yield, affords a relatively simple method
for removing it from the transplutonium
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Diethylbenzene is as efficient a diluent
as xylene for the Aliquat 336-S-N03.
monium nitrate will minimize the solids
problem, which constantly confronts
and fission product lanthanide elements.
In addition, these results suggest the
industrial separation of yttrium and the
heavy lanthanide elements from the
light lanthanide elements in a multistage
system.
Although the primary purpose of this
separation is the recovery of the
trivalent actinide-lanthanide elements
from plutonium process waste solutions
before their final purification by the
group separation (1, 6), excellent de-
contamination is achieved from cor-
rosion products and a number of fission
products. Among these are iron,
aluminum, chromium, nickel, cesium,
strontium, barium, yttrium, zirconium,
and niobium, thus simplifying the sub-
sequent purification. Negligible extract
ability is exhibited by cesium (<0.01%)
and strontium (<0.1%). The extrac-
tion of ruthenium varied from 54-72%;
however, it is removed effectively in the
following group separation. No at-
tempt was made to increase the decon-
tamination further by scrubbing tech-
niques.
The trivalent actinide-lanthanide
elements are easily stripped from the
30% Aliquat 336-S-N03-xylene solution
into mineral acids or water. Dilute
hydrochloric acid solution is a con-
venient stripping agent prior to the
separation of the two groups.
Gravimetric Determination of Germanium in Germanium-Rich Alloys
Sir: Germanium-rich alloys are
widely used in the electronics industry,
and the difficulties associated with
determining germanium in these alloys
are well known. For the accurate
determination of this element the gravi-
metric method is still preferred. A
selective, gravimetric method is de-
scribed for determining germanium as
the oxide in various germanium-rich
alloys.
The proposed method is based on the
fact that germanium dioxide is relatively
insoluble in a solution of concentrated
nitric and sulfuric acids, and the diverse
sulfate salts are soluble. In using a
similar technique, Zuber (10) found that
germanium can be determined as the
oxide in a 12-wt. % germanium-
copper alloy by first dissolving the
sample in dilute nitric acid, evaporating
to dryness, and then adding concen-
trated nitric acid. Upon heating, the
copper salts become soluble, leaving
germanium dioxide which can be filtered
and weighed. This method, however,
is limited to alloys that are soluble
in nitric acid.
512 · ANALYTICAL CHEMISTRY
Doubtless, many other diluents can be
used.
Several experiments using macro
amounts of lanthanum indicated no
deleterious carrier effect at concentra-
tions of 10 mg. per ml.
By proper choice of conditions, the
radiochemist can effect high yields of
the transplutonium elements from many
metal impurities. Some of the signifi-
cant advantages of this method over
previous ones are as follows:
Relatively dilute solutions of
aluminum nitrate or other nitrate salts
can be used. The necessity of resorting
to such methods as evaporation or acid
deficient systems to produce highly
concentrated solutions of aluminum
nitrate is eliminated. In some cases the
concentration of aluminum nitrate
present from cladding material is
adequate.
Higher aqueous solubilities of the
actinide, lanthanide, and other elements
are possible than in systems requiring
concentrated aluminum nitrate.
Higher concentrations of free nitric
acid can be tolerated than in other
systems (2, 4, 5), thereby preventing
precipitation problems.
The neutron hazard which exists in
the lithium nitrate system is eliminated
by the use of aluminum nitrate.
In some situations the use of am-
The most convenient dissolution of
germanium-rich alloys is accomplished
by a solution of nitric, hydrofluoric, and
sulfuric acids (5). It is essential that
the acid solutions be evaporated at a
low temperature. Evaporations carried
out on the hot plate at 300° C. using
this solution did not give sufficiently
accurate results for germanium (2).
Apparently some germanium is lost as
a volatile fluoride. Citric acid has been
used by Cheng (2) in the analysis of
silicon-germanium alloys to complex
the germanium ions and keep them from
volatilizing in the presence of hydro-
fluoric acid. This method gives ac-
curate results for germanium only if the
impurities present (e.g., silicon) can be
volatilized in a mixture of hydrofluoric,
nitric, and citric acids.
Germanium can be determined gravi-
metrically as the magnesium ortho-
germanate (3, 7), or as the oxide after
precipitation with tannin (4~6‘), hydro-
gen sulfide (5, 8), or a solution of ß-
naphthoquinoline and oxalic acid (9).
Germanium tetrachloride distillates
added to hydrofluoric, sulfuric, and
both the analytical radiochemist and
the waste disposal engineer.
Excellent decontamination is achieved
from many corrosion and fission prod-
ucts associated with the trans-
plutonium isotopes.
ACKNOWLEDGMENT
The capable assistance of G. I. Gault
in the experimental work is gratefully
acknowledged. The author is indebted
to W. R. Laing for some of the analyses.
LITERATURE CITED
(1) Baybarz, R. D., Weaver, B., Leuze,
R. E., Nucl. Sci. Eng. 17, 457 (1963).
(2) Ferguson, D. E., U. S. At. Energy
Comm. Unclassified, Report, ORNL-
3408, p. 37, 1962.
(3) Maeck, W. J., Kussy, . E., Rein,
J. E., Anal. Chem. 37, 103 (1965).
(4) Marcus, Y., Abrahamer, I., J. Inorg.
Nucl. Chem. 22, 141 (1961).
(5) Marcus, Y., Givon, M., Choppin,
G. R,, Ibid., 25, 1457 (1963).
(6) Moore, F. L·., Anal. Chem. 33, 748
(1961).
(7) Ibid., 36,2158(1964).
(8) Ibid., 37, 1235 (1965).
F. L. Moore
Analytical Chemistry Division
Oak Ridge National Laboratory
Oak Ridge, Tenn.
perchloric acids can be evaporated on
the steam bath without loss of ger-
manium (5). The residue is ignited
and weighed as Ge02. The tetra-
chloride distillate can also be analyzed
volumetrically for germanium using
the iodimetric method, as modified by
Abel (1).
Conventional chemical methods for
the determination of germanium in
alloys often require dissolution of the
sample by Na202 fusion or separation
from the interfering elements by liquid-
liquid extraction, distillation, or in-
volved precipitation techniques. The
proposed procedure is simple, less
subject to error by manipulation, and
therefore allows greater accuracy.
EXPERIMENTAL
Procedure. In a 250-ml. high-
temperature polypropylene beaker dis-
solve a sample containing 100 to 1000
mg. of germanium alloy (small chips),
using an acid solution of 25 ml. of
distilled water and 10 ml. each of
concentrated nitric, hydrofluoric, and
sulfuric acids. Place a polyethylene
cover on the beaker and let the
sample react for 15 minutes. Remove TableAccuracy of Proposed Method
I.
the cover while washing with a minimum
amount of water. Start evaporating Weight of Rel.
the solution on a constant temperature Diverse elements present germanium , mg.“ error,
bath at a sample temperature of 70° and their weight, mg.° Taken Found %
to 75° C. and continue for 18 hours. Bi 150, Cu 40, Fe 44, In 59, Ni 48, Si 252,
When most of the nitric and hydro- Sn 135, Ti 22, V 68 106 105 0.9
fluoric acids have evaporated, the sul- Si 257 243 240 1.2
furic acid will cause the temperature to As 14, Co 32, Cu 60, Se 22, Si 364, Sn 200,
Te 32, Zn 62 324 329 1.5
rise and stabilize at 85° to 90° C. Be 15, Si 100 412 415 0.7
Wash down the sides of the beaker Cu 263, Si 377, Sn 144, Zn 119 476 474 0.4
using 8 to 10 ml. of water and evaporate Si 313, Sn 341 483 483 0.0
the suspension for an additional 2 hours. Si 2006 500 500 0.3
Transfer the precipitate to a 250-ml. Si 100 519 521 0.4
borosilicate glass beaker using water Si 546, Sn 62, Ti 5, V 5 585 583 0.3
as the washing agent. Police the beaker Al 30, Cd 75, Cu 158, Fe 27, Ni 16, Si 392, Zn 90 606 608 0.3
with a plastic scraper. Add 1.5 grams Al 31, Co 10, Fe 34, Mg 10, Si 30 647 648 0.2
A1 5, As 10, Fe 32, Si 182, V 21 655 656 0.2
of granular boric acid and 2 ml. of Cd 51, Cu 20, Fe 30, Se 10, Si 194, Te 10, Zn 107 681 681 0.0
concentrated nitric acid and evaporate Al 16, As 30, Bi 65, In 50, Si 166 744 742 0.3
carefully without a cover to the presence Si 300 749 746 0.4
of sulfur trioxide fumes. The use of Cu 48, Ni 6, Si 350, Zn 33 754 753 0.1
asbestos sheeting on the hot plate will Ag 45, Co 24, Ga 81, Hg 65, In 50, Mn 49, Se 60,
help to prevent the sample from bump- Si 94, Sn 14, Te 109 774 772 0.3
ing. Remove the sample from the hot Mean reí. error 0.4%
plate, cool and add 100 ml. of concen- “
All elements were added as elements.
trated nitric acid (sp. gr. 1.423 at 6
Average of 4 determinations.
60°/60° F.). Warm the sample to a
temperature of 70° to 75° C. and main-
tain this temperature for 10 to 15
minutes, so that the sulfate salts will
dissolve. Stir occasionally. There was some speculation that the
Cool the sample to 25° C. and under germanium precipitates collected by Table Effect of Various Acid
II.
the hood suction-filter germanium di- filtering the nitric-sulfuric acid solu- Solutionson Germanium Dioxide
oxide through a weighed, fritted 30-ml. tions might contain large quantities of Recovery
capacity porcelain gooch crucible which
Ge(S04)2 because of fuming of the
previously has been heated in a muffle Ger-
furnace at 750° to 800° C. Police samples with sulfuric acid. The pre- manium
the beaker thoroughly and wash the cipitates w'ere dried at 100° C. and sub- dioxide
mitted for x-ray analysis, which show'ed Components and volume re-
precipitate using 10 to 15 ml. of con- compositions of covered,
centrated nitric acid. Dry the gooch them to be almost pure Ge02. acid solutions," ml. mg.6
at approximately 250° C. for 10 min- Effect of Slow Evaporations and
utes on the hot plate and then transfer 100 glac. CHaCOOH, 10 H2S04 99.9
Boric Acid Addition. As the nitric 100 HN03, 10 H2S04 99.9
to the muffle furnace and heat at 750° and hydrofluoric acids evaporate from 50 HN03, 50 H3P04, 10 H2S04 99.8
to 800° C. for 10 minutes. Cool and the samples, silicon is completely llOHNOs 99.5
weigh the germanium dioxide. The volatilized as the fluoride. The sec- 100 abs. C2H5OH, 10 H2S04 98.6
gravimetric factor to convert the oxide 80 HN03, 20 H20, 10 H2S04 96.5
to germanium is 0.6941. ond evaporation after the addition of 60 HNOa, 40 H20, 10 H2S04 93.6
water helps to volatilize residual fluo-
RESULTS AND DISCUSSION rides and also aids in the formation “
All acids added in concentrated form
Table I show's the results obtained of a residue that is manageable. By and acid solutions containing Ge02 were
maintained at 25° C. for 2 hours before
when known quantities of germanium adding boric acid to the samples prior
to fuming with sulfuric acid volatile filtering.
(semiconductor grade) were doped w'ith Ge02 present 100 mg. in all cases.
6

various impurities. Twenty-twro ele- boron trifluoride is formed, providing a

ments are show'n not to interfere with
the method when the quantities listed in
the table are used. The purity of the
weighed germanium dioxide precipitates
was confirmed by optical emission spec-
trographic analyses.
An average relative error of 0.4% was
obtained after purposely making the
synthetic matrices of a troublesome
nature, as seen by the frequent appear-
ance of silicon and tin. Tin remains
soluble in the nitric-sulfuric acid solu-
tion, but readily hydrolyzes in concen-
trated nitric acid to form metastannic
acid. Iron and nickel, much in excess
of 50 mg., will cause interference. This
can be minimized by varying the sample
size for germanium evaluation. Anti-
mony cannot be prevented from hydro-
lyzing; lead and the noble metals inter-
fere. Blanks containing several metals
were run w'ith no precipitation or residue
formation noted.
final safeguard against loss of germa-
nium as the fluoride complex. The evap-
oration period need not be considered a
particular disadvantage, as samples can
evaporate overnight.
Acid Solutions Used. Table II
represents a search for an acid or
acid solution that would have the
most complete solvent action on the
diverse sulfate salts while leaving the
germanium dioxide insoluble. A com-
bination of nitric and sulfuric acids
met the requirements. The acetic-
sulfuric acid solution also made the
copper sulfate readily soluble, but
did not dissolve the iron and nickel sul-
fates as completely as the former solu-
tion. The mixture of nitric, phosphoric
and sulfuric acids appeared promising
initially but, because of its viscosity, it
filtered rather slowly and so was dis-
carded. Water, w'hen added to the
solutions, greatly increased the solu-
bilities of the various sulfate salts but
unfortunately also had a solvent effect on
the Ge02.
This experiment w'as conducted by
adding known quantities of Ge02 (water
soluble form) to the acid solutions which
were later suction-filtered, and the un-
dissolved Ge02 w'as w'ashed and weighed
according to the procedure previously
described. The Ge02 collected from
the ethanol-sulfuric acid solution filtra-
tion w'as washed with 10 ml. of absolute
ethanol instead of the regular nitric
acid w'ash.
ACKNOWLEDGMENT
The author thanks E. P. Bertin for
the x-ray analysis and A. M. Liebman
for the optical emission spectrographic

VOL. 38, NO. 3, MARCH 1966 · 513

analysis, which confirmed, respectively,
the identity and purity of the germanium
dioxide precipitates.
LITERATURE CITED
(1) Abel, G. J., Jr., Anal. Chem. 32,
1886 (1960).
(2) Cheng, K. L., Goydish, B. L., Ibid.,
35, 1273-5 (1963).
(3) Duval, C., “Inorganic Thermogravi-
metric Analysis,” p. 293, Elsevier,
Amsterdam, 1953.
(4) Hillebrand, W. F., Lundell, G. E. F.,
Bright, . A., Hoffman, J. I., “Applied
Inorganic Analysis,” 2nd ed., pp.
299-300, Wiley, New York, 1953.
(5) Kodama, K., “Methods of Quantita-
tive Inorganic Analysis,” pp. 209-11,
Interscience, New York, 1963.
(6) Krause, . H., Johnson, O. H.,
Anal. Chem. 25, 134 (1953).
(7) Mueller, J. H., J. Am. Chem. Soc.
44, 2493 (1922).
(8) Mueller, J. H., Eisner, A., Ind. Eng.
Chem., Anal. Ed. 4, 134 (1932).
(9) Willard, . H., Zuehlke, C. W., Ibid.,
16, 322 (1944).
(10) Zuber, J. R., Radio Corporation of
America, Somerville, N. J., private
communications, 1965.
W. W. White
Commercial Receiving Tube and
Semiconductor Division
Radio Corporation of America
Harrison, N. J. 07029

Rapid Preparation of Fatty Acid Esters from Lipids

for Gas Chromatographic Analysis
Sib : This paper describes a very rapid is followed by boiling the soaps with to a separatory funnel. About 20 ml.
technique for preparing methyl esters BF3-methanol in the same vessel for 2 of petroleum ether (b.p. 30-60° C.
from triglycerides and other lipids. minutes. This procedure resulted in reagent grade redistilled) is added to the
The method should find wide interest, quantitative conversion of the fatty separatory funnel. The funnel is
shaken vigorously for 1 minute and the
particularly in commercial fat and oil acids to methyl esters in a 10-minute
We had long been layers are then allowed to separate.
laboratories. operation. The methyl esters may then The lower aqueous layer is drained off
interested in extending the BF3- be floated out of the mixture using a and discarded. The petroleum ether
methanol esterification procedure (3) saturated salt solution. This salting out layer is drained through filter paper
to the direct formation of methyl esters technique almost completely overcomes into a 50-ml. beaker. The solvent is
from triglycerides, phospholipids, poly- the objectionable loss of lower fatty then evaporated on a 60° C. water bath
esters, and other lipids. Interesterifica- acids in the water layer of the original or removed by a stream of air at room
tion techniques were first explored. procedure. Quantitative recoveries of temperature. The esters are now ready
for GLC analysis.
However, even after refluxing a triglyc- fatty acid esters even from butter have The above procedure is readily
eride one hour with BF3-methanol, the been made.
transesterification was still incomplete. applicable to free fatty acids by adding
3 ml. of BF3-methanol to a 150-mg.
A transesterification technique was EXPERIMENTAL
sample of acids.
recently reported that uses benzene as a Reagents. BF3-Methanol Rea-
solvent combined with BF3-methanol gent. BF3 gas was obtained from DISCUSSION
(4)· the Matheson Co., Inc. One liter of
When fatty acids are esterified, a
A new approach using a rapid reagent-grade methanol, in a 2-liter
saponification technique that does not flask is weighed and cooled in an ice simple titration for free fatty acid is a
cause isomerization was used (1). This bath. With the flask still in the bath, good indication of the completeness of
BFS is bubbled through a glass tube esterification. However, when a tri-
into the methanol until 125 grams is glyceride or other lipid is converted to
taken up. This operation should be methyl esters, the amount of conversion
Table I. Fatty Acid Composition of a performed in a good fume hood, and is difficult to determine. Thin layer
Butter Sample by Gas Chromatog- the gas should not flow so fast that
chromatography was found to be an
raphy of Methyl Esters Prepared by white fumes emerge from the flask.
Modified BF3-Methanol Procedure (The BF3 must be flowing through the
Hil- glass tube before it is placed in and
GLC, ditch USDA until it is removed from the methanol,
Acid or the liquid may be drawn into the gas
% (3) (5) A fl
Saturated cylinder valve system.) This reagent
has an excellent shelf life and has been
C4 3.9 3.72 3.8
1.1 1.20 1.8 used up to two years after preparation.
c6
c8 1.0 0.77 0.8 Preparation of Methyl Esters from
Cm 2.4 1.09 1.4 Triglycerides and Other Lipids. Ap-
Cn 0.3 proximately 150 mg. of fatty ma-
Cm 2.7 2¡76 2.5 terial is added to a 50-ml. volumetric
C13 0.1 flask. Four milliliters of 0.5Ar meth-
C,4 9.7 8¡il 8.3 anolic sodium hydroxide is added to
C15 0.9 the mixture which is heated on a
Cl6 26.0 22 ¡41 24.4-28.8
0.5 steam bath until the fat globules go
Cl,
Cl, 15.4 11 ¡61 9.8-13.9 into solution. This step will take
C20 0.5 0.87 about five minutes. With some lipid
Unsaturated materials it may take somewhat longer.
Cm 1 =
0.1 0.12 Five milliliters of BF3-methanol is 0
C12 1 =
0.1 0.20 added to the flask and the mixture is
Cl4 1 = 1.4 0.84 boiled for 2 minutes. Enough of a satu- a a
C14 2 = 0.3 rated sodium chloride solution is added
C,e 1 = 1.4 2 ¡95 2 ¡

0.3 to the flask to float the methyl esters up

Cl6 2
Figure 1. Thin layer chromatograms of
=

Ci8 1 =
28.8 36 ¡72 27.6-39.2 into the narrow neck of the flask where
Ci, 2 = 1.3 5.68 1.1-5.0 they may be readily withdrawn with a lipids
Cl, 3 = 1.8 0.4-1.2 syringe. If the esters are solid or it is A. Methyl esters made from cottonseed oil by
C20-22 Ó ¡ 72 0.3 desired to recover the anhydrous acids, the modified BF3 methanol procedure
then the entire mixture is transferred ß. Cottonseed oil spiked with fatty acids

514 e ANALYTICAL CHEMISTRY