PLATINUM METALS REVIEW

A quurterly survey of reseurch o n the platinum metuls urrd of

dwelopments i n their applications i n industry

VOL. 15 APRIL 1971 NO. 2

Contents

Some Biological Effects of Platinum Compounds 42

Surface Phenomena on Rhodium-Platinum Gauzes 52

'The Electrodeposition of Rhodium on Titanium 57

Platinum Metals Electrodeposited from Molten Cyanides 58

Pressure and Thermal E.M.F.s 59

The Platinum Metals in Organic Syntheses 60

Abstracts 68

New Patents 75

Communications should be addressed to

The Editor, Platinum Metals Review
Johnson, Matthey & Co Limited, Hatton Garden, London EClP IAE
Some Biological Effects of
Platinum Compounds
NEW AGENTS FOR THE CONTROL OF "MOURS
By Barnett Rosenberg
Department of Biophysics, Michigan State University

Certain complexes of the platinum group metals exhibit interesting

biological efects. At low concentrations some are efective baeteriocides;
others stop cell division and force bacteria to grow into long filaments.
These complexes can also induce destruction of lysogenic bacteria. Most
important, perhaps, some of these complexes are very potent anti-tumour
agents against a broad spectrum of tumours, and may shortly be used for
cancer Chemotherapy i n humans.

In a truly heroic effort the National Cancer
Institute of the U.S. Government has
screened approximately 140,000 compounds
for anti-cancer activity over the past 15 years.
Of this number, however, only a dozen or so
were inorganic compounds. This imbalance
between organic and inorganic compounds
reflects a fashion in chemotherapy that
started over 35 years ago. Prior to that, heavy
metals were extensively used in medical
therapy. About 1935, the discovery of the
sulfonamides introduced a new class of
organic chemicals which were effective
against many bacterial infections. Hard on
this came the development of the antibiotics
which coupled a high degree of efficiency with
a low toxicity. At present, excepting a few
outstanding drugs, heavy metals and other
inorganic chemicals have ceased to be of
active interest as chemotherapeutic agents.
The screening program of the National
Cancer Institute, occurring within the last
15 years, reflects this bias.
Recently a new class of potent anti-tumour
agents has been discovered. These are
inorganic complexes of the transition metal
Group VIIIb. I n this article we shall review
briefly the history of this new development
and discuss some of the properties that are
now known concerning the activities of these
compounds. It will be taken as granted that
the general reader of this journal will find, as
did the author, that biological and medical
terminology are "terra incognita". T o offset
this to some extent, a glossary of the more
important terms is appended to the article.
The germinal discovery was made about
1964 when platinum electrodes were used
to apply an alternating electric field across a
chamber in which bacteria were growing ( I ) .
Application of the electric field caused a
cessation of all division in the E. coli rods,
and since growth was not inhibited, resulted
in the appearance of long filaments, A
comparison of the normal appearing E. coli
rods and the filamentous rods caused by the
application of the electric field are shown
under the same magnification in Pig. I.
Extensive detective work was required before
we could conclude that the effective agent in
blocking cell division in the bacteria was a
small concentration (-10 ppm) of some
platinum complex in solution, electrolytically
formed by the applied electric field. It re-
quired much further work to determine that
these complexes were cis-dichlorodiammine-
platinum(I1) and cis-tetrachlorodiammine-
platinum(1V) (2,3).

Platinum Metals Rev., 1971, 15, (2), 42-51 42

 Fig. 1 l'hasc. rontrnst photomirrogmphs (j"E. roli 11. \ 600. ( 0 ) Aormal bactcria grown i n chornirally
rd mcdiuni. ( I ) ) Filanio~atorisbctrterin grown in sume medium but incorporating I 0 p p m I$ ris-
dejined
dichlorodi I I ) . The, nbility (tf thr rells to dividr and sc'paratc, 1 9 completely inhibited, so
orodinniniiiirj~latini~rri(
continiird groibth lrads to long filaments

The structures of these complexes and some
other differently acting agents are shown in
Figs 2, 3 and 4. With the verification that
these platinum complexes were indeed
capable of selectively blocking cell division in
bacteria, a series of investigations was under-
taken to determine the mechanism and the
generality of the effect. VanCamp discovered
that the hexachloroplatinum(1V) and tetra-
chloroplatinum(I1) double negative ions are
bacteriocides at low concentrations (I to 6
ppm in the bacterial growth medium). These
compounds undergo photochemical changes
in the bacterial media, leading to a subse-
quent replacement of first one and then a
second chloride by ammonia. The resulting
neutral molecules arc not bacteriocides until
very high concentrations ( - IOO ppm in

cis-dichloro- cis-dibromo- oxalato-

diammineplatinum( I I) diammineplatinum( 11) diammineplatinum(I1)

dichloroethylene- cis-tetrachloro- tetrachloroethylene-

diamineplatinum( I I) diammineplatinum( IV) diamineplatinum( IV)
I"ig. 2 Stri~rttrrrdj h r i i i l u i , of crrtiur nriti-trtmour comp1ew.s of platinum. Only n vrry f i i (
sprr<firronjigiuatioris are nrtivr

Platinum Metals Rev., 19 7 1, 15, (2) 43

 tetraammineplatinurn( 11) all complexes of cis-dichlorodiammine
ion platinum(I1) with methionine
Fig. 3 Structural formulae of low toxicity. non-actiur complexes of platinum. Some soluble
salts qf the nwtals are tolerated very zucll i n the animals, indicating that thr activity is not dzc~
to u general hravy metal poisoning

solution) are reached. Interestingly, the
trans forms of these neutral molecules are not
effective in blocking cell division in bacteria,
while the cis isomers are. Thus we have two
groups of compounds with different bacterial
effects; the negative ionic species which are
generally bacteriocidal, and the neutral
species, in the cis form, which block cell
division, but not growth. Gillard and his co-
workers have reported similar effects in
organic rhodium complexes (4), and Gale,
Howle and Smith (5) have extended these
observations to include photochemical re-
actions in ammonium hexachloroiridate,
which also parallel the platinum trans-
formations and bacterial activities.
A third class of bacterial effects of platinum
compounds was discovered much later by
Keslova (6). It is known that some strains of
E. coli have previously been infected by
viruses (bacteriophages) and that the genetic
material of the virus was incorporated into
and became part of the genetic material of the
bacterial cell. T h e viral genetic material
(genome) is repressed in these cells and is not
normally detectable. Such bacterial strains
are called “lysogenic” for the simple reason
that a number of agents, such as ultraviolet
light, X-rays, and some chemicals such as the
nitrogen mustards (alkylating agents), are
capable of inducing the development of partial
or complete viruses which lead finally to the
destruction (lysis) of the cell. The platinum
compounds which are effective anti-tumour
agents were found to be extremely potent
in inducing lysis of such lysogenic bacteria.
Fig. 5 exhibits the three types of effects on
the growth curves in test tubes of various

rrans-dichloro- tetrachloro- cis-dinitrato-

diammineplatinum( 11) platinate(I1) ion diammineplatinum(I1:
4+

oxalatoethylene- tris(cthy1enediamine)-
diamineplatinum( 11) platinum(I1) ion
b‘ig. 4 Strurturcd formulae of high toxicity, non-active complexes ofplatinum

Platinum Metals Rev., 19 7 1, 15, (2) 44

strains of E. coli reacting to the presence of
different compounds of platinum, showing in
Fig. 5a the bacteriocidal effect, in Fig. 5b
the cell division inhibition, and in Fig. 5c the
lytic effects of these compounds.
Anti-tumour Activity
Since the platinum complexes of Fig. z are
active in inhibiting cell division in bacteria, it
Platinum Metals Rev., 19 7 1, 15, (2)
suggested that they may also be interesting
compounds to test as anti-tumour agents.
Such a study was undertaken in our labora-
tory. We first determined the level of the
platinum compounds which would be
tolerated by the animals (LD,, doses), and
then whether, below these levels, they would
inhibit the growth of transplantable tumours
in these animals. The first test was with a
45
Sarcoma 180 tumour (a standard test tumour
in cancer research) in Swiss white mice. We
found that the animals would tolerate single in-
jections of cis-dichlorodiammineplatinum(I1)
at a level (8 mg/kg) which could almost
completely inhibit the growth of the trans-
planted tumour, while the LD,, level was
14 mg/kg. This was the first evidence that
these complexes are active anti-tumour
agents (7). This compound was then sub-
mitted, along with cis-tetrachlorodiamminc-
platinum(1V) to the National Cancer Institute
for screening against the Leukaemia L I Z I O
tumour in mice, their present standard
screening tumour. Their results showed that
cis-dichlorodiammineplatinum(I1) has a a large number of other laboratories are
potent activity against this tumour, producing
an increase in life span of the tumoured
animals of 380 per cent, and a “cure” rate of
4 out of 10, with single injections at the
therapeutic dose, 8 mg/kg.
I n addition to inhibiting the development
of newly transplanted Sarcoma 180 tumours
in mice, it was later shown that one could
wait for a period of 8 days for the trans-
planted tumour to grow to a very large size,
before instituting treatment with the cis-
dichlorodiammineplatinum(I1). A single
injection, intraperitoneally, of 8 mg/kg of this
drug caused the complete regression of the
large tumours in close to IOO per cent of the
animals (8). These results are illustrated
in Fig. 6. I n addition to producing such
extensive “cures” of advanced sarcomas, we
found that even up to 11 months afterward,
the animals remained immune to a re-
challenge with the same tumour. Thus the
“cure” produced long-lasting immunity to
this tumour system (9).
This first anti-tumour complex of platinum
has now been tested extensively on many
other transplantable tumour systems. Kociba
(10) demonstrated that it can produce 100 per
cent “cure” in rats of the Walker 256 carcino-
sarcoma and the Dunning Ascitic Leukemia.
Again, in his studies he has shown that one
could wait until the tumour is in a highly
advanced state, i.c., four days before the
Platinum Metals Rev., 19 7 1, 15, (2) 46
animal would die, before instituting treatment,
and still rescue IOO per cent of the animals.
The drug has been tested now at the National
Cancer Institute and at the Chester Beatty
Institute in London by Haddow and Connors
(11) on a number of other tumour systems
such as the Lewis Lung carcinoma, the €3-16
melanocarcinoma, the P388 leukemia, and the
ADJ-PC6A tumours. It has shown marked
effectiveness in all of these tumour systems.
The latter group have also shown a lack of
activity of the complexes against the Rabbit
VX2 carcinoma, the Gardner tumour, and a
strain of the Walker 256 carcinosarcoma that
is resistant to alkylating agents. At this time,
investigating the anti-tumour activity of these
complexes against a host of additional
tumour systems. Their results will be re-
ported in the near future. We conclude from
this series of studies on the anti-tumour
activity of cis-dichlorodiammineplatinum(I1)
that it is a very effective agent against a
wide spectrum of transplantable tumours in
animals. Anti-tumour activity has also been
exhibited by the other compounds shown in
Fig. 2. I n some tumour types, other com-
pounds have been shown to be more effective
than the cis-dichlorodiammineplatinum(I1).
We have then a new class of drugs which
could form a set of specific chemotherapeutic
agents against specific types of tumours.
While transplantable tumours form the
best screening systems for evaluating the
effectiveness of new anti-tumour agents, there
are other types of tumour systems which are
more relevant to the cancers that occur in
human beings. Two other such types of
tumours are those caused by injections of
chemical agents (carcinogens) into the animal
which induce the formation of tumours, and
those which are caused by the injections of
certain classes of viruses. It is of interest,
therefore, to determine whether these
platinum complexes are capable of exhibiting
anti-tumour activity against carcinogenically
or virally induced tumour systems. Recently,
Welsch (12) has investigated the activity of
Fi?. h The, rrgrossion of u large Saxoniu-180 turnour in the! Swiss white rnouse by a single intraperitoneul
1 1 ) ut the therapeutic dosc (8 mg/kg)
injrction of’ c:is-rlichlorodiarnrnine~Z~itiniini(
ci,-dichlorodiammineplatinum(I1)against the
dimethylbenzanthracene-induced mammary
tumour in the rat. He has reported the
complete regression of a very large number of
extensively developed mammary tumours in
the rats, with at least three out of 14animals
completely “cured” of all tumours. Since
this particular tumour is the bcst model
system for human mammary tumours, these
results are of significant interest. Hinz (13)
has tested the same compound against a
virally induced tumour of the chicken. The
chicks were injected with the Rous Sarcoma
Virus, which, after a period of weeks, pro-
duces a large Sarcoma tumour in the wing
web of the chick. Again, therapeutic doses
of the complex were capable of causing
complete regression of these tumours in 95
per cent of the animals. From the accumu-
lating results of the anti-tumour activity of
Platinum Metals Rev., 19 7 1, 15, (2)
some platinum compounds against trans-
plantable, carcinogenically induced, and
virally induced tumours we can conclude that
these compounds have one of the broadest
spectra of action of any class of anti-tumour
agents yet discovered. From the fact that it
can cause regression of large tumours, and
rescue animals when injected a few days
prior to their death, we conclude that these
compounds are very potent anti-tumour
agents.
A major approach of the National Cancer
Institute chemotherapy program is the use
of combinational drug therapy. The basic
idea is to mix drugs, all of which hit the
target tumour, but each of which have
different side effects. Usually these com-
bination drugs have shown enhanced activity
over and above the best of the individual
drugs involved. However, only very few
47
combinations have been found which pro- liver and kidney. However, the damage to
duced synergism of anti-tumour activity. these latter organs is negligible, whereas the
Recently Venditti (14)showed that a com- tumour, of course, is destroyed. A significant
bination of cytoxan (an alkylating agent) and fraction ( - 15 per cent) of the injected drug
cis-dichlorodiammineplatinum(I1) produced is still detectable after six days. It has been
a large number of “cures” against an advanced found, both by Kociba and Toth-Allen, that
leukaemia LIZIOin mice, whereas each of the drug primarily affects those cells of the
them individually produced only a small body which are most rapidly dividing, such as
percentage increase in the lifespan, even up to the cells of the intestinal lining, and of the
toxic doses. This would appear to be a very bone marrow. It is, therefore, a cytotoxic
promising method of treatment, since the drug, and must be used with caution. These
drugs are both used at levels where side side effects are those generally expected with
effects are minimal. I will describe below, in anti-tumour drugs and techniques for their
the section discussing the mechanism of action amelioration have been developed. I n the
of the drug, a possible rationalisation for the case of the platinum complexes, the damage is
apparent therapeutic synergism of these two always reversible, and the animals recover.
drugs. They exhibit no long-lasting side effects
caused by therapeutic treatment.
The Toxicological Effects of
Platinum Complexes The Molecular Biology of
Experience teaches that it would be overly Platinum Complexes
optimistic to expect an anti-tumour drug to The interaction of the platinum complexes
be so specific in its action that it does not at all with cellular macromolecular syntheses has
affect adversely the normal tissues of the body. been investigated by Harder using tissue
I n general, one finds that all such drugs have culture techniques (16). He has measured the
side effects which limit the dose levels that ability of treated cells to manufacture nucleic
can be used in man. It is essential to predict acids (DNA and RNA) and proteins, using
from animal studies the kinds of toxicological radioactively labelled precursors for each of
effects one may anticipate when the platinum these species. Only those platinum complexes
complex is used in human patients. Such which are active anti-tumour agents are
studies have been undertaken in a number of capable of inhibiting the synthesis of DNA.
laboratories. Those which are inactive do not produce such
It is first necessary to determine how long inhibition. Further, at the dose level that
the drug remains in the animal after a pulse appears in the tumour tissues of animals, the
injection, and also its distribution as a function DNA replication is selectively inhibited,
of time in the various organs of the animal. while RNA and protein synthesis are not
Toth-Allen (15) has evaluated the distri- inhibited. Similar results have been found by
bution in mice using a neutron activation Howle and Gale in vivo (17). Such results are
technique which is sufficiently sensitive shown in Fig. 7. Harder has further proved
( 0.01 ppm) to measure accurately the low that the inhibition of DNA synthesis is not
N

concentration of the platinum complex caused by a blockage in the synthesis of the

generally found in tissues (-I to 5 micro- necessary precursors of DNA, nor is the
grams per gram of tissue) after injection. ability of these precursors to enter the cells
She has reported that there is no specific impaired. We conclude from these data that
uptake of the platinum complex in the the platinum complexes most probably act
Sarcoma 180 tumour tissue, and that indeed by causing a primary lesion in the DNA of
it appears in much higher concentrations in the cell. It is of interest now to determine the
the filtering and excretory organs such as the nature of this primary lesion.

Platinum Metals Rev., 19 7 1, 15, (2) 48


Ihobnik (IS) suggested, on the basis of the
similar occurrence of the two active chloride
groups in bifunctional alkylating agents and in
the cis-dichlorodiammincplatinum(II), that
the platinum complexes act similarly to the
bifunctional alkylating agents. Information
we have gathered up to now indicates that
there is indccd a similarity in the actions of
both of these classes of compounds, but it is
by no means an idcntity. For example, they
are both capable of forcing giant cell forma-
tion in mammalian tissue culture, and of
forcing filamentous forms in bacteria. They
both selectively inhibit DNA synthesis at low
concentrations in mammalian cells, and are
Platinum Metals Rev., 19 7 1, 15, (2)
very effective in inducing lysogenic strains of
bacteria. The present understanding of the
action of the bifunctional alkylating agents is
believcd to be the formation of an interstrand
crosslink between the guanine bases, at the
N-7 position, in double stranded DNA. I n
order to accomplish this interstrand crosslink,
the two active chloride groups must be
approximately 8A apart. I n the cis-di-
chlorodiammineplatinum(II), the spacing be-
tween the two active chloride groups is 3.3A.
It would appear, thcrcforc, that such platinum
complexes cannot be causing the same primary
lesions, i.e., interstrand crosslinking, as do the
bifunctional alkylating agents. On the basis
of some recent evidence that the platinum
complexes inhibit a single stranded bacterio-
phage as well as it does the double stranded
bacteriophage (19); that it reacts in vitro
primarily with purine bases rather than
pyrimidine bases; and taking into account
that the stacking spacing of the bases in the
Watson-Crick model of DNA is about 3.4A,
we arc led to suggest that the primary lesion
caused by the platinum complexes is an
intrastrand purine dimer. This is a new type of
lesion that has not been investigated before.
In vitro studies with purine dimers tend at
this time to validatc this hypothesis, but much
further work must be done to prove or dis-
prove it.
If indeed the platinum complexes do form
an intrastrand purine dimer, while the
bifunctional alkylating agents form an inter-
strand crosslink, it may then be that a
ccllular repair mechanism, which normally
operates within the cell to eliminate lesions in
the DNA, would have more difficulty in
simultaneously repairing both types of lesions,
than either one of them individually. This
could provide a rationale for the therapeutic
synergism described above.
Speculation on the Mode of Action
of the Anti-tumour Effects
Reslova (6) has shown that all platinum
complexes which are active anti-tumour
agents are capable of inducing lysis in lyso-
49
genic bacteria; those which are non-active do
not produce such lysis. These results provide
a clue as to the mode of action of the platinum
complexes in specifically damaging tumour
cells. It has been suggested by a number of
scientists that viruses may be the sole agents
which transform normal cells into tumour
cells. Howerer, since viral particles (virions)
are rarely found in tumour tissues, it is more
likely that the mechanism of transformation
operates after viral infection by the in-
corporation of the viral genome into the
cellular genome. Normally this viral genome
is repressed and unable to exhibit its presence.
Agents such as X-rays, radiation, other
viruses, and chemical carcinogens could
partially derepress these viral genomes,
forcing the manufacture of a number of new
proteins in the cell. It is hypothesised that
some of these new proteins are the active
agents causing transformation into tumour
cells. This hypothesis is consistent with the
theory of Huebner (20). If we now take the
evidence of Reslova, obtained from bacterial
cells, and apply it to the mammalian cells, we
can suggest that the primary lesions in the
DNA caused by the platinum complexes act
to derepress completely the viral genome.
This then leads to the active multiplication of
the viral particles, which may or may not be
defective. I n any case this will almost
certainly increase the antigenicity of the cell,
and therefore stimulate the immune system
to produce retaliatory antibodies to the
tumour cells at an enhanced rate. It is also
possible that, if the viral genome and the
viral particles can be eliminated from the cell
without concommitant cell death, the cell
should revert back to its normal status. Such
effects have been known to occur in the past.
This speculation suggests a number of
possible tests, and these are under way in a
number of laboratories.
Future Outlook
One platinum complex, the cis-dichloro-
diammineplatinum(I1) is currently on test at
the National Cancer Institute in preclinical
Platinum Metals Rev., 19 7 1, 15, (2)
trials. It is anticipated that it will be tested on
human patients some time in the spring of
1971.It will be many months before sufficient
clinical data will be available to allow a
judgment of the efficacy of this new
compound, either alone or in combinational
drug therapy, in human tumours.
I n the meantime, research must be pursued
to develop analogues of the original com-
pounds, and to continue testing these
analogues on screening tumour systems.
Without hesitancy I suggest it is now appro-
priate for inorganic chemists to join their
organic brothers in submitting samples of
their syntheses to appropriate Cancer
Institutes for screening for anti-tumour
activities. I n addition to this chemical
synthesis activity, it is desirable to know in
more detail, and with greater security, the
mechanisms of action of this new class of
drugs, as well as their general toxicological
and pharmacological properties in mammalian
systems.
‘This class of complexes of the platinum
group metals form a promising new class of
drugs to be added to the medical armamen-
tarium.
References
I B. Rosenberg, L. VaiiCamp and 7’. Krigas,
Nature, 1965, 205, 698
2 €3. Rosenberg, E. Renshaw, L. VanCamp, J.
Hartwick and J. Drobnik, J . Bact., 1967, 93,
716
3 B. Rosenberg, L.VanCamp, E. Grimley and
A. J. Thomson,Q. Biol. Chem., 1967,242,1347
4 K. J. Bromfield, R. H. Dainty, R. D. Gillard
and 13. T. Heaton, Narure, 2969, 223, 735
5 G. R. Gale, J. A. Howlc and A. B. Smith,
Arch. Int. Pharmacodyn., 1971, in press
6 S. Reslova, International Symposium
“Bacterial, Viral and Anti-Tumour Activities
of Platinurn Compounds”, Mich. State Univ.,
Sept. 1970
7 B. Rosenberg, I,. VanCamp, J. B. Trosko and
V. H. Mansour, Nature, 1969,222, 385
8 €3. Rosenberg and I,. VanCamp, Cancer Res.,
197% 3% I799
9 L. VanCamp, 1970, personal communication
10 R. J. Koeiba, S . D. Sleight and R. Rosenberg,
Cancer Cheniother. Rep., 1970, 54, 325
X I 1’.A. Connors and A. Haddow, International
Symposium “Bacterial, Viral and Anti-
Tumour Activities of Platinum Compounds”,
Mich. State Univ., Sept. I970
12 C.Welsch, ibid.
50
13 R. Him, ibid.
I4 J. Vcnditti, ibtd.
15 J. ’Toth-Allen and B. Rosenberg, 1971,
submitted for publication
16 11. C:. IIarder and R. Rosenberg, Z n t . J .
Cancer, 1970, 6 , 207
17 J. A. I h w l e and G. R. Gale, Bioclicm.
l’hurinacol., 1971, in press
18 J. Drobnik, 1970, personal communication
19 J. Drobnik, A. Krekulova and A. Kubelkova,
submitted for publication, 1971
20 K.J. Huebner and G. J. ’I’odaro, Proc. Natl.
Acud. Scz. U S . , 1969, 64, 1087
GLOSSARY
Alkylating agent. A reactive chemical which
replaces a hydroxylic hydrogen atom by an alkyl
group. Bifunctional alkylating agents have two
attachment sites (e.g., nitrogen mustard); mono-
functional alkylating agents have one available
attachment site (e.g., methylmethanesulphonate)
Antibodies. Protein components (gamma
globulins) of an immune organism which attach,
with great specificity, to antigens and incapacitate
them.
Antigen (antigenicity). Any substance (usually
proteinaceous) which when injected into an
organism causes the formation of antibodies.
Bacteriocide. Chemical agents which kill
bacteria, usually important only if they produce
tolerable effects in the host organism.
Bacteriophages. A class of viruses which
attack bacteria only.
Carcinogen. Any agent (chemical, physical,
bacterial or viral) which can produce a cancer in an
organism.
Carcinoma. A specific form of cancer which is a
malignant tumour of lining cells and glands in the
body of an organism.
Carcinosarcoma. A mixed tumour with charac-
teristics of both a carcinoma and sarcoina (see
below).
“Cure”. A complete disappearance of all de-
tectable symptoms of a cancer for a minimal
period of time (in humans, it is usually about
five years). The double quote marks usually
imply that the results are reported before this
minimal time has elapsed.
Cytotoxic. Refers to cell destruction or damage,
usually caused by agents deleterious to any
essential process of the cell.
Cytoxan. Commercial name for cyclophos-
phamidc, a very potent anti-tumour agent of the
bifunctional alkylating agent class.
DNA. Deoxyribonuclcic acid. A very long
chain polymer consisting of alternating phosphate
and sugar groups with attached purine and
pyrimidine bases. The genetic information of the
cell is coded in the sequence of these bases.
Escherichia Coli (E. coli). A bacterium found
in normal intestines. It is probably the most
intensivcly studied organism in biology.
Genome. The total genetic information of a cell.
Interstrand Crosslinks. A chemical (covalent)
link between two bases, each situated on one of the
Platinum Metals Rev., 19 7 1, 15, (2)
two strands of double stranded nucleic acid
(DNA, RNA). I t is generally believed that this
link prevents the separation of the two strands
which is necessary for genetic replication.
Intrastrand purine dimer. A chemical bond
(covalent) formed between two adjacent purine
bases (adenine or guanine) attached to the same
strand of a nucleic acid molecule.
In Vitro. Refers generally to experiments done
in a cell-free system. Here, however, it also
encompasses the growth of mammalian cells in
dishes.
In Vipo. Refers to experiments done in an intact
organism.
LD,,. The dose, given under specified conditions,
of any agent, which causes death in 50 per cent of
the organisms.
Leukaemia. A mass of relatively undifferentiated
cells in uncontrolled growth, disseminated in the
blood system. Specifically a disease of the blood
and blood forming organs characterised by a
permanent increase in the number of white blood
cells.
Lysis (Lytic). The bursting of a cell caused by
the destruction of the cell membrane.
Lysogcnic bacteria. Bacteria that contain the
genetic information (genome) of a bacteriophage
incorporated in the cellular genome.
Melanoma. A tumour containing melanin, the
black, polymeric pigment normally made in special
skin cells.
Purines. Aromatic, nitrogen-containing, ring
moleculcs (adenine and guanine) with basic
properties. One of the two classes of bases
defining the genetic code by their sequences in
nucleic acids.
Pyrimidines. Cytosine and thymine. The
second class of aromatic, nitrogen-containing ring
structures, that occur in nucleic acids, and define
the genetic code.
Repression (derepression). The forcing of a
gene into an inactive state. A repressor molecule,
believed to be a protein, blocks substances which
turn genes on, or interferes with the genes’
ability to eventually produce a specific protein.
RNA. Ribonucleic acid. A long chain polymer
consisting of alternating phosphate and sugar
groups with attached purine and pyrimidine
bases. May be the sole source of genetic informa-
tion in the organism, and additionally acts as an
intermediary to transfer the genetic code into
specific protein manuf.xture.
Rous Sarcoma Virus. An RNA containing
virus which is the causative agent of tumours in
fowl.
Sarcoma (S-180). A specific form of cancer
which is a malignant tumour of supporting
tissue in the body of an organism.
Virus (Virion) Defective-Active. Infectious
disease-causing agents which are smaller than
bacteria and which always require an intact host
cell for replication. They may contain either
DNA or RNA as the genetic material. The
nucleic acids may be double stranded or single
stranded. Defective viruses are incapable of
infecting host cells, or cannot replicate once their
genome has invaded the cell.
51
Surface Phenomena on
Rhodium-Platinum Gauzes
CATALYST ACTIVITY DURING AMMONIA OXIDATION

By J. E. Philpott
Johnson Matthey Metals Limited

The rare occurrence of inactive catalyst gauzes for no obvious reason has
led to comparative studies of the structures of rhodium-platinum wires
from both active and inactive gauzes. Active gauzes showed the regular
development of octagonal crystal faces on the nodular growths on the
wires. Inactive gauzes showed no crystal development and an amorphous
growth appeared on the wires. Segregation of rhodium and iron at the
surface occurred in this case, perhaps due to unusual plant operating
conditions, and may have caused deactivation.

The use of rhodium-platinum alloy gauze
as the catalyst in the modern process for
ammonia oxidation is well established, as
shown by the large number of papers re-
viewed previously in this journal ( I ) and
elsewhere (2). At the present time there are
in the world more than 450 nitric acid plants
and almost without exception they use plati-
num alloy catalyst gauzes, usually of 10
per cent rhodium-platinum.
T h e oxidation process is highly efficient
and over a wide range of operating conditions
a nearly quantitative conversion of ammonia
to nitric oxide can be obtained. Conversion
efficiencies of between 92 and 96 per cent are
commonplace and are consistently achieved
throughout the lifetime of a plant. I n general
the shortfall from maximum efficiency is
probably due to some decomposition of the
ammonia feedstock before it reaches the
gauzes, rather than to significant yields from
possible alternative reactions ( I , 2) that can
take place on the gauzes.
On rare occasions, however, a case is found
of a catalyst gauze pad that is inactive.
Although apparently indistinguishable from
other gauzc pads, the inactive gauze pad does
not maintain its initial conversion efficiency
and uneconomical yields are obtained only a
short time after igniting the pad. It would
appear that the high selectivity of the catalyst
gauzes for promoting the desired oxidation
reaction steadily declines and that yields from
alternative side reactions become significant.
Treating the inactive gauzes with constant
boiling hydrochloric acid and replacing them
in the plant does not improve their per-
formance. Replacement of the inactive pad
by a fresh pad of gauzes has always overcome
the problem but has done nothing to explain
it.
Analytical examinations of inactive gauzes
and of the material from which they were
woven and cut do not give any indication of
the cause of inactivity. The chemical
composition of the gauze material has always
been found to lie within the tolerance limits.
Analysis to determine whether some unusual
impurity had been sealed into the wire
surface during the wire drawing process, or
whether the retention by the gauzes of
impurities entrained in the feedstock gas
might account for the drop in activity, did
not reveal any cause of the inactivity.
Although inactive gauze pads occur in-
frequently and are more of an occasional

Platinum Metals Rev., 1971, 15, (2), 52-57 52

 Fig. 1 Carcful inspa tLon of gauzes fabricated by .Johnson Matthey Metals before dispatrh
to nitric nccd plants. Y’he fiat rircuEar pattze mil2 be Enstalled in a mediuin pressure plant
and the smaller hemgonal g a m e s zn high pressure plants. The largi, rolled czrcular g:cizcze
loill be installed En a plant operating at atmospheric presnuro

embarrassment than a constant cause of
trouble, a niore detailed examination of them
was undertaken as part of a research pro-
gramme to study the fundamental mech-
anisms involved in ammonia oxidation for
nitric acid production.
Examination of Inactive Ganzes
’To this end a number of inactive gauzes
from two medium pressure plants were
examined at various periods in their lifetime
and the results, together with the results
from a more general examination made of
spcnt gauze pads taken from all types of
plant in various parts of the world, were
compared with those obtained from an
examination of several inactive gauzes from
two inactive gauze pads. A description of the
results follows with a series of scanning
electron microscope and electron microprobe
analyser photographs illustrating the state of
the gauze surface at various stages.
It has been previously reported (3) that
rhodium-platinum gauzes develop nodules or
“brussels sprout” growths on their surfaces
while in operation in nitric acid plants. The
catalytic activity of the gauzes appears to
be related to the development of this nodular
growth, since fresh gauzes with smooth as-
drawn wire surfaces are inactive and need to
be activated before they will oxidise ammonia
efficiently. For this reason replacement
gauzes are usually installed beneath some of
the older activated gauzes already in the
catalyst pad. When a new pad is being
commissioned, each gauze in the new pad is
activated by playing a hydrogen flame over
its surface until the gauze just glows red.
Alternatively, a few activated gauzes obtained
from a plant already in commission are
inserted on top of the fresh gauze pad and
serve to ignite the remainder.
The photograph in Fig. 2 shows a gauze
of 0.003 inch diameter wire with the wire in

Platinum Metals Rev., 19 7 1, 15, (2) 53


the as-drawn condition. T h e uniform grain
structure and absence of nodules on the
individual wires can easily be seen. Fig. 3
shows the same gauze after it has been
Platinum Metals Rev., 19 7 1, 15, (2)
F‘ig. 2 l O P ( , Rh-l’t gauze ioire 0.003 inch diameter
i n the as-drawn condition showing the uniforni
grain structure and absence of nodules on the
wires
k’ig. 3 The gauze of Fig. 2 after half the normal
gauze life installed i n a nitric acid plant showing
the nodular pattern typicctl of a n active gauze
l+‘ig.4 A n eizlarged a i e u of the crossoz’er point of
two gauze wires .from the gaua:! i n Fig. 3 showing
the octagonal crystal structure and the nodules.
iohich are concmtmted on the wire surfaces between
crossover points
installed in a nitric acid plant for half the
normal gauze life period. Its surface shows
the development of the nodular pattern
typical of an active gauze. An enlarged view
of the crossover point of two gauze wires
from the same gauze is seen in Fig. 4. A
clearly developed octagonal crystal structure
can be seen in the enlargement and also the
development of the nodules, which appear
to be concentrated on the surfaces between
the crossover points. Perhaps nodular
growth at crossover points is inhibited by the
slight movement of the wires that occurs while
the gauze is in service. The structure seen
here is generally typical of active gauzes
whether they have been operated in low,
medium or high pressure plants.
When individual gauzes from an inactive
pad are examined, a markedly different
structure is observed. The regular develop-
ment of octagonal crystal faces cannot be
distinguished and an amorphous “cauli-
flower”-like growth as illustrated in Figs. 5
and 6 is seen, in contrast to the “brussels
sprout” nodules usual on active gauzes.
Segregation at Wire Surfaces
The obvious visual difference in these
highly magnified photographs suggested that
electron image determinations might produce
interesting results. Accordingly, two sets of
active and inactive gauzes were examined,
each set taken from one of two different
medium pressure plants many thousands of
miles apart. The electron image photographs
54
Fig. 5 AIIinactive puuze after a f h (lays installed
in a nitric m i d plant showing the rrbsence of
octcrgonul crystal ,faces
Vig. 6 An, edarged v i w of the g a m e toire shown
in Fig. 5 with the cnullflozuer-lilce amorphous
,growth clmrcrcteristic of innetiiie gauzes

of both sets of gauzes were similar and those

taken from one set are shown.
Examination of the electron images from
the active gauzes (Fig. 7) shows that the
wires were homogeneous and no unusual
features are visible. In the electron images of
the inactive gauzes (Fig. 8) a clearly defined
concentration of material is seen on the
surface of the wires. This segregation on the

Fig. 7 (right) Electron and X-ray images of spent active gauze showing its homogeneity. n (top) l<lectron
imugge of rross-section of gnitse. b (middle) Pt M u X-ray image. c (bottom) K h 1,cr X-ruy image. x 360

Platinum Metals Rev., 19 7 1, 15, (2) 55

 Fig. 0 l+:lrrtron and X-rmy images of spent
inactiiie gauze showing srgrrgation of material at
the surjacr
(I Elrctron image of cross-sertion of gauze
6 l’t M E X - r a y image
r Hh I,a X - r a y image Y 360

the effect is really due to the micro-section

being a plane through the middle of the
gauze so that more of the wire surfaces is
visible at the crossover points where the
wires dip and rise in crossing each other.
The composition of the material shown in
Fig. 8c is very probably rhodium present as
rhodium oxide Rh,OB. A similar electron
image was seen showing a concentration of
iron, probably as FerOa, which was as-
sociated with the surface concentration of
rhodium. Neither of the active gauzes
examined showed any sign of surface con-
centration of rhodium or iron oxides.
On both sets of inactive gauzes the cauli-
flower-like nodular structure and the con-
centration of rhodium and iron oxides on the
wire surfaces were found to be present on all
the gauzes in the pad although they became
less severe from the top gauze downwards.
Surface concentrations of rhodium and
iron have not been found on material from
which the gauzes are cut out so it is thought
that they develop within the plant itself. The
factor or factors which initiate the con-
centrating process may be connected with
some flaw in the manufacturing procedure but,
since reports of inactive gauzes are related to
individual ammonia burners rather than to
batches of woven material from individual
suppliers, it seems more likely that these
factors will be found to lie in some unusual
operating condition in the plant itself. A
possible cause is a prolonged period of
operation at low temperature, thereby en-
couraging the slow separation and con-
centration of rhodium oxide on the surface
together with the preferential retention of
small particles of iron oxide from the fecd-
stock on the rhodium oxide, whereas at
wire surface appears to be more marked at temperatures above 900°C rhodium oxide
the crossover points but this is not so because would be expected to volatilise.

Platinum Metals Rev., 19 7 1, 15, (2) 56

Fig. 9 (;awe fabrication vn
tl7e looms in the .Johnson
Matthey Metals g a i m shop.
i ~ h f ) f ~ i u m - p l f l t i n igauzes
Ln~ 7 ~ p
to 140 in (3.56 metres) wide
(ire wot~eri f r o m 0.003 in
diamrtw w i r e

‘The development of
these inactive surfaces is
the subject of further
research work and in a
later article it is hoped
that an explanation will be
given of the fundamental
causes that lie behind these
observations.

Acknowledgements
The author is much indebted to Dr G. J. I<.
Acrcs for helpful discussions and to Mr J. G.
l h y , who obtained the scanning electron micro-
scope and electron microprobe analyser photo-
graphs.
References
I H. Connor, Z’latinum Metals Rev., 1967, 11,
(I), 2-9 Ibid.; (2), 60-69
2 T. E L Chilton, Chem. Engng. Prog. Mon. Ser. 3
3 A. W. Holmes, Platinum Metals Rev., 1959, 3,
( I ) , 2-8

The Electrodeposition of Rhodium on Titanium

The protection of titanium by a thin coating
of platinum is well known in chemical
technology but, although platinised titanium
anodes are commonly used for industrial
electrochemical purposes, little attention has
been given to titanium coated with other
platinum group metals.
A recent paper by K. P. Ratashev and
V. P. Zverev ( TT.Leningrad. I’oiitekh. Inst.,
1970,(304), 130-134)now reports on studies
by the polarisation curve method of the
electrodeposition of rhodium on titanium and
indicates the feasibility of such plating. It
can produce both protective and decorative
coatings and also insoluble rhodium/titanium
anodes. T h e features of rhodium for these
purposes are its lesser density and greater
hardness than platinum.
Titanium alloys were degreased chemically
and then were etched in sulphuric acid
solution at 60 to 90‘C before plating in a
bath containing 1 . 2 to 2.0 g/l rhodium and
40 to 50 g/1 sulphuric acid at current densities
between 0.1 and 1.5 A/dm2 and at tem-
peratures between 20 and 75°C. Insoluble
anodes of platinum and rhodium-plated
titanium were used and efficiency increased
with lower current density and higher bath
temperature.
The rhodium coatings obtained at low
current density adhered well and were
satisfactory as regards hardness, reflectivity
(brightness) and corrosion resistance. Tests
were carried out to determine the properties,
strength and optimum thickness of rhodium
coatings on insoluble titanium anodes.

Platinum Metals Rev., 19 7 1, 15, (2) 57

Platinum Metals Electrodeposited
from Molten Cyanides
By D. Schlain, F. X. McCawley and G. R. Smith
US. Dept. of the Interior, Bureau of Mines, College Park, Maryland

While conducting research here at the
Metallurgy Research Center on thc elec-
trodeposition of platinum group metals from
molten cyanide baths we have prepared
platinum metal objects by electroplating or
electroforming. The electrodeposition of
platinum group metals on various substrates
from molten cyanide baths was described
by Rhoda ( I ) . We have described our
modified methods to electrodeposit thick
protective coatings of platinum, iridium (2),
palladium (3), and rhodium (4)from molten
cyanides.
Three crucibles were electroformed. One
is of iridium, one inch inside diameter and
$ inch deep with a 5 mil wall. The second
crucible is formed of platinum, 2 inch inside
diameter and one inch deep with a 5 mil
wall. The third, also of platinum, is electro-
formed with a thermocouple well for differen-
tial thermal analysis work, inch inside
diameter, 2 inch deep with a 15 mil wall.
Crucible tongs were coated with platinum,
2.5 mil thick on the arms and 5 mil thick on
the tips. I n addition, such items as thermo-
couples, a nickel-chromium-iron rod used

,
I hree c:rucibles urtd two pairs of crucilrles tongs fdwictited und coated with platinum metals.
I

T h e largcst crurible was electrofornied of iridium, the others of platinum. The tongs it1er~
couted with plntinum. Wall and coating thicknesses range ,from 2.5 mil to 15 mil.

Platinum Metals Rev., 1971, 15, (2), 58-59 58

as a seed holder in a molten calcium germa-
nate bath, and 8 copper thermal E.M.F.
probe have been heavily coated with platinum
or iridium for corrosion resistance. Objects
were electroformed of platinum or iridium
using suitable mandrel metals.
A molten cyanide process has also been
developed for treating substrates before
plating with platinum group metals in
aqueous baths ( 5 , 6).
Pressure and Thermal E.M.F.s
TEE EFFECT ON RHODIUM-PLATINUM THERMOCOUPLES
A thermal e.m.f. is not only a function of
temperature, it is also affected by pressure,
a fact that is not as widely known. T o the
geophysicist studying chemical and physical
behaviour at pressures of several thousand
atmospheres correction for the effect of
pressure is essential.
I n a recently published paper I. C. Getting
and G. C. Kennedy (I) describe a technique
for determining corrections on single thermo-
elements where, under thermally symmetrical
conditions, one-half of a homogeneous wire
is pressurised while the other half is main-
tained at atmospheric pressure. This is a
method previously used by Wagner (2),
Hridgman (3) and Bundy (4) among others.
Getting and Kennedy's apparatus con-
sisted of a piston-cylinder device with talc
as a solid pressure medium. T h e thermocouple
wire was fed through a tube at atmospheric
pressure to the thermal centre of the furnace
where it entered the cell through a pressure
seal. Inside the cell the wire was coated
with binderless boron nitride to preserve
electrical insulation yet ensure uniform
pressure transmission. T h e temperature of
both seals was recorded so that the temperature
gradient along which the pressure was
applied could be calculated. The cell was
heated internally by a co-axial graphite heater.
A number of excursions were made into
the pressure-temperature field ranging up
to a maximum of 1o0o"C and 35 kbars. T h e
thermocouples selected were Chromel :Alumel
and platinum: 10per cent rhodium-platinum
since these are two of the most commonly
used combinations. These thermocouples
have previously been the subject of investi-
gation by Bell et al. ( 5 ) , and Hanneman and
Strong (6) among others.
Platinum Metals Rev., 19 7 1, 15, (2)
References
I R. N.Rhoda, Plating, 1962, 49, (I), 69-71
2 R. I,. Andrews, C. 13. Kenahan and D. Schlain,
U.S. Bur. Mines R e p t . Invest. 7023, 1967
3 R. L. Andrews, G. R. Smith, C. B. Kenahan
and D. Schlain, U.S. Patent 3,5 17,789
4 G. R. Smith, C. B. Kenahan, R. L. Andrews
and D. Schlain, Pluting, 1969, 56, (7), 805-808
5 S. I). Cramer and D. Schlain, Ibid., (s),
5 16-522
6 S. D. Cramcr, C. €3. Kenahan and D. Schlain,
U.S. Patent 3,3og,2g-o
1
Extrapolation of the results obtained shows
that Chromel: Alumel may read as much as
z8'C high at IZOO'Cand 50 kbars while
platinum : 10 per cent rhodium-platinum
reads low by a similar amount at zooo"C
and 50 kbars.
T h e authors acknowledge that pressure is
only one of several factors affecting the e.m.f.
generated by a thermocouple and observe
that chemical contamination is a particularly
difficult problem. Unfortunately their paper
does not indicate whether any steps were
taken to measure the degree of contamination
and if so how their results were adjusted to
allow for this factor. Curiously they also omit
an expIanation of the value of extrapolating
to 2000 C when the platinum limb of a
thermocouple normally melts at 1772'c.
The reader is left to infer that pressure
raises the melting point sufficiently to make
this a meaningful exercise.
These criticisms apart the results should
prove to be valuable to workers in this
experimentally exacting field of research
where reliable data on e.m.f. correction are
still very scarce.
P. H. W.
References
I I. <;. Getting and G. C. Kennedy, J . Appl.
PhYS.9 1970, 41, (II), 4552-4562
2 E. Wagner, Ann. Phys., 1908,27,955
3 1'. W. Bridgman, Proc. Amer. Acad. Arts Sci.,
1918,53,269
4 I;. P. Hundy, J . Appl. Phys., 1961, 32, (3),
483-488
5 1'. M. Bell, I:. R. Boyd and J. L. England,
Carnesie Inst. Wash. Yr. Bk., 1968, 66, 545-547
6 R. €7. Hanneman and H. M. Strong, .7. Appl.
Phys. 1966, 37, (2), 612-614; J . Appl. Phys.,
1965, 36, ( 2 ) , 523-528
59
The Platinum Metals in Organic
Syntheses
ORGANOMETALLIC COMPLEXES AS PREPARATIVE REAGENTS
By B. F. G. Johnson
University Chemical Laboratory, Cambridge
r ,
1 hc. synthesis of organic molecules is
of growing importance to the chemical
industry but conz1entional methods are
becoming increasingly inadequate.
'I'ransition metal complexes, i n p a r -
ticular those of the platinum nzeiuls,
provid(> routes i n s.vnthetic chemistry
to many usefil and interesting com-
pounds. TIrre the principles involved
are explained and ( I . number of the
reactions ore dtwrihetl.
It is now apparent that the application of
transition-metal organometallic compounds
to the synthesis of organic molecules is one
of the most powerful preparative tools avail-
able to the chemist. This article is an attempt
to present some of the current ideas con-
cerning the structure and reactivity of such
organometallic complexes of the platinum
metals and to apply them to the preparation
of organics.
To date much of the emphasis has been
placed on complexes of iron and conse-
quently some of the principles are explained
by reference to that metal but there is growing
interest in the platinum metals, which havc
already proved their versatility in so many
fields of chemistry. I n no way is this a
rigorous and complete exposition but it is
hoped that an introduction to these ideas
will serve to indicate the synthetic potential
of reactions involving organometallic rcagents.
Coordination
In synthetic reactions involving metal ions,
activation of simple molecules such as H,,
Platinum Metals Rev., 1971, 15, (2), 60-67
CO, olefins, acetylenes, aromatic species and
many other compounds takes place through
coordination. This act of coordination has a
number of effects.
Change in Reactivity
The act of coordination alters the electron
distribution within the organo group. This
very often involves donation of electron
density (z)from the organic molecule (e.g.,
as with olefins) to the metal so that electron
distribution within the molecule can be
extensive. When coordinated to Pd(II),
for example, an olefin, normally susceptible
to electrophilic attack, now reacts with
nucleophiles.
I<:,H, PdCl,{I OH--?CH,CHO
Equally important is the manner in which
a change of metal can modify the reactivity
of the organic within an analogous series of
compounds. This is especially true for
olefin complexes. Recently, Pettit extended
his studies of cyclobutadiene complexes to
derivatives of ruthenium, molybdenum and
tungsten tricarbonyl and was able to show
that, whereas C4H,Ru(CO), resembles
C,H,Fe(CO), and behaves as a pseudo-
aromatic species, the related molybdenum and
tungsten complexes C,H,M(CO), ( M Mo
or W) did not, emphasising the importance
of the metal ion within this particular system.
Within this account we will in fact be
concerned to a large extent with the variation
in reactivity of coordinated olefins and it is
perhaps pertinent at this stage to discuss the
nature of the metal-olefin bond and thereby
rationalise (or attempt to rationalise) the
60
modification in behaviour or change in metal.
T h e bonding of olefins to metal ions is
generally considered in terms of the Chatt-
Dewar-Duncanson Model. This simply
views the bonding as being composed of two
parts :
(u) the donation of electron density from
the filled ethylene z-orbitals into an
appropriate metal 0-orbital, e.g. dspz
in the case of four coordinatc plati-
num(I1) having a square planar con-
figuration.
ii Pt
C 5P2
( h ) back donation from the filled d-orbitals
of the transition metal (e.g. dxz with
I’t(I1)) into the empty anti-bonding
orbitals of the olefin.
TT a n t i bond I n y .-._.
orbital
I
I i’t
For such a metal the metal-olefin bond
obviously depends upon :
(i) T h e metal, its electronic configuration
and oxidation state;
(ii) the auxiliary ligands present; and
(iii) the olefin itself.
Consider, for example, Zeise’s salt, an
ethylene complex of platinum(I1). Since the
metal is in a relatively high oxidation state
a drift of electron density away from the
ethylene to the metal via the o-bond ((a)
above) would be expected. For the same
reason little drift of electron density back to
the olefin via the x-bond is expected to
occur. Consequently the ethylene acquires
a net 8 character and undergoes nucleo-
philic addition reactions.
Platinum Metals Rev., 19 7 1, 15, (2)
I /’
6+ c-.
I n contrast for olefin complexes of Fe(O),
Ru(O), or Os(O), e.g. C,H,M(CO), (M Fe,
Ku or Os), since the metal in this situation
has a large degree of electron density as-
sociated with it, o-bond formation is poor,
whereas back donation would be expected
to be good with the formation of a strong
;7-bond. I n this case, the net result is electron
density build-up on the olefin leading to
susceptibility to electrophilic attack.
The role of auxiliary ligands or groups is
also understandable under these terms. Highly
clectronegative ligands result in electron
drift away from the metal and this is re-
flected in the enhancement of the activation
of the olefin towards nucleophiles, whereas
highly electronegative substituents on the
olefin (e.g. CF, groups) would cause an
even greater electron movement from the
metal to the olefin. Many of the reactions of
metal-olefin complexes may be rationalised
in these simple terms. Other factors, of
course, must also be considered. Often, for
example, auxiliary ligands produce strong
steric effects which cause modification of the
reaction path.
Stabilisation of “Unstable” Organic
Moleeules
Perhaps one of the most dramatic aspects
of this field is the stabilisation of organic
molecules which do not exist in the free
state. Beyond question the most notable
example of this type of behaviour is cyclo-
butadieneiron(tricarbony1). Cyclobutadiene
has excited organic and theoretical chemists
61
alike for many years but
prior to the work of Pettit
and his co-workers no good
evidence for the existence
of this molecule was avail-
able. Cyclobutadieneiron-
(tricarbonyl) shows many
of the properties associated
with aromatic systems.
Thus the ring system
readily undergoes electro-
philic reactions (see scheme
on right).
An important facet of this work is the ease
with which the free organic is produced on Another example is provided by cyclo-
oxidation with Ce(IV), for instance liberation octatetraene which coordinates to a variety
of cyclobutadiene in the presence of a of metal ions including Fe(O), Rh(1) and
dienophile leads to the production of Dewar Pd(I1). The conformation adopted on co-
benzene derivatives. This is important since ordination depends entirely on the metal
if such reactions are to have any potential ions employed even though all have the same
synthetic use then it must be possible to (d*) electronic configuration. Thus with
remove the metal under conditions which are Rh(1) and Pd(I1) the tub conformation is
not too violent, such that the organic group preferred whereas with Fe(0) a chair form
is not decomposed. is observed (in the solid state). (See Figs.
1-111).
Stabilisation of Unusual Conformers or
Tautomeric Forms
Very often the organic molecule under
consideration can exist in a number of con-
formations or tautomeric forms. In such
cases, because of the stereochemical require-
ments of the metal ion, the organic group
may be “forced” to adopt a particular
arrangement. For phenol, for example, two
tautomeric forms may be written.

!a) (b) Fe (CO),

In the free state only

tautomer ( a ) is observed.
By the reaction sequence 0

shown here (right), it is

possible to isolate an iron-
(tricarbonyl) derivative in
which the ketonic form ( b )
is stabilised.

Platinum Metals Rev., 19 7 1, 15, (2) 62

It is relevant to note that a further form of
CHH, has been noted for osmium complex
CHH,Os(CO), (See Fig. IV).
It is then possible to examine the reactivity
of such usual modifications of the organa-
group (albeit modified on coordination)
(see below).
Reduction of the Reaction Course
Finally it is important that we realise the
behaviour of organic groups coordinated to
metal ions can be modified
in rather subtle ways.
Cyclooctatetracne does not
undergo any of the typical
aromatic reactions under e M CI,
the usual “organic” con-
ditions. For example, = Pd or Pt
under Friedel Crafts con-
ditions, rather than acetyla-
tion, polymerisation occurs
with only minute yields of
the expected acetyl deriva-
tive. In fact the majority
of the chemistry of cyclo-
octatetraene is concerned with such polyrneri-
sations. However, recently it has been
shown that on coordination to a Fe(CO),
or Ru(CO), unit the reactivity of cyclo-
octatetraene is modified sufficiently to allow
acetylation, formylation and other electro-
philic reactions to occur
readily. One could con-
sider this modification in
reactivity to be subtle in
the sense that the molecule
is susceptible to electro-
philic attack both in the (3)
free and coordinating state
but that the act of co-
Platinum Metals Rev., 19 7 1, 15, (2)
ordination simply redirects the course of this
attack. Here the M(CO):,unit may be regarded
as a protecting group.
Some Reactions Described
Formation of Carbon-Carbon Bonds
Olefins readily undergo nucleophilic ad-
dition in the presence of Pd(I1) or Pt(I1)
salts. The reactions of many nucleophiles
have been examined but possibly those of
greatest interest to us are those involving
carbanions. By such reactions carbon-
bond formation is possible*
Reaction of (cycloocta-1,s-diene)palladium
dichloride or (cycloocta-1,s-diene)platinum
dichloride with the conjugate bases of malonic
esters, keto-esters, or p-diketones leads to
complexes (1~2) which contain a new carbon-
carbon bond; e.g.
CH!C02R)2
\
CH(COM4,
The complexes (1~2) have ISand z bonds with
the metal and in certain cases undergo further
transformations on treatment with base, the
course of the transformation depending
very much on the strength of the base
employed. Treatment of (IU) with a strong
I
CH(CO,R),
(5)
63
base produces a bicyclo [6, I , 01 nonene
derivative (3) and palladium metal. Another
moleculc of malonate gives rise to a compli-
cated reaction sequence. Attack occurs
intermolecularly at the x-complexed olefinic
bond and is followed by a transannular
reaction of the eight membered ring to form
a bicyclo [3, 3, 01 octane ring system con-
taining two malonate groups (4). I n contrast,
if attack of a second carbanion is encouraged
by reaction with tertiary phosphine as with
complex (2) a cyclooctene is the product
when M Pd, but a chelating a-bonded
cyclooctane when M Pt (6):
Carbon-carbon bond formation is not
restricted to thc nucleophilic addition of
carbanions to co-ordinated double bonds. It
is also possible by oxidative coupling of
olefinic and aromatic compounds in the
presence of, for example, palladium(I1)
acetate.
Pd(0Ac)
ArCH CH, ArH ,Ar<:H CHAr
Possibly the most remarkable observation
in this area is the coupling of benzene in the
presence of Pd(II)/NaOAc/HOAc to produce
diphenyl as shown below.

z-Allylpalladium chloride reacts with ethyl

malonate to give allyl- and diallyl malonates.

the thermal
Related to thedecomposition of x-allyl-pal-
behaviour discussed above is
ladium acetylacetonate (7) to give allylacetone
@
>
.
I
Pd ( = )H/ N
OAa co % CJgg
(8) via ligand coupling.
Other coupling reactions find their uses :

Platinum Metals Rev., 19 7 1, 15, (2) 64

 Whereas carbon-carbon bond formation
takes place by nucleophilic addition to
olefins coordinated to palladium or platinum
entities, on coordination to iron, ruthenium
or osmium tricarbonyls it rakes place by
electrophilic addition. I n general this is not
of particular synthetic utility since olefins
themselves undergo such reactions. However,
in particular cases, it is of tremendous
importance. One case, that of cyclobutadiene,
has been described above in some detail.
Other important examples are the cyclo-
octatetraene and cycloheptatriene complexes
of iron or ruthenium tricarbonyl. Both
organics polymerise under normal electro-
philic conditions but, on coordination,
addition reactions take place efficiently,
CH, = C HC H,CO,R
allowing a complete systematic chemistry
to be built up.
Carbonylation and Decarbonylation
The carbonylation of olefins in the presence
of transition metal catalysts forms the basis
Platinum Metals Rev., 19 7 1, 15, (2)
of several important industrial processes. By
this means many useful and important CO-
containing organics may be produced. Most
important is the carbonylation of ethylene,
e.g.
CH, CH, co PdC12->
CICH,CH,COCl : Pd
CE-I, CH, co PdCl, , ROH
CH,CH,CO,R 1
CH,CH,COCH,CH,CO ;R
CH, CH, <: 0 l’dC1; i H, ->
CH,CH,CHO C,H,
Such reactions have been studied extensively
and are, of course, catalytic. However, car-
bonylation of more “exotic” organics pro-
vides a useful route to many interesting
cyclic systems, e.g. (9) and (10)
Carbonylation of z-allylic derivatives pro-
vides a direct route to unsaturated acids,
acid chlorides and esters:
t Pd + HCI
The carbonylation of acetylenes also
provides routes into useful organic molecules.
Numerous transition metal complexes are
known to be active for cyclisation or oligo-
merisation of acetylenic compounds. Of
particular use is the employment of transition
metal units to produce cyclic ketones. Here
65
the carbonyls of Fe, Ru or 0 s and various Pd derivatives are of particular note.

Ph
WP
Ph C E CPh + CO
- JO
(

Systems containing N may also be carbonylated by these methods.

Large Ring Chemistry

It is often of considerable use to be able or platinum undergo nucleophilic addition to
to carry out specific substitution reactions give complexes of the type:
on ring systems. Here metal com-
plexes can be extremely useful. Con-
sider the chemistry of coordinated
1,s-cyclooctadiene. Complexes of this
[;)-ptA"

'CI
- 50- - C_yq
compound may be formed with Fe(O),
Ru(O), Os(O), Rh(I), Ir(I), Pd(I1)
or Pt(I1). As discussed above (commencing In contrast, the analogous complexes of
on page 63) for the formation of carbon- Rh(I), Ir(I), Fe(O), Ru(0) or Os(O), do not
carbon bonds, the complexes of palladium undergo such additions but rather electrophilic
reactions of the type:

Platinum Metals Rev., 19 7 1, 15, (2) 66

 I n fact for M Fe,
form I11 is ob-
served; for M -
Ru, form I1 and
for M - Os, a mix-
R ture of I1 and 111.
In the last case
form 111 fairly
rapidly converts to
form 11. Thus on
simply changing
from M Fe to
M - Ru or 0 s
different tauto-
meric forms of
CsH8' may be
to produce allylic derivatives by H abstrac- stabilised and their chemistry examined.
tion. These salts then undergo subsequent Thus on reaction with nucleophilic reagents
nucleophilic addition to give derivatives in neutral bicyclic or monocyclic derivatives are
which an alternative type of substitution was obtained:
obtained as shown above.
- -
Earlier we noted the
ability of metal containing
units to stabilise organic
1
o R u ( C

L-
O &

J
1 -+ + I?@- RU(CO),

molecules in unusual con-

firmations or tautomeric
forms. This enjoys wide R = (0.g 1CN -
synthetic application and
here we will consider the
cyclooctatetraene com-
I
plexes, CxH,M(CO):,, of Fa(CO),
iron, ruthenium and os-
mium. All three are
readily protonated by Conclusions
strong acids such as HHF,, HPFo or I n the work outlined above, examples of
<F,,CO,H to give cationic species of general useful synthetic procedures involving metal
formula C,H,M(CO),'. For the organic part ions having the d8 configuration have been
of this cation a number of tautomeric forms given. Many of these reactions are impossible
are possible, remembering that each form or difficult to attain by other methods. Often
must retain the ability to coordinate to the these procedures are useful not only for
metal. Some of these tautomers are shown: stoichiometric reactions but also in catalysis.
This is particularly the case for palladium

0 . (+I )I
'.__I

a (In)
derivatives. I n the main this facet of this
chemistry is poorly explored. T h e role of
the metal and the auxiliary ligands is obviously
critically important but relatively few sys-
tematic studies have yet been done.

Platinum Metals Rev., 197 1, 15, (2) 67

ABSTRACTS
of current literature on the platinum metals and their alloys
PROPERTIES
Vapour Pressure and Ireat of Sublimation of
Platinum
B. R . FLANTE, A. R. SESSOMS and K. n. PITCH, J .
Res. X B S , Pt. A, Pliys. Cheni., 1970, 74A, (5),
647-653
The vapour pressure of Pt was measured by the
Langmuir method at 17oo-zoooK and the
results are tabulated. The mean value of the
third law heat of sublimation is 564.49.; 2.1
kJ,'mol, but second law values tended to be
lower due to experimental error.
Photoelectric Iletermination of the Work
Function of Gold-Platinum Alloys
K. ~ O U W M A Nand w. 11. M. SACHTLER, J . Catalysis,
1970, 19, ( 2 ) , 127-140
Films of Pt, Au and their alloys were prepared
by vapour deposition. The photoelectric emission
of these films was investigated. Equilibrated
alloys of compositions within the miscibility
gap of the Pt-Au phase diagram possessed
identical work functions. This result agrees
with the expectation that the Au-rich alloy
envelops crystallites of the coexisting Pt-rich
alloy. CO causes an enrichment of the Pt in rhe
surface.
Orderiug in Fe-Pt Alloys
E. N. VLASOVA and T. P. SAFOLIIKOVA, Fiz. Metal.
Metalloved., 1970, 30, (s), 980-985
X-ray studies of the ordering of monocrystalline
32 at.'):, Pt-Fe during isothermal annealing at
750 C indicated initial formation of a metastable
homogeneous structure succeeded by separation
into two ordered phases FePt and Fe,Pt.
IZesistive Hehaviour of Dilute PdFe Alloys
about the Curie Temperature
M. P. KAWATKA, J. I . RUDNICK and J. A. MYDOSII,
I'hys. Rev. B., 1970, 2, (6), 1587-1592
The behaviour of the magnetic part of the
electrical resistivity pm of 0.1-1.0 at.;!, Fe-Pd
near the Curie temperature was analysed. The
ferromagnetic critical temperature was deter-
mined from the location of the maximum in
dp,.'dT, and varies with concentration as Cn,
where 11 1.65 : 0.05.
Thermodynamic Properties of Solid Nickel-
Platinum Alloys
K. A. WALKBK and J. B. DARRY, Acta Metall.,
1970, 18, (12), 1261-1266
'The activities and free energies of solid Ni-Pt
Platinum Metals Rev., 1971, 15, (2), 68-75
alloys at 1625 K were calculated from vapour-
pressure measurements. Heats of formation at
298 K were measured by liquid Sn solution
calorimetry. The results reflect the ordered
structures that exist at low temperatures in the
h'i-Pt system.
Magnetic Investigations of the Isoelectronir
Palladium-Platinum System
W. THEUTMAN, %. Angew. PhyS., 1970, 30, ( I ) ,
5-8
The magnetic susceptibility of Pd-Pt was
measured at 14-800 K, and shows a sharp
increase with increasing Pt concentration. New
electronic band and density of states calculations
are presented, and x(O,c) results for the Pd-Pt
system are discussed in terms of these and the
Stoner-Wohlfarth enhancement formula.
Thermal Stability and Structure of the 7";
Rh-Pt Alloy in Relation to Prior Defor-
mation
E. I . RYTVIS and L. A. MLDOVYI, Metalloved.
Term. Obrabot. Metal., 1970, ( I I ) , 53-55
The amount of deformation of an annealed
7(;,>Rh-Pt alloy affects its structure and the rate
of creep. At 1400 C the minimum resistance to
creep corresponds to IS":, deformation; at
1200 C to 8?, deformation.
Electrical and Tensile Properties of Cu-Tho,,
Au-ThO,, Pt-ThO, and Au-Al,O,, Pt-A41,0,
N. FUSCIIILLO and M . L. GIMPL, -7. Mater. S'ci.,
1970, 5, (12), 1078-1086
Dispersion-strengthened alloys of Pt, Au and Cu
containing l h O , and Al,O, were prepared by
precipitating the elements from a solution
containing a suspension o f the oxide phase.
Alloys containing C : Z vol.%, oxide phase could
be made into wire. Tensile strength, elongation,
hardness and resistivity were measured as a
function of temperature up to IOOOT. The
alloys exhibit high conductivity and superior
strength, hardness and oxidation resistance at
high temperatures.
Thermal Expansion of Khodium, Iridium
and Palladium at Low Temperatures
G. K. WHITE and A. T. FAWLOWICL, J . Loeo Temp.
~'Jz.Ys.>197% 2, (5-61, 631-639
Coefficients ( x ) of linear thermal expansion of Rh,
I r and Pd are 8.45, 6.65 and 11.78 :: Io'/deg K
at 283K and 3.50, 3.43 and 6.21 x ro6/deg K
at 75K. At temperatures below IOK cc may be
represented by
68
 ro.052'l'J (Rh)
I O ~ " C C- 20T
10~0% 9T o.070T3 (Ir)
TO"'% 40.'j'I' 0.43'j?'3 (Pd)
The ?' and T3terms are identifiable with electron
and lattice vibrational components.
New Data Concerning the Migration of
Hydrogen and 1)euterium 1)issolvcd in
Palladium under the Action of an Electric
Field
A . 1iEROI.Dand j.-ti. RAT, c. R., sir. c, 1970,
271, (I3), 701-704
The previously described migration of H, and D L
dissolved in a I'd wire under the action of a
continuous current cannot be reproduced in the
presence of traces of hydrocarbons. The mobilities
obtained from the flow of the transported gas
are less than those calculated using thermal
diffusion coefficients, which indicates an in-
complete ionisation of the dissolved atoms.
Note on the Debyc: Temperature of Palladium
J . s. BROWN, J . Ph-yr. C , Solid State Phys., 1970,
3> (91, L,I75-L177
A comparison of the values of the Debye tem-
perature for f.e.c. I'd is given for several different
model calculations, and a correlation with various
experimental results is discussed.
Study of the Diffusion of Hydrogen in Pd
and I'd-Ag Alloys with a Pulse Method
Naturf. A , 1970, 25, (IO), 1490-
Ir. Z ~ C H N E R ,%.
I496
LXffusion coefficients of H, in Pd and I'd-Ag
alloys were determined at low H, concentration
and 0-60 C by an electrochcmical pulse method.
'l'he pre-exponential factor D, decreases slightly
with rising Ag content. The energy of activation
depends on the Ag content, going through a
minimum at NN 15'2,Ag.
1. Study of the Adsorption of Hydrogen on
Filanients of Purr Palladium
€3. TARDY and s. J. TEICHNBK, J . Chim. Phys.,
1970, 67, (11-12), 1962-1967
The adsorption of H, on evacuated Pd filaments
was studied by flash desorption. The desorption
curves are complex due to impurities (CO and
H,O) which are also desorbed. Gas analysis
shows adsorption of a single species of H, on
Pd in an amount less than the value corres-
ponding to a monolayer.
11. Adsorption of Hydrogen on a Series of
Gold-Palladium Alloys
Ibid., 1968-1972
The adsorption of H, on Au-Pd alloy filaments
was studied. The amount of H, adsorbed in-
creases with the Au content up to 30(%~, then
decreases when the Au content is 50'2,. The
latter value corresponds to complete filling of the
d orbitals of Pd.
Platinum Metals Rev., 197 1, 15, (2)
Investigation of the Pd-Ba Composition
Diagram
E . M. SAVITSKII, v. 1'. POLYAKOVA and E. M.
KHORLIN, Izv. Akad. Nauk S.S.S.K., Metally,
1970, (6), 143-145
,.
I h e composition diagram for up to 33 at.%,
Ha-I'd alloys was constructed and showed that
BaPd, and BaPd, are present.
Energy Bands in P'-PdIn
s. J . CHO, I'hys. Statzts Solidi, 1970, 41, (I),
179-189
The energy bands for ordered P'-PdIn were
calculated by the augmented plane wave method.
The possible open orbits were studied, and the
electronic density of states curve was obtained
from the energy bands. Estimates of the elec-
tronic specific heat coefficient, the magnetic
susceptibility, and the cyclotron effective masses
are given. Results are compared with existing
optical data.
Remarkable Interstitial IIydrogcn Contents
Observed in Rhodium-Palladium Alloys
at High Pressures
T. €3. FLANAGAN, €3. BAKANOWSKII and S. MAJCHRZAK,
.7. I'hw Chem., 1970, 74, (24, 4299-4300
A H:Pd atomic ratio greater than I was found
in an alloy system, Rh-Pd, where the added metal
is probably a nonabsorber of H,. At 2300-5100
atm stoichiometric I :I hydrides were obtained
for the 20'2, and 30'%,Rh-Pd alloys. Either Rh
can absorb H, but at a higher pressure than Pd,
or Rh functions as a €1, absorber only when in the
I'd matrix
The Thermodynamic Properties of Solid
Palladium-rich Pd-Cd, Pd-In, Pd-Sn and
Pd-Sb Alloys
J. n. DAKBY, K . M. MYI.BS and J. N. PRATT, Acta
Metall., I97X, 19, (I), 7-14
Vapour pressure measurements were used to
calculate the activities and free energies of for-
mation, at 1350 K, of Pd-rich Pd-Co alloys.
Entropy of formation values were found by
combining free energy results with heats of
formation (AHf) at 298 K. AHf values were also
found at 298 K for the =-phase I'd-rich alloys
of the polyvalent solutes In, Sn, Sb and for the
intermediate phases PdSb and PdSb2. Results
suggest some correlation between the four alloy
systems.
Thermoelectric Power of Palladium Based
Dilute Alloys
D. GAINON and J. SIERRO, Helv. Phys. Acta, 1970,
43, (6-7), 541-554
The thermopower, S, of I at.?, M-I'd (where
M Ti, V, Cr, Mn, Fe, Co, Ru, Re, Os, Te)
was measured at 1.5-273 K. For the ferromagnetic
alloys a change of slope of S exists near the Curie
temperature. Pd-Cr shows a large positive
69
value of S at low temperature, but for the other
alloys S is both positive and greater than when
the same dilute elements are dissolved in noble
metals, but is not anomalously dependent on
temperature.
Composition 1)iagram of the Ti-Ir System
v. N. BKIWENKO and T. D. sIimrA, Izo. &ad.
~ v a u kS.S.S.R., Mctully, 1970, (6), 197-203
Studies of the T - I r system indicated a stable
CsC1-type phase in 30-40 at.';!;, Ir-Ti at high
temperatures based on T - I r stabiliscd with
extra T i . No eutectoid decomposing to P-phase
at 500"<: tvdS found.
Plnotoelectric Determination of the Work
Function of 1111 Filnis as a Function of
Sintering Temperature (BK--925K)
K . BOUWMAN and w. H. M. SACHTLBK, Surface
Sci., 1971, 24, (I), 14e-148
The photoelectric work function 9 of a Ku film
on a Pyrex substrate rises from 4.52.10.03 eV
at 78K to 5.02 ,.0.03 eV at 573K after sintering.
For Ku on quartz and annealed above 7 m K ,
9 5.10 ! 0.05 eV. The emission constant con-
tinues to decrease even beyond the temperature
where '2 ceases to increase. Theoretical values of
'p for Kh and 0 s are given as 5.1-5.2 and 4.9-5.0
respectively.
Physieo-chemical Hehaviour of Kuthenium
in Sea Water
11. GUEGUENIAT C o m n. EnerKie Atom. Bull.
Inform. Sci. Tech., r970, ( I ~ I ) 27-32
, (IO), 1083-1086
Kesults are presented of a physico-chemical
study of nitrosylruthenium compounds dis-
charged into the sea by spent fuel processing
plants. Various forms of these derivatives are
separated on an ion exchange resin, and their
concentration is correlated with time and with
certain properties of the water.
Optical Properties of Molybclenum and
Ruthenium
.7. opt.
K. A. KRIBS and G. J. I.API'.YRI<., SOC. Aw.,
1970, 60, (IZ), 1681-1684
Keflectance values for Ru were obtained at
0.5-14 eV. The graph of the imaginary part of
the dielectric constant E~ against h v has 3 shoulder
at 1.6 eV, and the loss functions Imlr , ' E ] and
Im[I ' I 1 - E J shows peaks at 10.2 and 8.7 eV
respectively.
Electron Work Function in Alloys of
Tantalum with Kutheniuni
0 . K. KUI.TASHEV and A. 1'. MAKAKOV, Fiz. Metal.
Metalloe'ed., 1970, 30, (s), 924-928
Thermoelectronic emission studies showed a
sharp rise in the electron work function of
>5c;(l solutions of Ru and Ta, explained by the
formation of monoatomic films of Ru on the
surface of the solid solution, and a work function
Platinum Metals Rev., 1971, IS, ( 2 )
for solid solutions of T a in Ru near to that of pure
Ru, 4.75 eV. The !L phase has the largest electron
work function in the system, 5.05 eV.
CHEMICAr, COMPOUNDS
Nuclear Magnetic Resonance in PtSb, and
PtAs,
G. R. MAI.LICK and 1'. R . EMTAGZ, I'hys. Rev. u,
1970, 2, (s), 1251-1260
Analysis of n.m.r. results for Sb'"', Sb"", and
Pt'!'" in PtSb, and PtAs,, and of the observed
anisotropy in the Pt resonance suggest that 1%
is in the formal valency state (-z), and that all
bonds in these compounds are primarily covalent.
Free Enthalpy of Formation of Palladium
Oxide
II. KI.EYKAMI',%. Phys. ChCihelu/., 1970, 71, (1-3),
142-148
'I'he free enthalpy of formation of PdO was
obtained using a solid cell Pt 'Fe,FeO,'
%rO,,Y,O, Pd,PdO:Pt. The standard entropy
of PdO was calculated using the specific heat and
entropies of Pd and 0 , as 8.8.. 0.5 cal g:mol.
Using this and the free enthalpy functions of Pd,
0 , and PdO, the value of .28,20011 500 calimol
was got for free enthalpy of formation of PdO.
Metal-Boron Compounds. X. Diboryl-
amines as Tc-Ligands in Palladium Complexes
G. SCIIMID and I.. WBUEK, %. Naturf. I?, 1970, 25,
Ris(dimethy1amino)boronchloride reacts with
(C,II,CN),PdCl to form complexes of the type
Cl,Pd[(CH,)&I,UX (X Cl, CH,). The analo-
gous bromo- and iodoboranes react with co-
ordinated benzonitrile to form C,H,,C(X,)N-
B(N[(CII,),.I),PdX (X Rr, I) which are probably
dimeric. I'he B-N groups act as x ligands.
Synthesis and Structure of a New IIigh-
pressnre Form of Kh,O,
R . n. SIIANSOS and c. T. PREWITT, J . Solid State
Chew., 1970, 2, (I), 134-136
A new high pressure form of Kh,O, was prepared
at 64 kbar and 12oo'.C:. The material is a semi-
conductor with a resistivity of 130 f2cm at room
temperature and an activation energy of 0.16 cV.
T h e structure is orthorhombic with a 5.1686,
~
b -5.3814, c 7.2426& Z -4, Dabs --8.~8
g 'cm8, and is described as containing layers
of a corundum-like structure cut parallel to
(IOII) and then stacked together.
Starting Materials for the Preparation of
Orgunometallic Complexes of Platinum and
Palladium
F. R. HARTLEY, Organornet. Chem. Rev. A , Subj.
Re% 1970, 6 , (I), 119-137
The preparation of zerovalent and divalent com-
70
plexes of Pt and Pd with PPh, and divalent
benzonitrile, ethylene and amine complexes with
Pd and Pt are described.
The Chemistry of Transition Metal Carbonyls.
Synthesis and Reactivity
I:. w. ABEI. and F. G. A. STOKE, Q.12ev., 1970,24,
(41,4983'52
The preparation and properties of many transition
metal carbonyls including those of the platinum
group metals are described.
ELECTKOCHEMIS'JKY
ISlectrocatillytic Activity of Platinum-Ruth-
eninni :Way Black for Mctlianol Oxidation
M. WATANABI;, T. SUZUKI and s. MOTOO, Denki
Kajiakzi, TWO, 38, (IZ), 92.7-932
'I'he dependence of the activity on the composition
of l't-Ru alloys was investigated. Pt and Ru
were alloyed with T i and developed in HI;
solutions to give the black, which is a f.c.c. solid
solution of Ru in 1% The catalytic activity
increased sharply till the Ku:l't ratio was 2 , then
decreased sharply till the ratio was 3. It is proposed
that the Pt atom requires 2-3 Ru atoms as its
nearest neighhours for maximum clectrocatalytic
activity.
Anion Adsorption on Palladium
v. s. VII.INSKAYA, K. H. BUKSHTEIK and M. K.
TARASEVICH, Elekrrokhimiva, 1970, 6, (IO), 1497-
I502
Bond strength and H, chemisorption on Pd
decrease and anion adsorption increases when Pd
powder is observed in the series of acids H,SO,,
II,PO,, HCl, IIHr.
Meelranism of the Chlorine Electrode Ileac-
tion on Platinum, Iridiuni and Rhodium
in Aqueous Aydrochlorie Acid
T.Y O K O Y A M A M.
~ ~ ENYO,
~ Blectroclaim. Acta,
1970,
15, 1921-1943
(IZ),
The mechanism of the reaction zCl-+Cl, I.2e
was studied on smooth Pt, Ir and Rh in aqueous
HCl. For Pt and Ir the reaction occurs in two
distinct steps; which of these is the rate deter-
mining step depends on the electrode potential.
For Rh the results are incomplete.
ELECTRODEPOSITION AND
SURFACE COATINGS
Precious Metal Plating
P. ti. L. VIVIAN, Electroplating Met. Finish.,
1970,23, (I I), 20-22, 24, 26, 28
A review of electroplating techniques for Pd and
Kh is given. The type of deposit, different
methods, and the problems involved are dis-
cussed. Pt and Ru are briefly mentioned. A
short account of electroless plating is also given.
Platinum Metals Rev., 19 7 1, 15, (2)
The Nucleation and Growth of Electroless
Metal Deposited on Plastic Substrates
A. KANTBLL, Trans. Inst. Metal Finish., 1970,
48, (51, 191-198
A technique is described for obtaining electron
micrographs of very thin electroless metal films
deposited on plastic substrates. During the early
stages of growth, electroless metals are deposited
as island structures, growth beginning at active
sites created by the SnCl, 'PdCl, treatment.
,-
I hese active Pd sites are less numerous on sur-
faces where the depositing metal is chemically
bonded to the plastic than when it is not.
Electroplating of Osmium
A. J. AITLERY, J . filectrochem. Soc., 1970, 117,
(IZ),1610
Attempts were made to form an 0 s electrode
using a Au cathode, and a graphite anode in a
molten electrolyte of 81,1(: OsC1, in KCN-NaCN.
At 10-20 mA/cm2 a bright, adherent though
granular deposit was obtained. At higher current
densities black deposits occurred. Typical
roughness factors for bright deposits were 6-7.
HETEROGENEOUS CATALYSIS
Reaction between Deuterium and Cyclic
Olefins on Platinum/Alumina in the Liquid
Phase
J. J. PHILIXWN and K. L. BUKWELL, J . Am.
Chem. Soc., 1970,92, (21), 6125-6133
'The liquid phase reactions between D, and
cyclopentene, cyclohexene, cycloheptene, cyclo-
octene, bicyclo(~,~,o)-z-octeneand I-hexenc on
Pt A1,0, were studied in various solvents. T h e
exchange reaction proceeds rapidly, the D*/H*
ratio increasing over the low value obtained with
no solvent or in TIfF. The distribution of
products and effect of solvents are discussed.
Poisoning Studies in a Single-pellet Catalytic
Reactor
J. I,. HAIIN and B. 0. PETERSON, Canad. J . Chenz.
lipignx., 1970, 48, (2), 147-150
The activity of a 0.25~x~ Pt/q-A1,0, catalyst was
measured using the cyclopropane hydrogenolysis
reaction. The catalyst was progressively poisoned
from the outside to the centre plane non-
uniformly. Results suggest a bi-modal pore size
distribution in the pellet.
Mathematical Description of Platforniing
Carried out in Severe Conditions
YU. M. KHOKOV, G . AI. PANCHENKOV and I. Y A .
SHAPIKO, Khim. l'ekhnol., Topliv Masel, 1970,
(II), 37-40
A matheinatical model of the reactions occurring
during petroleum reforming over Pt catalysts is
based on the conversions between gas, paraffins,
naphthalenes, and aromatic hydrocarbons.
71
Structure of Platiniim/Alumina Catalysts for Mixed Adsorption Catalysts. V. Catalysis of
Gasoline Reforming Hydrogen Peroxide by Platinum-Silver Sys-
M. MOSER, L. VAJTA and I BENYI, Kent. Kozlenz., tems on 1)iamagnetic Charcoal from Sugar
1970, 33, (3), 255-263 Zh. I'iz. Khiin., 1970, 44, (IO),
I . A. Z u m v r c r r ,
Electron microscopy showed the distribution of 2536-2540
Pt in Pt,'Al,O, catalysts. Micrographs are given of Studies of the activity of Pt-Ag catalysts sup-
Sinclair Raker 0.35':;. Pt 'A1,0, and Soviet ported on batches of decalcified diamagnetic
AP-56 0.55-0.60"(, I't 'Al,O,. sugar charcoal in the reaction of H,O, at 23,
35 and 5 5 ' C showed that reductions in activity
The Role of C5- and C,,-I)eliydrocyclisatiorr are caused by formation of mPt.nAg complexes
in the Aromatisation of r~-Octaneon Plati- on the surfice, where m and n are the simplest
num/~llumiiiaCatalyst stoichiometric ratio. Apparent activation energies
V. G. VIASOV, YU. V. FOMICHIW alld R . A . KAZANSKII, and the pre-exponential multiple in the Arrhenius
Nefzekhirniyu, 1970, 10,(6), 821-825 equation are dircctly related but the activity of
Studies of the conversion of n-octane and rz-pro- the catalysts is inversely related to them.
pylcyclopentanc on Pt 'A1,O:: with added alkali,
( 0 . 6 ~ ~ Pt
0 0 . 8 ~ ) ; ,Na2OJ/y-A1&L,, showed that Contrast between Sickcl and Platinum
aromatisation of n-octane is accompanied by Catdysts in IIydrogenolysis of Saturated
C,,-dchydrocyclisation to form alkylcyclopcntancs I Iydrocarbons
in both acidic and alkaline catalysts and that, on 11. MATSUMOTO, Y . SAITO and Y . YONEDA, .7.
acidic catalyst, alkylcyclopentancs play a signifi- Catalysis, 1970, 19, ( z ) , 101-112
cant part in aromatics formation. Decreasing the
The mechanisms of hydrogenolysis on Ni,'SiO,
acidity of Pt'Al,O, by Na,O addition causes
and Pt SiO, are compared. The reaction on Pt
unsaturated hydrocarbons to appear in the
occurs via heterolytic splitting of the C-H bond
conversion products.
on adsorption. On Ni the splitting is homolytic.
Isomerisation and Dchydrocyclisation of This is due to the greater stability of Pt-11 co-
Hexanes over Monofimctional Supported ordination over Ni-H coordination.
Platinum Catalysts
F. M. DAUTZENBEKG and J. c. Pr.KrTmuw, .7.
Adsorption of 15cnxene and Cyclohexane on
Caralysis, 1970, 19, (I), 41-48 Zeolite Y Supported Platinum Catalyst
Isomerisation and dehydrocyclisation reactions M . KOHAYASIII and T. SHIKASAKI, Kogyo Kagaku
of hexanes in the presence of Pt,'A1,0, catalysts Zasshi, 1970, 73, (6), 1245-1247
werc studied. The dehydrocyclisation of iz-hcxane The adsorption of (:,€lo and cyclohexane on
to C,H, goes by two different routes; by a Pt- Pt,'Zeolite Y catalysts containing water was
catalyscd six ring closure, or, by a thermal six studied. 'The water did not desorb on adsorption
ring closure of hexatrienes by dehydrogenation of of cyclohexane, but did with C,H,. On changing
n-hcxane over Pt. the carrier gas from X, to H, adsorbed C,H,
was convertcd to cyclohexane which was desorbed.
Electron Microscope Investigation of Plati- The results indicate three types of catalyst site; a
num Catnlysts. I. Platinum on Aluminium vacant site, sites with adsorbed water and having
Oxide Pt particles, and sites with adsorbed water but no
I.. M. KEFI!I.I, Zh. Fiz. Khinz., 1970, 4,( I I > ,
Pt particles.
2820-2823
The formation of Pt crystals on Als03 by the Effect of the Nature and the Amount of
thermal decomposition of €I,PtCl, comprises the Secondary Components of Binary Pal-
formation of a crystal lattice from Pt atoms, its ladium Alloys on their Catalytic Activity in
coarsening, growth of these first crystals on Relation to the Dehydrogenation of Cyclo-
single centres, their agglomeration, and the role hcxane
of the carrier in the process. V. M. GKYAZNOV, V. P. POLYAKOVA, E. M . SAVITSKII,
L. FRADES, E. V. KARAPOVA, 8. KIIUKES and G. V.
Rheniforming Scores High in Commercial SIIKOLA, Izv. Akad. Nauk S.S.S.R., Ser . Khim.,
Runs 1970, (II), 2520-2524
G. D . GOULD and c. s. McCOY, oil G'as.7., 1970, 68, Studies on the catalytic dehydrogenation of
(48, Nov. 30), 49-53 cyclohexanc showed that activity increased with
The performance of Re-Pt catalysts for petroleum Pt content up to r.5'%; Pt-I'd but that it decreased
reforming is reviewed. They are found to main- with Ag content in the range 20 up to SO'^;, Ag-Pd.
tain selectivity, to give stable yields and can bc 51)il Ni-Pd is more active but IO~;;! Xi-I'd is less
regenerated. They have a lower fouling rate and active than I'd. Apart from Pt-Pd alloys, the
greater stability than Pt 'A1208 catalysts. They apparent activation energies of these alloys in this
operate efficiently at reduced pressures, which reaction are similar to that of Pd. T h e activity of
increases the yield and quality of the product. R-Pd alloys is not large and is unstable.

Platinum Metals Rev.,19 7 1, 15, (2) 72

Relation between Drift Potential of Cata- for aliphatic secondary alcohols at 200°C on Pt,
lyst and Reaction Rate in Liquid-phase I’d and Rh on kieselguhr. The initial rate of
Hydrogenation Processes. VTI. Investi- dehydrogenation depends on the alcohol partial
gation of the Catalytic Properties of Kaney pressure. On Pt the initial reaction rate and
Nickel I’romotecl by I’allacliinn
v. A. DKUL’,T. D. GLADYSIIEVA and D. v. SOKCK’SKII,
Kinet. Karuliz., 1970, 11, (5), 1274-1278
‘Ihe introduction of I’d to Kancy Xi catalysts
does not change the effectiveness of the catalyst
surface but greatly increases its useful area,
apparently because Pd increases the amount of
dissolved H, and its diffusion rate. The greater
number of active centres may be due to the
formation of Ni-Pd centres.
Adsorption and Catalytic Yropcrties of
Pallaclium-Iriclinm Electrode Catalysts
A. A. SUTYAGINA, I.. G. KOPEVA and G. P.
KHOMCIIENKO,, Vest. Mnsknv. Univ., Scr. 11,
Khini., 1970, 25, (s), 562-567
A study of the adsorptive and catalytic properties
of electrodeposited Pd, Ir, and Pd-Ir alloys
showed that H, adsorption decreases with
increasing Ir content and that catalytic activity
relates to alloy composition; e.g. the catalytic
activity of :-IS%, lr-Pd in hydrogenation and
CH:,NO, elcctroreduction in 0.1 N II,SO, was
greater than that of pure Pd or Ir.
Adsorption of IIydrogen on IIydrogenation
Catalysts in Solution. V. Adsorption and
Heat of Adsorption of Hydrogen on 0 s and
Ku Blacks in 0.1. N €II,SO, Solutions
YU. A. POIWYALIN and G. P. GRECHUSIIKISA,
Zh. Fiz.Klaim., 1970, 4, (IO), 2529-2531
Charging curvcs were used to study the adsorp-
tion of H, on 0 s and Ku blacks in 0.1 N H,SO,
at 0-50”<;, and the differential heat of adsorption
of H, was calculated. It decreased linearly from
12.5-1.7 kca1,hole as H, coverage of 0 s black
rose from 0.1 to 0.9. Kesults for Ru were similar.
Hydrogenation of Dinicthylethynylcarbinol
on Ruthenium-l’alladium Snpported Cata-
lysts in Various Solvents
D. v. SOKOL’SKII,T. M. DUKHOVNAYA and K. K.
D Z I M ~ A M ~ L I B V A ,Zbid.,
(I I), 2833-2836
’I‘he maximum activity of Ru-Pd,‘Al,O:, catalysts
for hydrogenation of dimethylethynylcarbinols
occurs with 20.8 at.‘):, Ru-Pd and is unrelated to
the solvent in tests with H,O, C,H,OH and
aqueous and alcoholic KOH solutions. The
solvents do not affect the kinetics of the process.
Changing the reaction temperature does not
alter the general form of the relation.
Effect of the Structure on the Dehydrogena-
tion Rate of Secondary Alcohols on Plati-
num, Palladium and Khodiuni Catalysts
hi. IIAJEK, J. c. DUCHET and K. KOCHLOEPL, Cnll.
Czech. Chem. Cnmmun., 1970, 35, ( 8 ) 2258-2274
The kinetics of dehydrogenation were studied
Platinum Metals Rev., 19 7 1, 15, (2)
adsorption coefiicient are influenced by sterie
effects of the substituents; on Kh or Pd polar
effects have more significance.
HOMOGENEOUS CATALYSIS
The Palladium Chloride Catalysed Cyclo-
dimerisation of 1-RIethylcpclopropene
F. J. WEIGERT, R. L. BAIRD and J. R. SHAPLEY,
.?. Am. Chem. Sac., 1970, 92, (22), 6630-6635
I-hlethylcyclopropene undergoes a thermal oligo-
merisation in the presence or absence of free-
radical inhibitors. With the Pd catalyst a facile
eyclodimerisation predominates.
Specificity of the Kinetics of Oxidation of
Ethylene to Acetaldehyde in the Presence
of Complexes of Palladium with 1,2-Naphtho-
quinone-4-sulphoxide
N. B. SIIITOVA, K. I. AL+.TVEEVand G. I. ELIZAROVA,
Kinet.Kataliz., 1970, XI, (s), 1152-1158
’I’he mechanism of Pd in the oxidation of C,H,
to CII,<:HO with complex catalysts of Pd with
1,z-naphthoquinone-4-sulphoxide (NQSO) was
explained by comparing the regularity of the
reaction kinetics with results based on the
stages of oxidation of Pd in the process and on the
formation of the complex of Pd(I1) with NQSO.
Organic Synthesis by Means of Noble Metal
Compounds. XLII. Reaction of Butadiene
and Aldehydes Catalysed by Palladium
Triphenylphosphine Coniplexes
K. OHNO, T. MITSUYASU and J. TSUJI, Tetrahedron
Letters, 1971, (I), 67-70
Butadiene reacted with aldehydes such as ben-
zaldehyde to give products such as r-phenyl-
z-vinyl-4,6-heptadien-1-ol and 2-phenyl-3,6- divi-
nyltetrahydropyran. The relative amounts of the
two products was controlled by the molar ratio
PPh, I’d in the catalyst. A mechanism is discussed.
The IIydroformylation of Nitroalkenes with
Rhodium Carbonyl
and w. WAKAMATSU, Bdl. Chem.
M. T A K ~ S D A
Sot. .7a~un,1970, 43, (7), 2191-2194
Nitrobenzene was hydrogenated to aniline using
[ Kh(CO),], above ISO’C. Other nitroalkenes
were also converted to their corresponding
aldehydes; good yields were obtained at 60-7o0C.
IIydroformylation of Olefins in the Presence
of Ku,,(CO),2
G. BRACA, G . SBRANA, F. PIXCENTI and .’l PINO,
Chim. E Ind., 1970, 52, (IS), 1091-1096
The hydroformylation occurred in more drastic
73
conditions than with Co catalysts. The isomeric Homogeneous Hydroformylation of Alkenes
distribution of products is not altered by the with Hydridoearbonyltris(tripheny1phos-
conditions in the area studied. The influence of phine)rhodium(I) as Catalyst
the concentrations of the reactants and catalyst c. K. mowN and G. WILKINSOS, J . Chem. SOC.,
A,
was investigated for cyclohexene. Znorg. I'hys. Thcor., 1970, (17)~2753-2764
RhH(CO)(PPh,),, is an excellent catalyst for
Decarbonylation of Allylic Alcohols Using hydroformylation of alkenes at z5,C at I atm.
Itlioclium(1) Complexes I:rom alk-I-ems high ratios of straight chain to
A. BMBKY, A. C. OEIIISHIAGEK and A. M. USHAU, branched chain aldehydes can be produced. The
Tetrahedron Z2ctters, 1970, (so), 4401-4403 dependence of rates and products on catalyst and
Ikcarbonylation of allylic alcohols, c.g. converting substrate concentrations and partial pressures of
cis-but-2-ene-1,4-diol to I-propanol was carried H, and CO, temperature and added excess of
out using (Ph,P),RhCl at IIO-I~O"Cin aceto- PPh, are described.
and henzonitrile.
The Protonation of Ruthenium- and
A Study of tlie Hydrogenation of Cyclo- Rhodium-bridged Carboxylates and Their
alkenes with IIomogeneous Rhodium ( h i - lJse as IIomogeneous Hydrogenation Cata-
plexes as Catalysts lysts for Unsaturated Substances
Y . TAKBUCHI, Diss. Abstr. H , 1970, 30, (IO), .'1 LEGLDINS, K. W. MITCIlELI,, G. I.. KEMPEI., J. D.
4572-4573 nuDDIcI< and G . WILKINSOX, J . Chem. Soc., A,
The use of (Ph,P),RhCl as a homogeneous Znorg. Ph-ys. Theor., 1970, (IS), 3322-3326
catalyst in the hydrogenation of cycloalkenes in a The protonation of rhodium(I1) acetate by non-
benzene or benzene-ethanol solution is reported. complexing, non-oxidising acids such as HBF4
Effects of using different solvents and varying gives the green Kh"'. The interaction with PPh,
the ligands of the Rh(1) complex are discussed. and CO gives complexes Rh(PPh,),Blj, and
Rh(CO)(PPh,),HF4. The acetate Ru,(OCOMe),
Speed of Homogeneous Catalytic Hydro- and its adducts with PPh, and pyridine were
genation of Unsaturated Compounds with characterised. Methanolic HHF, solutions of
RhCI[ P(C,3€16):j]:j Kh(1I) and Ku(I1) acetates and of Ku,(OAc),lCl
W. STROHME:II',K and R. ENDKES, %. Nuturf. n., in the presence of PPh, are active catalysts for the
197% 25, (91, 1068-1069 homogeneous hydrogenation of alkenes, alkynes
'The rate of hydrogenation depends on the nature and other unsaturated substances.
of the unsaturated compound. Olefins and
esters react more quickly if they contain terminal IIomogeneous Polymerisation of Butadiene
double bonds. For olefins the rates are; I-olefins Catalysed by Ruthenium Complex-Tertiary
. '2-ci.7- -2-truns- ,-> 3-trans-olefins; also, alkenes 1% Phosphine System
alkynes. Substitution of a H atom by halogen K. IIIKAKI and H. HIKAI, Macromolecules, 1970, 3,
decreases the reactivity.
(4), 382-387
The Reactivity of the Hydrogenation Cata- Hutadienc was polymcrised using dichloro(dodeca-
lysts MCH(CO)[I'(C~H~)~~]~~ (Me Rh, Ir) 2,6, I o-tricne- I, ~z-diyl)ruthcnium(
1V)- or di-
chloro-p- chlorobis(2,7 - dimethylocta-2,6 - diene-
on Unsaturated Compounds 1,8-diyl(diruthcnium(IV)tertiaryphosphinc cata-
w. STKOIIMEIBR and s. HOFMANN, Ibid., (II), lyst. The polybutadiene had cis-1,4-, trans-1,4-
1309-1 3 10 and trans-~,z-unit contents of 37-60, 20-32 and
T h e K h complex was more active and selective 13-34"4>; the molecular weighr was 2.6-4.8 x 10,.
than the Ir one in all cases. This behaviour, and The n.m.r. spectra of the catalysts was
the difference in adduct formation and dis- investigated.
sociation in benzene between the two complexes
is discussed in the light of increased electron
density of the Ir atom over the Rh. CHEMICAL TKCHNOLOGY
Further Observations on the Catalytic Anodic Ilischarge of Chloride Ions on Pt-Ir
Transformation of Renzoic Anhydrides into Alloy Electrodes
Fluorenones and Ijiphenyls G. PAITA, G. PIOKI and A. NIDOIA,J . Electrochem.
J. BLUM, D. MILSTBIN and Y. SASSON,J. Org. Chem., SoC., 1970, 117, (101, 1333-1335
1970, 35, (IO), 3233-3237 The behaviour of Ti-supported Pt-Ir alloys in
A study of the catalytic conversion of benzoic the electrolysis of NaCl was examined as a
anhydrides into fluorenones and biphenyls by function of Ir content, NaCl concentration and
several Kh complexes indicated that mixtures of electrolysis time. An Ir content as low as 0.5'x1
aromatic anhydrides react generally as if they was sufficient to eliminate the passivation effects.
were mixed anhydrides, leading to the formation Not less than ~-IO(%,Ir is necessary to have low
of assvmetricallv substituted products. potentials after thousands of hours.

Platirium Metals Rev., 19 7 1, 15, (2) 74

ELECTRICAL AND ELECTRONIC Selection of Thermocouples for Temperature
ENGINEERING Profiling of Semiconductor Diffusion Fur-
naces
Semiconductors Produced by Doping Oxide- I. O. NIEISON, Solid State Technol., 1970, 13,
glasses with Ir, Pd, Kh or Ru (101, 33-38, 55
c. c. SAKTAIS, w. D. KYDEN and A. w. LAWSON, Pt :I 3 ~;~~,Rh-Pt
thcrmocouplcs are discussed in
g. Non-crystallim Solids, 1970, 4, 231 terms of their best characteristics for temperature
Semiconductors were produced by diffusion profiling. The criteria for selection, care of the
doping oxide glasses with more than I wt.';,,. thermocouples, cvaluation of the materials and the
of Ir, Pd, or Ru and by implanting 40 keV l r calibration are all discussed.
ions into several oxide glasses. The properties
and methods of conduction in the semiconductors Noncatalytic Coating for Platinum-Rhodium
is discussed. Thermocouples
J. I?. KENT, Combust. Fiame, 1970, 14,( Z ) , 279-281
A mixture of Y oxide and Be oxide ( I O - I ~ ' ~ ~ )
TEMPEKATUKE gave a good noncatalytic coating for 1%-Rh
MEASUREMENT thermocouples. A series of thin coats of a solution
of 6-8');) Re oxide in a solution of YCl in HCl
Kcw Reference Tables for Platinum 1O(yo was applied to give a coating ~ o . 0 1 5mm on
Rhodium/Platinum and Platinum 13'%, 0.12 mm wire, after firing at 16ooOC.
Khodium/Platinum Thermocouples - An
Interim Report Measurement of Temperature in Corrosive
K . E. BEDPOKD,Z.S.A. Trans., 1970,9, (3), 248-253 Melts
Existing reference tables for Pt :Io'?,,Kh-l't and V. B. PDRFII.OVA, S. V. BODYACHEVSKII, L. A.
Pt :13';&h-Pt thermocouples are known to be AVVAKUMOVA and A. s. DEKMAN, Zzo. Akad. Nauk
partially inaccurate and are being revised jointly S.S.S.R., S e r . Fiz., 1970, 34, ( 6 ) , 1203-I205
by the NBS, NPI, and NRC ((:andda). Dctails A 1%-clad Rh-Pt thermocouple is superior to
are given of the progress to date and some of the refractory-clad Rh-Pt thermocouples at 900-
results are presented and discussed. 1400°C in HaO-R,O, and PbO-PbF,-B,O, melts.

NEW PATENTS
METALS AND ALLOYS
Gold-based Spinnerette Alloy
JOIINSON, MATlIIhY & GO. LTD.
U . S . Patent 3,529,959
A gold-based spinnerette alloy contains between
so':,, and Eo",,, Au, between 0.04 and 0.5';,) I r
and the remaining part Pt, apart from the
impurities. ,4 method of making the alloy con-
sists of induction melting the components, casting
a sheet and homogenising.
CIIEMICAL COMPOUNDS
Osmium Carbonyl
JOHNSON, IMATTHEY & CO. LTD.
U .S. Patent 3,508,870
Method of prcparing 0 s carbonyls is described.
A solution of OsO, in an inert hydrocarbon
solvent is heated to an elevated temperature
under super-atmospheric pressure in the presence
of CO. The product is primarily Os,(CO),,
with traces of Os,O,(CO), ,.
E1,ECTRODEPOSITPON AND
SURFACE COATINGS
Coating or Inlaying
JOIINSOS, MATTHEY & CO. LTD.
British Patent 1,207,970
A C u or Cu alloy is coated or inlaid with a thin
layer of a noble metal such as Au, Ag, Pd or Pt
or alloys thereof by interposing between the two
a layer of Ni, Ye, Co, Mo, or V, and heating
the three layers under pressure to bond them.
Reductive Vapour Deposition of Osmium
EKGLISH ELECTRIC VALVE CO. LTD.
British Patent 1,209,318
High purity 0 s deposits are obtained on a sur-
face by vapour deposition from an OsO,/Hz
mixture. OsO, is dissolved in water at room
temperature and H, (or a gas containing H,)
bubbled through the solution. The resulting gas
is mixed with another reducing gas to give a
predetermined ratio of OsO, to reducing gas.
In contact with a hot body this gas deposits
metallic 0 s .

Platinum Metals Rev., 1971, 15, (2), 75-80 75

Electroless Noble Metal Plating
MOBlL OIL CORP. U.S. Patent 3,511,683
Pt and other noble metals are deposited on metal
or mainly metal colloidal particles by displace-
ment plating in non-aqueous solution. The
particles must have an outer sheath of a reactive
metal which is above the noble metal in the
electrochemical series. In an example Sn-coated
C black particles are coated from a solution of
PtCl, in CfiH6. The coated particles are used in
fuel cell manufacture. Other compounds used
for displacement plating are a Au octadiene
complex, Ag acetylide, Ir ally1 and Ag perchlorate.
Plating IAJWStress Bright Rhodium
SE1.-REX CORP. U.S. Patent 3,528,895
An aqueous acid electrolyte for the deposition
of bright low stress Rh contains Rh and Cu ions
in synergistic combination with sulphamic acid.
Gold and Kutheniuni Plating Baths
TECHNIC INC. U.S. Patent 3,530,049
An aqueous electroplating bath for depositing
Ru contains a chelate of Ru with ethylenediamine
tetraacetic acid, nitrilotriacetic acid or cyclo-
hexanediamine tetraacetic acid. The above
chclatcs are also used as grain refining agents in
acidic Au plating baths.
Electrodeposition of Palladium
JOHNSON, &CATTHEY & CO. LTD.
U.S. Patent 3,530,050
Electrolysis or electrodeposition of Pd is carried
out with an aqueous neutral or alkaline bath
containing a Pd compound and an ammonium
salt of a weak organic acid which does not form
an insoluble compound with the I’d compound.
Metallising Coniposition Conductor
IXTIRNATIONAL BUSINESS MACHINES CORP.
U.S. Patent 3,537,892
A conductive metallising composition for deposi-
tion and firing at 72s-yooT on an insulating
substrate to form a conductive element consists
of a metal component of 60-70‘,)(, Au, 10-20lb
Pt and 10-30:(, Pd, a vitreous frit and a vehicle.
Ruthenium Complex
JOEINSON, MATTIIEY & CO. LTD.
German Appl. 1,959,907
A new complex suitable for electroplating baths
has an anion of general formula:
Ru,NClxBr, x(H20)2,where x is 0-8.
Pore-free Coatings with Group VIII Metals
H. GUENTHER et al. East German Patent 71,678
1%coatings are produced on metals such as Ti
or ‘J’l by electrolytic polishing of the surface,
then coating with a thin layer of Pt followed by a
diffusion annealing treatment at 650-800°C for
at least 20 min. This may be followed by the
deposition of an additional Pt layer.
Platinum Metals Rev., 19 7 1, 15, (2) 76
LABORATORY APPARATUS
AND TECHNIQUE
Pulse-activated Polarographic Hydrogen
netect6Jr
NATIONAL AEKONAUTICS & SPACE
ADNIINISTRATION U.S. Patent 3,509,034
A polarographic H, detector has three electrodes,
a platiniscd anode, a <;u rcference electrode and
an auxiliary electrode, and a system for periodic
reactivation of the platinised anode by means of
potential pulsing.
HETEROGENEOUS CATALYSIS
Oxidation Catalyst
JOHNSON, MATTHEY& CO. LTD.
British Patent 1,208,101
In a continuous process for the preparation of
gluconic acid or glucosaccliaric acid, an aqueous
solution of glucose containing Na or I< carbonate
or bicarbonate is contacted in a trickle column
with an 0,-containing gas and in the presence
of a supported P t group metal.
Catalytic Conversion of Gases
SHELL INTERNATIONAL RESEARCH MIJ. N.V.
British Patent 1,210,867
An apparatus is described in which the activity
of a catalyst, e.g. Pt, for the reduction of HNO:,
tail gases, is not reduced by the presence of solid
particles in the gases.
Oxidation Catalyst
& HAAS G.m.h.H.
ROHM I3riti.di Patent 1,214,793
Dicyanogen is obtained by the oxidation of
gaseous HCN admixed with C O or steam in the
presencc of a Pt group metal, e.g. a P t gauze.
Hydrogenation Catalyst
TOKAY INDUSTRIES INC. British i’atent 1,214,958
Cyclohexane is produced by the hydrogenation
of COHO in the presence of Pt on a carrier.
Oxidation Catalyst
ZAKLADY AZOTOWE IM. P. FINDEVA
Rritish Pateat 1,216,019
Oxidation of N H , to HNO, is catalysed by PtO,.
Catalyst
CEKTRE NATIOXAI. D’BTUDES SPATIALES
British Patent 1,216,240
A catdyst for the decomposition of N,H,, and its
derivatives (for use in rocketry) consists of 25-45
wt.l%, of I r on a porous A1,Q carrier, the com-
bination being free from both S and Rr,.
Curing of Organosilicon Compositions
DOW CORNING CORP. British Patent 1,217,618
Si resin compositions are cured with 0.1 ppm of
l’t and a tetramethyl guanidine carboxylate in an
amount representing 0.01-4 moles per g.atom
of 1%.
Hydrocracking Process
TEXACO DEVELOPMENT COKP.
British Patent 1,217,815
High octane fuels are produced by two stage
hydrocracking. The first stage uses a base metal
catalyst and the second stage a noble metal
catalyst.
Unsaturated Ester Production
MITSUI PETROCHEhlICAL INDUSTRIES LTD.
British Patent 1,219,510
The reaction of an alcohol and 'or aldehyde with
0 , to form an ester of an unsaturated carboxylic
acid is catalysed by Ru, Rh, Pt, I'd or an oxide
of one of these metals on a support.
Aromatic Compound Production
ASAHI KASEI K . K. K. British Patent 1,219,704
Aromatic compounds are produced from
petroleum fractions by contacting rhem with
11, at 400-650"C in the presence of a supported
catalyst. The catalyst consists of A1,0, or another
support impregnated with 0.1-1 "., Pt, 0.1-1
Pd and 5-25':;, Cr oxide. The catalyst is treated
with 11, after impregnation with the active
metals.
IIy(lrogenationCatalyst
SISCLAIK KESI'.AKCII INC. U.S. Patent 3,506,566
Clarified or decant oil is converted to distillate
fuel by a two-stage catalytic hydrocracking-
hydroisomerisation process. The second-stage
catalyst is a noble metal catalyst, e.g. Pt/A1,0,
or Pt Uumino-silicate.
Catalytic: Keforming Process
CHEVKOS RESEARCH CO. U.S. Patent 3,507,780
A reforming process using a catalyst containing
0.01-0.3';~;, Pt, 0.01-0.3";, Re, and o.oor-o.r?;,
Ir associated with a porous solid carrier is
started up by contacting the naphtha with the
catalyst in the presence of an inert gas, for
example., iK2. The pressure in the reforming
zone should be about 200 p.s.i.g. and the catalyst
temperature about 650 I' when the naphtha is
first contacted with the catalyst at a space velocity
of I v v'h. T h e catalyst temperature is increased
to 900'F over a 2-3 hour period while building
up autogcneous pressure of produced H,. See
also [J.S. Parent 3,507,781.
Catalytic Production of LPG
UNIVERSAL 011. PRODUCTS CO.
U.S. Patent 3,511,773
A hydrocarbon feedstock is converted to LPG
and high octane reforinate using a catalyst of a
Pt group component and a halogen component
combined with a carrier containing A1,0, and
about I-Io~:, of crystalline aluminosilicate. Pt
Platinum Metals Rev., 19 7 1, 15, (2)
is the preferred catalyst for the selective cracking
of paraffins to C , and C,, hydrocarbons and
production of a high octane reformate.
Paraffin Conversion Cataiyst
SIIELI. OIL CO. U . S . Patent 3,511,888
A new catalyst for paraffin dehydrogenation and
dehydrocyclisation consists of 0.01-5":) P t and,'
or I'd modified with Sn or I3i on inert SO,.
Purifying Hydrogen Separated from 11
Catalytic Reforming Efiluent
UNIVERSAL 011. PRODUCTS CO.
U.S. Patent 3,520,799
A process is described for the catalytic reforming
of hydrocarbons in the presence of H, to produce
high quality gasoline boiling range products.
Relatively impure hydrogen for recycle purposes
and other uses is provided by compressing and
contacting this hydrogen with a portion of the
liquid reformed product. Catalysts are e.g.
Pt;Al,O,. U.S. Patent 3,520,800 is similar.
Hydrocarbon Conversion Process
UNIVERSAL OIL PRODUCTS CO.
U.S. Patent 3,523,914
A hydrocarbon conversion catalyst consists of a
Pt group metal and a Re component combined
with a carrier material containing Al,O, and a
finely divided crystalline aluminosilicate. In
one example it contains 0.05-1.0');) Pt and 0.05-
I.O~<,Re, combined with yAl,O, carrier material
having 0.5-20 91 of the H, form of mordenite
uniformly distributed.
Hydrogenation Catalyst
UNIVERSAL OIL PRODUCTS CO.
U.S. l'ateizt 3,529,029
Aromatic hydrocarbons are hydrogenated to
cycloparaffins in the presence of a catalyst which
contains 0.01--2.0 wt.'X Pt or I'd, 0.01-2.0wt.'::,
Re and 0.01-1.5 wt.'):, of an alkali metal,
preferably Li.
Catalytic Dehydrogenation of Cyclohexanol
and/or Cyclohexanone
INSTITUT FKANCAIS DE P ~ T R O I X , DES
CARBURANTS ET 1,UBRIFIANTS
U.S. Patent 3,534,110
Phenol is made by the catalytic dehydrogenation
of cyclohexanol or cyclohexanone where the
catalyst contains Pt and preferably also Ir on a
SiO, carrier of 1 m 3 m m,/g specific surface
and 0.7-1.1 cm3/g porous volume.
Dehydrogenation over Platinum-Rhenium
Catalyst
CHEVRON RESEARCH co. U.S. Patent 3,535,402
Paraffins with 3-5 C atoms are dehydrogenated
by contacting the paraffins with the catalyst
containing 0.1-3(%, Pt and o.r-g[~/,Re associated
with a non-acidic porous solid carrier. I>e-
77
hydrogenation conditions include a temperature
of c)oo-1100"1 and a pressure of 3-100 psig.
Catalytic Ilydroge~iationof Xitrobenzene
INTBKNATIOSAI, ii1CICBL LTD.
I;reizrh Patent 1,587,963
An aqueous solution of nitrobenzene is hydro-
genated to aminophenol in the presence of a
I't-Ru catalyst, e.g. Pt-Ru/l:.
Hydrogenation of' Unsaturated Aldehyks
JOIISSON, MATTHBY & CO. I.TD.
Gerinaii Appl. 1,568,861
L'nsaturated aldehydes are reacted with H, in the
presence of a catalyst containing P t activated by an
alcoholic alkali metal hydroxide or oxide solution.
Improwil Selective Catalyst Reduction
JOHNSON, 'MATTIIEY & (XI. I.TD.
Gemaiz Appl. 1,568,8?4
A new process is intended to increase the
selectivity and thus the yield of alcohol in the
reduction of an aroniatic aldehyde or ketone. For
the process a known I'd catalyst, e.g. palladised
wood charcoal, is used in the presence of a n
amine, especially an aromatic aminc.
Cat;1lyst
W. K. GRACE 8r CO. <~errnarzAppl. 1,933,240
HCX is produced by the gas-phase reaction of a
hydro-carbon (e.g. CH,) with NH:, in the presence
of a catalyst of 0.1-0.6 wt."., Pt!mullite.
1)ewaxing Catalys~
( ; e ~ i n a nflppl. 1,954,368
CIIEVKOS K ~ ~ S I ~ A K C0.
CII
IIydrocarbons arc dcivaxed by reaction with H,
in the presence of a catalyst which consists of
0.01-3 wt.",, Pt and 0.01 to 5 wt.":, Kc on a
porous solid support.
IIydrocwicking Catalyst
CIXHVKOS KESBAKCH co. Gerinaii A p p l . 1,956,715
A hydrocracking catalyst consists of a layered
crystalline alumino-silicate on which is deposited
of Pt, Pd, Ir or their compounds and
of Re or a Re compound.
IIy(lroc;raeking Catalyst
m1ivnoS KKSBAKCII CO. l)i.itclz clppl. 70.02,354
A hydrocracking catalyst consists of a hydro-
genating metal deposited on an amorphous
aluminosilicatc carrying 0.0-5.0 wt
fluoride. T h e Al,O,,:SiO, ratio is 70:30 to 5 3 5 .
T h e catalytic metal is o.oo~-z.o",, of Pt, Pd,
I r and'or their compounds and 0.005-2.0'~;, of
Re and or Re compounds.
1)ehyclrogenation Catalyst
INSTITUT FKANCAIS DE P ~ T K O L I Z DIZS
, Hydrogenation Catalysts
CARBUKANTS ET LUBKIFIAiiTS
I > i l t C h f l p p l . 70.04,770
A new catalyst for the dehydrogenation of
saturated hydrocarbons consists of A1,0,, sup-
Platinum Metals Rev.,19 7 1, 15, (2)
porting 0.05-2 Wt.",, P t and 0.01-0.5 wt.',,, Ir,
Ru and an alkali or alkaline earth metal represent-
ing 0.3-10 times the amount of noble metals.
HOMOGENEOUS CATALYSIS
New Platinum Catalysts
GENEKAI, ELECTKIC CO. Rritash I'ateizt I,ZI 1,699
Significantly improved hydrosilation of aliphatic
unsaturated materials can be obtained by using
as catalyst a 1%-siloxane complex, e.g. P t com-
plexed with ~,~-divinyl-tetra~iethyldisiloxane or
1,3-divinyltetraphenyldisiloxane.
Catalyst
I'AHBENI'ARRIKIIN BAYEX A.G.
British I'ateiit 1,213,779
Organic-silicon compounds are obtained by the
addition of a silane or siloxane to an olefinically
unsaturated organic compound in the presence
of Me,Py,PtI.
Production of Hydroquinone
LONZA LTD. British I'azatent 1,215,568
C,H,, <:O and H, are combined at increased
temperature and pressure in the presence of
[ Ru(CO), I:,.
Catalytic: Iiyclrogenation or Nydroformy-
lation
JOHSSON, MATTHEY & CO. LTD.
British Patent 1,219,763
A hydrogenation or hydroformylation process is
catalysed in the presence of a base by a Pt metal
hydride, halide or pseudohalide complexed by
an organic isocyanide or a Group VB or VIH
compound. For Rh and I r halides a Sn or C c
dihalide may also serve as the complexing
agent. Particular catalysts are [PPh,),RuCl, and
RhI I(CO)(PPh,) s.
Platinum Complexes
RIIONE-POUI.ENC S.A. U.S. Patent 3,522,327
New complexes of PtCl, with triaminophosphincs
arc useful catalysts for curing organopolysiloxane
resins. They have the general formula:
I't(.:l,.zP(NR'R''),, and are formed by simple
addition.
1Iomogeneous Dehydrogenation of Paraffins
ETHYL CORP. U.S. Pateiit 3,524,898
6-20 C parafins are dehydrogenated by contacting
them with a carbonyl halide Group VIII metal
catalyst complex, such as IrCl(CO)(PR,)2, at
300-425'<:, optionally in the presence of a H
acceptor.
IMPEKIAI. CHEMICAL INDUSTKIBS LTD.
U.S. Patent 3,524,899
Catalysts for the hydrogenation of ethylenic or
acctylenic coinpounds are the reaction products
78
of a Ru compound in which the metal has a
valency of two or more and a simple or complex
halide of an element of Group IA, IIA or IIIB.
Examples are RuCI,(II,O),, RuCl,,:SEt,),,
Ku<1: .(IT hJ and KuCl ,(Aslit
I~ynrocarbox?-lationof Olefins
UNION 011. CO. U.S. Patent 3,530,r 55
Olefins are hydrocarboxylated by contacting the
olefin under liquid phase conditions with a
catalyst which consists of a Pt or I'd complex
with an aromatic phosphine, H,O and CO. High
reactivity and high 5-ields of the normal acid are
obtained by incorporating an anionic or nonionic
surface active agent in the reaction medium.
CopolymerisutioJi Catalysts
CESKOSLOVESSKA AKADBMII! VBD.
(;ertnaii Appl. 2,008,427
A siloxane is copolymerised with an unsaturated
compound in the presence of a Group VIII
metal complex, which may be, e.g. RhCl(PPh:,):,,
RuCI(H)(PPh,):, or H<CO)Kh(PPh:,),.
FUEL CELLS
Three-layer Fuel Cell Electrode
UNIOS CARBIDE cow. British Patent 1,216,794
I he fuel cell electrode structure consists of a
I .
fine-pored porous metal layer on the electrolyte
side, a gas-permeable plastic-bonded catalysL
layer and a coarse-pored porous metal layer.
'I'he plastic-bonded layer may contain a noble
metal catalyst, e.g. Pt.'C in p.t.f.e.
G a s Diffusion Electrodes
KOBERT BOSCH G.m.b.H. BritiSh Patent I,22O,OI3
Gas diffusion electrodes for fuel cells are pro-
duced by coating a gas-permeable base with a
varnish containing the catalyst metal. I n one
example Au and Pt dioxide dispersed in a
cyclised rubber varnish are used to produce a
catalyst layer on a p.t.f.e. plate.
Metal Boride Fuel Cell Catalyst
LEESONA GORP. U . S . Patent 3,513,028
New catalysts for fuel cells are Group 111-VIII
transition metal borides. 'I'he preferred catalysts
are Xi, Ku, Rh, Pd, Os, Ir and P t borides. They
may be produced by coating a porous substrate
with a metal black and then treating the coating
with an alkali meral borohydride.
Fuel Cell Electrode Production
M T S U S H I T A E1,ECTKIC INDUSTKIAI. CO. LTD.
German Appl. 1,964,568
A mixture of Ni and Sb is produced by reduction
from a solution containing ions of both metals.
This mixture is then added to a solution of a
Pt group metal salt and the Pt ions reduced to
Pt metal.
Platinum Metals Rev., 1971, 15, (2)
CHEMICAL TECHNOLOGY
Heating of Corrosive Vapours
I.APORTE TITANIUM LTD.
British Patent 1,219,573
' I X I , , vapour is heated in a plurality of tubes
having inlets and outlets made of I't or an alloy
of Pt with Kh, Ru or Ir.
1)egassing Platinum Powders
E.I. DU FONT DE XEMOURS & CO.
U.S. Parent 3,511,640
A process for preparing degassed P t powders
consists of mixing finely divided Pt powder with
at lcast an equal volume of a diluent metal oxide
powder and heating the mixture until all gases
have evolved. The powder mixture is cooled and
the Pt powder separated from the diluent. The
degassed powders are particularly suitable for
application to "green" ceramic sheets used in the
production of monolithic multi-layer ceramic
circuit components.
Catalytic Igniter iMernbers
R0I.I.S-ROYCE LTD. U.S. Patent 3,527,680
The activity of a Pt or Pt alloy catalytic igniter
for a gas turbine engine is improved by etching
the igniter to remove the initial surface layer,
plating the member with a layer of Pt which
supports catalytic ignition and heat treating.
Separation of Hydrogen from Gas Mixtures
JOHNSON, MATTHEY & CO. LTD.
Germari Appl. 1,567,601
A H, diffusion membrane consists of a Pd alloy
containing 0.7-0.8';:, R and 4.5"{, Ag, or 4.3% Ag
and 0.75% 13.
Diffiision Device
JOHNSON, MATTHEY & CO. LTD.
German Appl. 2,005,494
A device for the separation of €1, from gas
mixtures consists of a stack of spaced Ag-Pd
diffusion members.
Platinum Coating of Refractories
CORNING GLASS WORKS tierman Appl. 2,007,056
Refractory materials are coated with Pt or Pt
alloys by flame spraying with a plasma flame at a
rate of at least 30 m,sec. The powder is classified
to 20-44 y. before spraying. 'The coating is heated
to at least IZSO"<;.
GLASS TECHNOLOGY
Stirrer for Molten Glass
PILKINGTON RROS. LTD. British Patent 1,211,797
A stirrer for molten glass consists of a M o core
coated with a refractory material (e.g. A1,0,)
and sheathed with Pt or Pt alloy. The gas space
between core and sheath is charged with inert gas.
79
ELECTRICAL AND ELECTRONIC
ENGJNEERING
Capacitor
EKIE TECHNOI.OGICAL PRODUCTS I S C .
British Patent 1,212,820
A capacitor consisting of a central ceramic layer
sandwiched between two outer layers of the same
ceramic has painted-on electrodes of Pt-Pd,
for example, and electrode terminals of Ag
paint.
Field Effect Transistor
TEI.EPUNI<EN PATENTVEKWEKTUSGS c;.m.b.Ei.
Briti.sh Patent 1,217,665
In a field effect transistor, metal clectrodes are
applicd to its semiconductor body as a source and
drain and, together with the body, for metal-
semiconductor rectifying contacts. Au, Pt and
Pd are suitable contacts.
Self-regulating Heating Elements
JOHNSON, MATTHEY & GO. LTD.
U.S. Patent 3,520,043
Self-regulating heating elements have first and
second components connected in parallel so that
the resistivity of the element increases with
temperature. Preferably one component forms
a sheath for a core made from the other com-
ponent. Suitable materials for the sheath include
Xi-Cr and Fe-Ni-Cr alloys; suitable materials
for the core (apart from Fe, Fe alloys, Ni and
S i alloys) include CO, Mo, W, Pt, Pd and Ta.
Semiconductor Connections
IEWL>,TT-IW:KAKD CO. U.S. Patent 3,521,134
A metallic contact pad is formed on stripped
areas of a semiconductor to reduce the thermal
and electrical resistance. Pt silicide covered with
Au and Mo provides a suitable material for the
pad.
Glass Electrode
BECKMAN INSTKUMbNTS INC.
1J.S. Patent 3,523,777
In a method of sealing an internal half-cell
(Pt AgIAgCl) into a constricted portion of an
inner glass tube, the constricted portion is
painted with Ag paint and then sealed on to the
Pt wire by induction heating.
Platinuni Coated Electrode
MATTHEY BISHOP INC. C.S. Patent 3,532,556
A process of coating substrates with Pt involves
reacting a Pt-type oxide with a reducing and
dispersing medium composed of a 2-5 C aliphatic
alcohol. A aater-soluble inorganic salt or acid
is added and most of the dispersion medium is
removed from the platinised substrate while
retaining the P t wet and oxidising rcsidual
adsorbed organic matter, and removing water.
Platinum Metals Rev., 19 7 1, 15, (2)
The reducing and dispersing medium preferably
also includes formaldehyde.
Electric Film Resistance
SIEMENS A.G. German Appl. 1,480,606
An electric film resistance, applied to glass or
ceramic, consists of 40-60'2, Au, ro-15U/;I Pt,
25-30";~ Pd and ~ - I O ' ; { ~ Rh or Rh,O,,.
Printed IIeater Elements
JOHNSON, MATTHEY& CO. I.TD.
German Appl. 1,912,216
Resistor compositions for use as heating elements
may be applied by screen or other printing
techniques to various ceramic substrates. They
consist of a mixture of IC-80 wt.% (especially
46-65 wt.:;,) of finely divided RuO, and balance
glass. Alternative compositions include finely
divided Ag and compositions of matter formed by
heating RuO, with a Group V metal oxide, such
as NbO,. See also German Appl. 1,640,561.
Anode for X-Ray Tubes
METAI.I.WEKKE PLANSEE A.G.
Gennun Appl. 1,952,526
The anode is made from an alloy of W containing
0.05-5 I;(>, preferably 0.15-1.5 ",, 1%.
Brine Electrolysis Electrode
IMPERIAI. METAI. ISDUSTKIES (KYNOCH) LTD.
Dutch Appl. 70.06,285
An electrode is made with a surface of film-
forming metal coated with Ru and/or RuO, mixed
with a chemical compound containing the film-
forming metal, C1, and 0,. The film-forming
metal may be Ti, Ta, N b or their alloys. A
suitable chemical compound is T i oxychloride.
MECHANICAL ENGINEERING
Drawing Ruthenium and Alloys to Wire
INTEKNATIONAL NICKEL CO.
U.S. Patent 3,528,862
Improved results in drawing Ru or Ru alloy wire
arc obtained with a new process involving
special control of the die temperature at ION+
1300 C in a non-oxidising atmosphere. The metal
is drawn through a wire drawing die at 90-
I050 c.
TEMPERATURE
MEASUREMENT
Thermocouple
GENERAL MOTORS COW. U.S. Patent 3,527,620
A high-temperature thermocouple system con-
sists of a pair of interconnected thermoelectric
elements, one an alloy containing 55 wt.% I'd,
31 wt.";, Pt and 14 wt.%, Au, and the other
65 wt.":, Au and 35 wt.":, Pd.
80