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E . G .

R O C H O W
THE UNIQUE ELEMENT
Slabs OfgcmurniUm. Abo
is t ht pofycrystdfim- and
GERMANI UM
Aside from semiconductors, germanium has several potentially important
uses such as for elastic and viscous polymers, alloys, and therapeutic com-
pounds. The missing link is research
ost chemists make a mistake about germanium.
M They think of it in terms of transistors and solid-
state physics, and thus dismiss it as a rare element which
has important but highly specialized urn. It is true
that germanium now has no practical connection with
the chemical arts of metallurgy, organic synthesis, or
heavy chemicals, but each element has its own growth
potential. Germanium goes beyond this-it is so dif-
ferent and special that it warrants a long hard look by
those who have their minds on the future.
Elements that are familiar emerged early and proved
their worth by satisfying human needs. They emerged
because they were readily available, either in the native
form-e.g., sulfur, gold, silver, and copper-r in the
form of minerals which investigators learned to reduce-
e.g., tin, iron, and lead.
As chemistry advanced, experimental means for
recognizing a great many new elements improved.
Most elements are metals, and therefore the flow of
new materials during the 18th and 19th centuries re-
sulted mostly in commercial adoption of new and
superior metals such as nickel, cobalt, manganese, and
chromium. Of course, isolation of oxygen, chlorine,
and nitrogen led eventually to new arts too.
.*
BENDING OQ0 ~~ 8 0 - 1 0
RAW MATERIAL CHLOWNATION HYDROLYSIS
PUWFlCATlON GSCL
32 INDUSTRIAL AND ENGINEERING CHEMISTRY
Not all new elements were discovered in response
to need, nor were uses developed soon after discovery.
Development of uranium and tungsten, for example,
lagged a long time, as did bromine, fluorine, and beryl-
lium. I n fact, even though all elements in the periodic
table are known, fewer than half are utilized to any
substantial degree. Yet with each element and its
unique properties, we can do things we have not been
able to do before. Inorganic chemistry has been that
slow in development.
Instead of forming a distinctive binary mineral com-
pound of its own, germanium crystallizes with many
other elements. Mendeleefs prediction of its existence
initiated a search, and finally it was found in minor
amounts closely associated with zinc, silver, copper,
arsenic, and iron. However, this high degree of dis-
persion is now an asset rather than a liability: ger-
manium can be recovered at will in rather large quan-
tities with existing plant facilities for winning copper
and zinc. Separation procedures are simple and re-
liable. Present and potential producers assure us that
usable quantities can be made available immediately.
Reserves of germanium are plentiful, more abundant
than those of boron, cadmium, or antimony, and at
least as abundant as arsenic and beryllium. Further-
more, germanium is readily separated from other elements
as the volatile tetrachloride; unliie other metals with
which it is crystallized in the earths crust, it has a
prominent covalent chemistry with many volatile
compounds.
After purification by distillation, the tetrachloride
may be hydrolyzed to pure GeO,. Reduction of the
dioxide with hydrogen gives metallic germanium,
which may be relined by zone-melting to the purity
required for electronic uses. From the chloride and
oxide are made GeO, GeS, GeCl,, GeBr2, GeL, GeFz,
GeBr,, GI, , GeH,, GeS,, GeTe,, Ge(C&IJ,, Ge(CeH&,
Ge& Ge(C&),, GeHC18, Na,Ge08, and the complex
sodium pentagermanate. All of these compounds are
available commercially.
Information abut germanium is easily obtained.
Major producers have organized a Germanium Re-
search Committee which collects and discleminates the
latest material. I n this country it operates a Ger-
manium Information Center at the Midwest Research
Institute.
Detailed information abut the element and its com-
pounds, including organic derivatives, is available in
FILTRATION
Gmelins Handbuch der Anorgankchen Chemie.
Fortunately the volume on germanium has been revised
recently (System No. 45, published 1958) and is now
printed with English headings and index.
Behavior
The first practical application of germanium was
made in 1925 (3) when several glass compositions were
prepared with GeOz instead of SiO,. Refractive index,
dispersion, and other properties of the new glass were
studied, but at that time little was known about the
compounds of germanium. Clemens Winkler, who dis-
covered the element, had succeeded in preparing the
compounds predicted by Mendeled plus a few more,
but few other chemists joined in the work. The element
had to be extracted from a crude ore difficult to obtain.
L. M. Dennis at Cornell, who became acquainted
with Winklers work in Germany, developed a source
of germanium in this country (a commercial zinc oxide
which contained 0.25% GeO, (4) and interested his
young student Laubengayer in research on the element.
Today Laubengayer is our foremost authority, and a
long list of publications from Cornell on the hydrides,
halides, divalent compounds, and organic derivatives of
germanium provides much of the information in Gmelin.
Germanium-containing glass is now available com-
mercially, and its high refractive index is exploited in
wide-angle camera lenses and microscope objectives.
Magnesium germanate glasses, more transparent in
the infrared region than silicate glasses, are used in
spectroscopes and other infrared devices. Germanate
glasses even permit extension of fiber optics to the in-
frared region (7). For high temperature materials,
fused mixtures of GeO, with TiO, and ZrOz are of
interest, especially because GeO, stabilizes the zirconia
against phase changes. Undoubtedly germanium di-
oxide and the germanates hold many more surprises
in ceramic chemistry, but this aspect has not been
studied extensively.
Because germanium is almost a metal, it has important
potentials in metallurgy. The tough, golden-colored
alloys of germanium and copper stimulate the imagina-
tion, and several studies already have been made.
Brazing alloys based on nickel, iron, chromium, and a
minor proportion of germanium are promising materials.
Alloys with copper and gold are good jewelers solder.
Germanium suppresses the formation of UAl, in ura-
U
6002
)Elm HYDROGEN 0 1
REDUCTION e
60 MAL
VOL 5 5 NO. 3 MA RCH 1963 33
Germaniums tetracovalent chemistry is closer to carbon than silicons is
nium-aluminum alloys, which helps in fabricating fuel
elements. Also it renders beryllium more ductile.
Its toughening of copper, aluminum, and magnesium
cannot be purely a matter of precipitation hardening,
because the rolling properties are improved at the same
time. This oddity of behaving differently from silicon,
yet doing some of the same jobs, makes germanium
unique in its relation to the metals.
Much misunderstanding has resulted from the mis-
conception that germanium is identical with silicon.
This view, probably originating in the days of Men-
deleefs ekasilicon, has been perpetuated by the textbook
repetitions of Mendeleefs predictions us. TYinklers
findings. Actually, germanium is more negative than
the usual group interpolation would have us believe,
and in its tetracovalent chemistry it is closer to carbon
than silicon is. This is particularly apparent in the
behavior of the hydrides. Although SiH4 and SnH4
ignite spontaneously in air and are reactive toward
water (especially in the presence of small amounts of
alkali), GeH, does not flame in air and is quite indif-
ferent to water. I n fact, the favorite way of preparing
it at present is to drop GeOz into a stirred solution of
sodium borohydride in water (6).
Similarly, the hydroxide, (CH,) 2Ge(OH) 2, is more
acidic than (CH3)&3n(OH) 2, and all physical measure-
ments of comparative attraction for electrons put ger-
manium on a level of electronegativity above silicon
and tin (7). Hence even though germanium began as
ekasilicon, and is used with silicon in the semiconductor
field, it occupies a unique place chemically. Those
who work with the organic compounds of germanium
are strong adherents of this view, and they uncover new
evidence for it almost every day.
Since Winkler made tetraethylgermanium and demon-
strated its stability, there has been an interest in com-
pounds containing carbon-germanium bonds. Today
organogermanium chemistry is a very fast-growing area,
and a mere summary of developments since publication
of the latest Gmelins Handbuch has required a 97-page
bookIet. The summary, prepared in English by Rij-
kens of the Institute for Organic Chemistry TNO in
Utrecht, Holland, is available through the Germanium
Research Committees Information Center, Kansas
City, Mo.
The current interest centers on polymers and thera-
peutic compounds, with theoretical overtones in the
regions of free radicals, hydride behavior, and hydrogen
bonding in the hydroxy derivatives. Analogs of the
silicones have been investigated for 15 years but no
particular advantages have been found ; the more recent
polymer work centers around combinations of ger-
manium and tin atoms with aromatic and conjugated
aliphatic groups to produce elastic and viscous polymers
containing bifunctional R2Ge units (5). The favorite
method for making such compounds involves adding
organogermanium hydrides (such as R2GeH2) to olefinic
or acetylenic compounds, which is really a hydrogen-
transfer polymerization. Polycondensation of ger-
manols with carbinols and silicols is also an easy way of
inserting organogermanium groups, but of course this
is limited to the formation of Ge-0 linkages which are
far more water-soluble than their silicon or tin counter-
parts.
Chemot herapy
Interest in the chemotherapy of germanium was
inevitable, because of its position above tin and lead,
and next to arsenic. I n 1922 GeOz \vas reported to
be useful for treating pernicious anemia, and the race
was on. For a long time it was difficult to use the mar-
ginal or specific toxicity of germanium, because investiga-
tors were limited to inorganic compounds of low solu-
bility or unsuitable pH ranges.
After simple, reliable methods of synthesizing organo-
germanium compounds were developed, their biocidal
properties were investigated by J . G. van der Kerk
and his colleagues at Utrecht, who had done much of
the pioneering work on organotin compounds of bio-
logical interest. They found that, although germanium
compounds of suitable solubility have 10k.i- mammalian
toxicity, the antimicrobial activitJ - of some R3GeX
compounds was marked. The most interesting results
were obtained against the gram-positive bacteria Stre)-
tococcus lactic and Mycobacterium phki , the fungi Tri-
chojhyton mentagrophytes and Glomerella cingulata, and
the yeasts Torulopsis nenformans, Candida albicans, and
Debaryomyes nicotianae.
Several of these organisms are pathogenic, and treat-
ment with other agents has not been effective. Of
even greater interest, of course, is the possible use of
related but as yet unsynthesized compounds for patholo-
gies such as carcinoma and leukemia. On the other
hand, perhaps existing organic compounds of demon-
strated but limited therapeutic value could be modified
by substituting relatively electropositive organoger-
manium groups for some of the usual modif)-ing (nega-
tive) groups.
The conviction that germanium hzs a place in medic-
inal chemistry is supported by its strange role in the
history of plant life. Germanium occurs in coal, but
few have realized how widespread or how vast is the
potential supply from this source. For example, a
J apanese project on extraction from coal dust has been
started. For some time it could have been argued that
germanium was a part of the coal ash, despite the fact
that it does not associate with aluminum and silicon
in geochemistry. Recent work, however ( Z) , shows that
low-ash coals actually are richer in germanium than
high-ash ones, and that the element is associated with
organic rather than mineral components. Either the
germanium was important to plants of the carboniferous
age, or the molecular structure of coal makes it chemisorb
34 I NDUSTRI A L A ND E NGI NE E RI NG CHEMI STRY
PROPERTIES OF GERMANI UM"
General
Atomic weight 72.59 (based on
Atomic number 32
Density at 25 " C., g./cc. 5.323
Boiling point, " C. 2830
carbon-12)
Melting point, O C. 937.4
Vapor pressure at 27O C., atm. 1.1 x 10-9
Electronegativity 1.8-2.0
Electrical
Band gap at 0" K., e.v.
Intrinsic resistivity at 27 " C.,
Dielectric constant, E
Electron mobility drift, ern."-
volt/sec.
Hole mobility drift, cm.2,' -
volt/sec.
Density of intrinsic electrons,
ni, at 300" K., per cc.
nfl, (where k =Boltzman's
constant)
Thermal
Debye temperature, O K.
Thermal conductivitv. cal./
ohm-cm.2
, I ,
sec./cm.2/ " C.
SDecific heat (0-100 " C.) cal./
0.75
47
15.7
3800 (3900)
1800 (1900)
2.4 x 1013
3.1 X 1032T3 exp
(-0.785/kT)
362
0.15
0,074
, .
- g . / o c.
Thermal expansion coefficient
Latent heat of fusion, cal./g.-
Heat of vaporization, cal./g.- 79,900
6.1 x 10-6
8100
(linear) at 25 " C. (0-300 O C.)
atom
atom
Mechanical
Hardness (Mohs scale)
Bulk rigidity modulus, dyne/
Elastic constants, dyne/sq. cm.
sq. cm.
Young's modulus
Bulk modulus
Shear modulus
6
1.3 X 1012
C111.292 X 10'2
C120.479 X 1012
C440.670 X 1012
Ylil 1.558
Gill 0.494
B 0.750
Optical
Refractive index, no
Refractive index at 2.0 microns
Refractive index, temperature
dependence at 2.25 microns:%
3.994
4.125
5.25 x 10-4
Magnetic
Specific susceptibility, ~106
Diamagnetic susceptibility, X 106
-0.122 at 20" C.
-0.146 at -183C.
(Ge+2) -16.8
(Ge+4) -10
(Ge-4) -100
Electrochemical
Ge =Ge+2 +2e-
Ge + 50H- =HGeO; +2H20 EO =- 1.0~
EO =0. 0~
+4e-
4e -
4e -
a From the Germanium Information Center.
Ge +2H20 =GeO2 +4H + EO =-0.15~
Ge +3H20 =H2Ge03 +4H++ EO =-0.131~
AUTHOR Eugene G. Rochow is a professor in the Depart-
ment of Chemistry at Harvard University, Cambridge, Mass.
germanium from its geologic surroundings. I n either
case, the phenomenon is important in applying ger-
manium to biological chemistry.
Uses
Despite research in organic and inorganic compounds,
the major use of germanium continues to be for solid-
state electronic devices of increasing number and variety.
However, the most recent devices use films or chemically
treated surfaces, and thus raise more chemical problems.
For example, a recent Philco device, which uses con-
trolled internal field emission to obtain a direct
current power gain of 30 db., consists of thin films of
aluminum, aluminum oxide, and germanium. Sim-
ilarly, new-type radiation detectors use large-area
germanium surface-barrier diodes. Smaller and faster
tunnel diodes of germanium are very much in the
picture, too: A new General Electric device has a
switching time of less than 5 picoseconds, and because
of the design, the inherent relaxation time of the semi-
conductor material itself is about one millipicosecond.
Its use in computers would allow an entire program to
be completed in the time it now takes a computer to
make a single addition.
SOME PROPERTIES OF COMMON
GERMANI UM COMPOUNDS
Compound
GeO2
GeC4
GeBr?
GeS2
GeH4
GeH6
G(CH314
Ge(C2Hh
Ge(CeH5)4
Sublimation.
M.P.," C. B.P.," C. D no
1086 ... 6.24
-49.5 83.1 1.879'0 1.464
26.1 186.5 3.13229
800 600. 2.9414
- 109 29.0 1.98-lOg
- 88 43.4 1.0060 1.44317
- 90 163 1.1980
235.7 >400
- 165 -90.0 1.532-14'
Chemists have always lent their talents to such prob-
lems of manipulation in the area of solid-state physics,
and this productive relationship will continue. On
the other hand, chemists have not realized the full
potential of germanium compounds in industrial, bio-
logical, and ceramic chemistry. More industrial in-
terest and imagination directed toward germanium
would result in more government support and university
research. Reserves of the element are abundant, but
imaginative thinking about it is not. Old impressions,
repeated endlessly, should be discarded in favor of new
concepts formed through research.
LI TERATURE CI TED
(1) Allred, A. L., Rochow, E. G., J. Inorg. Nucl. Chem. 5, 269
(2) Corey, R. C., Meyers, J . W., Schwartz, C. M., Gibson, F. H.,
(3) Dennis, L. M., Laubengayer, A. W., J. Am. Chem. SOC. 47,
(4) Dennis, L. M., Popish, J ., J. Am. Chem. SOC. 43, 2131 (1921).
(5) Noltes, J . G., van der Kerk, G. J . M., Chimia 16, 122 (1962).
(6) Piper, T. S., Wilson, M. K., J. Znorg. Nucl. Chem. 4, 22 (1957).
(7) Pontarvelli, D. A., Kapany, N. W., J. Opt. SOC. Am. 50, 1128
(1958).
Colbassani, P. J., Bur. Mines Bull. 575, 1959.
1945 (1925) ; J. Phys. Chem. 30, 1510 (1926).
(1 960).
VOL . 5 5 NO. 3 M A R C H 1 9 6 3 35

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