau of Standards tool steel samples, 50a and 132.
In view of the extreme conditions in these two analyse5 and
the small error in nickel in each case, it was concluded that these
elements do not interfere 11-ith the determination to any appre-
ciable extent. In the analysis of ordinary chromium-nickel stain-
le?. steel., no interference by chromium was observed.
A D V A N T A G E S OF M E T H O D
The most important advantages of the method are its rapidity
and its freedom from manipulation9 requiring exceptional pre-
rautions or a high degree of analytical skill. It is well suited for
routine use. When a group of five samples was analyzed by a
worker only recently familiar with the method, the total elapsed
time, exclusive of weighing, was 1 hour and 10 minutes (reTults
reported above in paragraph on reproducibility). If a large num-
ber of samples is run a t one time, one thoroughly familiar cvith
the method can reduce the time required per sample to about 8
minutes.
LITERATURE CITED
(1) Murray and Ashley, IXD.ESG.CHEM..
~ A L ED.,
. 10,1 (1938).
picrate originally present may have been simply rendered richer
in nicotine by recrystallization. *Such a recrystallization proves
neither the presence nor the absence of nornicotine.
The proposed method differs from that of Shmuk in the
isolation of the alkaloids and in the position of the methylation
step. The steam-volatile tobacco alkaloids are separated from
all other amines and methylated before the picrate is formed.
The melting points of the picrates formed are compared before
and after methylation. Since they are not recrystallized no
fractional crystallization can occur.
Markwood (6) introduced methylation as a step in the deter-
mination of nornicotine, but since his method did not depend on
melting points, he failed to report the melting point of methylated
nornicotine picrate as an indication of the formation of nicotine.
The method presented here is based on the quantitative methyl-
ation of the nornicotine and also on the elevation of the melting
point of the alkaloid picrate. Consequently, the methylation
of nornicotine to nicotine was investigated. The nornicotine
used in preparing the standard solution was identical with that
used by Markwood ( 7 ) , had been isolated from Robinson’s Me-
dium Broadleaf, a strain of Maryland tobacco, and formed a
picrate melting a t 190-191” C. The absence of nicotine was es-
tablished by finding no alkaloid in the distillate after treating a
sample with nitrous acid, making the aqueous solution just basic
to phenolphthalein, and steam-distilling.