PMR v19 I1 002 040

UK ISSN 0032-1400
PLATINUM METALS REVIEW

A quarterly survey of research on the platinum metals and
developments in their application in industry
VOL. 19
JANUARY 1975
of
NO. 1
Contents
Exhaust Purifiers for Compression Ignition Engines
Organometallic Chemistry of Platinum
11
The Production of Acetic Acid
12
Superconductivity in Palladium-Hydrogen Alloys
14
Heavy Platinum Plating from a Molten Salt Bath
1.5
The Production of Heavy Water
16
Photocatalytic Properties of Materials
21
Trifluorophosphine Complexes of the Platinum Metals
22
An Age-hardenable Palladium Based Spring Alloy
29
Abstracts
30
New Patents
37
Communications should be addressed to

The Editor, Platinum Metals Review
Johnson Matthey & Co Limited, Hatton Garden, London EClP 1 A E
Exhaust Purifiers for Compression

Ignition Engines
CATALYTIC CONTROL OF DIESEL EXHAUST GASES
By E. J. Sercombe
Research Laboratories, Johnson Matthey & Co Limited
systcm in order to give acceptable efficiencies

over a wide speed range. These can compete
with petrol fuelled spark ignition engines.
The larger commercial vehicles are usually
fitted with direct injection (DI) engines where
adequate power is available without excessive
fuel consumption. Both types of engine are
highly reliable and can be operated for long
periods without needing major servicing.
In some of these applications, such as
mining, or inside factory and warehouse areas
where engines are operating in confined
spaces, it is necessary to ensure that exhaust
emissions are not hazardous to health or
to general safety. In contrast, emissions from
engines used in marine applications can be
freely discharged to the atmosphere without
causing an immediate nuisance or health
hazard. However, there is increasing public
awareness of the direct and indirect harmful
Compression ignition engines using diesel effects of all forms of environmental pollution.
oil as fuel are widely used as motive power in Therefore, extensive effort is being applied to
road, rail, or sea transport and for haulage or develop practicable and economic methods
lifting equipment in mines and factories. for the control of pollution emanating from
They range in size from small air cooled industrial manufacturing processes and from
industrial units of less than I litre cylinder the combustion of fuel in engines used on
displacement volume to large marine engines mobile or stationary applications.
of over 1500 1. The performance of these
The pollution from internal combustion
engines is highly dependent on the efficiency engines is due to the chemistry of the reactions
of the combustion process and considerable taking place between fuel vapour and air
effort has been applied to the development of mixtures during high temperature combustion
different types of combustion chamber in and to the effects that engine design and
order to balance the need for fuel economy engine operating conditions have on these
with the requirement for high power output. reactions. Although this article is primarily
The small high speed diesel engines used in concerned with diesel engines it is important
taxis, cars and other light duty vehicles are to remember that there is no fundamental
frequently based on an indirect injection (IDI) difference from the analogous pollution prob-
A new platinum catalyst system has

been developed at the Johnson Matthey
Research Laboratories for the OxidatiorL
of hydrocarbons and carbon monoxide
emitted by compression ignition internal
combustion engines. The catalyst was
evaluated during tests on a direct
injection diesel engine using the 13mode cycle devised by the California
Air Resources Board, thereby assisting
the design of catalyst systems to meet
specijc emission control targets in
particular industrial applications. The
new catalyst combined with retardation
of injection timing can provide overall
control of exhaust emissions, including
the nitrogen oxides, from diesel engines.
Platinum Metals Rev., 1975, 19, (l), 2-11
A Honeycat Diesel Exhaust Purijier unit forming part of the exhaust train of a FordStamford 40 kVA diesel alternator set assembled by John S. Allen & Son Limited. This
stationary generator is powered by a Ford model 2712E four cylinder diesel engine, which
is coupled to a Stamford brushless alternator giving a 415 volt three-phase 50 Iz output.
The set will be used within a building
concentration of individual components in

the combustion products will vary considerably according to engine type and engine
operating conditions. Typical exhaust from a
petrol engine may contain up to 10 per cent
carbon monoxide-due to the combustion
process taking place at, or near to, stoichiometric air/fuel ratios-together with about
1000p.p.m. hydrocarbons from unburnt fuel
or partially oxidised products. In contrast a
diesel engine operates with a large excess of
air, which is sometimes increased by turbocharging, so combustion is more complete.
Concentrations of 0.1 per cent carbon
monoxide and 300 p.p.m. hydrocarbons are
typical. Some sulphur dioxide may be present
due to combustion of organic sulphur compounds in the fuel, particularly for diesel oils.
Diesel exhaust may contain up to 0.5 g/m3
particulate matter, which becomes very
obvious as a dark smoke. This is due to
lem for petrol fuelled engines. Therefore the

principles governing application of catalysts
to the control of engine emissions and some
of the legislation are common to both spark
and compression ignition engines.
Engine Exhaust Emissions

Exhaust gases contain the oxidation products from combustion of the hydrocarbon
fuel and, if chemical equilibrium was reached,
these products would consist almost entirely
of carbon dioxide and water vapour. This
would OCCLU at high temperatures provided
the fuel vapour plus (at least) the stoichiometric quantity of air was homogeneously
mixed and the residence time was sufficiently
long. In practice the combustion processes
in an engine are extremely complex as fuel:
air ratios and temperature can vary considerably according to the position in the combustion zone. Therefore the composition and the
Platinum Metals Rev., 1975, 19, (l),
incomplete combustion, and smoke formation

is favoured by high pressures, high temperatures and low oxygen availability. Black
smoke due to presence of carbonaceous
material must be distinguished from the
white smoke caused by unburnt fuel droplets
and from the blue smoke due to combustion
of lubricating oil. Smoke formation does not
normally occur to any significant amount in a
properly maintained petrol engine.
The temperature of combustion in both
compression and spark ignition engines is high
enough to cause formation of nitrogen oxides
(NO,) from the nitrogen and oxygen present
in the air used for combustion, and up to
4000 p.p.m. NO, may be present in exhaust
gases. In a direct injection engine the formation of NO and smoke is highly dependent on
the conditions in the vicinity of the fuel injection nozzle and on the degree of &/fuel
mixing in the swirling action caused by the
geometry of the combustion chamber. Conditions which favour minimum smoke formation tend to promote NO formation and,
therefore, design of the combustion zone and
fuellair inlet arrangements has to be a compromise. Until recently emphasis has been
placed on minimising smoke formation.
The distinctive obnoxious odour of diesel

exhaust gases is a well know-i nr?;sance. It
should not be considered as a separate
emission because it is entirely due to the
presence of oxygenated compounds produced
by partial oxidation of certain fuel fractions
and is, therefore, included with hydrocarbon
emissions. Thus any method that reduces
these emissions or promotes complete oxidation to carbon dioxide and water will help
eliminate odour.
Legislation
The United States, Canada, Japan, South
Africa, and many European countries, including the United Kingdom, have introduced
legislation designed to limit the emission of
smoke from diesel engines used on road
vehicles. Precise limits, test procedures, and
methods of enforcement vary considerably.
Experience in the United Kingdom has
shown that although it is possible to ensure
that new engines, as delivered from the
manufacturer, meet the regulations there are
very obvious failures under actual use
conditions, particularly when heavy transport
vehicles are working under maximum load.
Until relatively recently no country has
Table I
American Legislation for Exhaust Emissions
Regulation
DateX
Test
Method
HC
Emission Limits
HC+
CO
NO*
1973-74
1975-76
1977
CARB
California, light duty vehicles
1975
California, light duty trucks
1975
cvs
cvs
California, heavy duty vehicles
CARB
CARB
U.S. Federal, heavy duty vehicles
1974
CARB
U.S. Federal, light duty vehicles
1975
1976
U.S. Federal, light duty trucks
1976-77
cvs
cvs
cvs
* Some of these regulations are n o t yet finalised
40
30
25
Units
16
10
5
g/bhp/h
g/bhp/h
g/bhp/h
0.9
9.0
2.0
g/mile
2.0
20.0
2.0
g/mile
40
16
g/bhp/h
0.41
0.41
3.4
3.4
3.1
0.4
g/mile
g/mile
2.0
20
3.1
g/mile
but have been proposed for the dates shown
The elimination of noxious emissions from equipment used in tunnel construction i s

obviously necessary to safeguard the health of those engaged in the work. This dump truck
owned hy Southdown Plant Limited has been Jitted with a Honeycat DEP unit before use
by Tube Headings Limited in driving a tunnel beneath a main road in north London
attempted to limit other emissions by legislation but pollution in the United States,
particularly in CaIifornia, has caused that
country to consider the overall pollution
problem in considcrable detail and to propose
regulations (some of which are now becoming
legally operative) for all types of road vehicle.
Table I shows the emission limits defined in
U.S. Federal and California State regulations
for various types of vehicle. For heavy duty
vehicles (which usually use diesel engines to
supply motive power) the total brake specific
emissions for a 13-mode steady state cycle
are determined by means of a weighted summation of mass emissions determined for each
mode. This cyclc has been defined by the
California Air Resources Board and is conveniently referred to as the CARE cycle.
U.S. Federal regulations for heavy duty
diesel and petrol powered vehicles over 6000

lb. (approx. 2.7 tonnes) gross vehicle weight
use the same test cycle with slight modification
of experimental conditions. Federal limits for
diesel light duty vehicles are based on a
constant volume sampling (CVS) cycle as used
for the I972 petrol engine regulations.
It may be possible to meet all these targets
for road vehicles by engine modifications (and
much development effort has been applied by
manufacturers to achieve this) but it is
believed that the very low combined figure
of 5 g/bhp/h for HC and NO, may be quite
difficult to obtain and maintain under actual
service conditions. In this and other special
cases, such as when engines are used in confined spaces where ventilation may be inadequate, additional means of control may be
necessary. Catalytic oxidation is a proven
system (I) that is being applied to the analogous problem on petrol engined vehicles
which are now becoming subject to stringent
exhaust regulations in certain countries.
Similar systems developed (2) in these
laboratories have also already been used in
diesel engine applications but lack of effective
legislation has not given users sufficient
incentive to abate the pollution from this
source.
cedures (3). The essential properties of the

catalyst are illustrated in Fig. I which shows
the effect of variations in engine speed (and
therefore volume of exhaust gases) and exhaust temperature on the conversion of hydrocarbons and carbon monoxide. Obviously
the key factor which determines whether the
catalyst will be effective is whether the
temperature of the exhaust gases is above
the ignition temperature (usually defined as
tS0per cent) of the catalyst. Values as low
as 150C for carbon monoxide to about
225C for hydrocarbons are typical of this
catalyst. Therefore it is necessary to examine
how exhaust temperature varies with operating mode on typical engines.
Properties of Oxidation Catalysts

Recent work in these laboratories has led
to the development of an improved type of
platinum group metal catalyst which can be
supported on a refractory monolith and can be
applied to the oxidation of diesel exhaust
gases. The supported catalyst module is
contained inside a sheet metal box similar in
external appearance to a standard automobile
silencer box. The overall system is known as
the Honeycat Diesel Exhaust Purifier (DEP).
A standard DEP unit taken from routine
production was evaluated for control of emissions from a Perkins 4.236 (-4 litre) direct
injection engine mounted on a dynamometer
test bed. Emissions before and after the
catalyst were measured by standard pro-
Diesel Exhaust Gas Temperatures

Exhaust temperatures vary considerably
with engine loadjspeed combinations and with
engine type. Values shown in Figs. 2 (a) and
2 (6) for direct and indirect injection engines
illustrate the general trend. Increasing the
load at a constant speed increases the temperature up to a maximum of 500-600C.
The isotherms also represent lines of equal
conversion which may be predicted from the
conversion data of the type shown in Fig. I
for particular catalysts.
*Johnson Matthey Chemicals registered trade name
Effect
Effectofofthe
theCataiyst
Catalyst
on
onEngine
EngineOperalion
Operation
TThe
h e effect
effectofof fitting
fittingaa DEP
DEP unir
unit
into
into rhe
the exhaust
exhaust system
system on
on fuel
fuel
ciinsumptim,
consumption, engine
engine power,
power, and
and
5rnrikt.
smoke pruduction
production isis negligible,
negligible, asas
shown
h e effect
effect on
on
shown inin Fig.
Fig. 3.3. TThe
exhaust
exhaustback
backpressure
pressurewill
willobviously
obviously
alter
alter Lvith
with the
the cross-sectional
cross-sectional area
area
and
volume
of
thc
and volume of the catalyst
catalyst chosen
chosen
LO meet particular emission conrrol
to meet particular emission control
targets
targets but
but tht.
the system
system used
used for
for
these experiments doubled the back
these experiments doubled the back
pressure.
pressure.
Control of Carbon Monoxide

Control of Carbon Monoxide
and Hydrocarbons
and Hydrocarbons
Thc volume and compositiun of

The volume and composition of
cxhaust fume varies with engine
exhaust fume varies with engine
opcrating condition. Hydrocarbon
operating condition. Hydrocarbon
crnissions show conccntrations beemissions show concentrations between 500 and 750 p.p.m. Over the
tween 500 and 750 p.p.m. over the
major part of the working range of
major part of the working range of
tlic cnginc in the ex-works con-
the engine in the ex-works con-
TTable II
Catalytic Oxidation of Hydrocarbons and Carbon Monoxide during CARB Cycle

Emissions, gjh
Per cent
Full
Engine Mode
Carbon Monoxide
Hydrocarbons
Power
Idle*
intermediate Speed
(1680 r.p.m.)
Rated Speed
(2800 r.p.m.)
,efore Catalyst 4fter Catalyst
iefore Catalysi
2fterCataiyst
24
18
22
21
2
25
50
75
100
70
59
51
46
57
68
67
78
11
9
44
56
24
11
5
2
403
12
57
I00
75
50
25
2
62
93
97
115
151
6
14
21
31
48
489
318
252
291
212
14
17
17
23
17
Brake specific emissions, g/bhp/h
2.52
0.78
6.8
0.7
* Average over the three idle periods for 13-mode cycle. Data obtained on 4.236 D.I. engine
fitted with standard Honeycat Diesel Exhaust Purifier
dition, and less than 250 p.p.m. after catalytic treatment during the load/speed range
where the catalyst is operating above ignition temperature. The absolutc amount of
emissions obviously increases with increase in
engine speed and will be approximately
proportional to speed. There is only a limited

area at virtually zero load where the catalyst
is not able to operate due to insufficient temperature. Similar data is available for carbon
monoxide and shows that, as expected, conversion efficiencies for this easily oxidised
Table Ill
Emissions before and after Catalytic Oxidation for Direct and Indirect
Injection Engines
Engine
Brake Specific Emissions, CARB Cycle, g/bhp/h
Catalyst
Geometry
injection Type
Timing
Direct
Standard
Standard
Direct
Indirect
HC
CO
NO*
Before After IBefore After
Before After Before After
2.5
2.2
0.8
0.8
6.8
6.8
0.7
0.9
10.5
10.3
10.3
10.5
12"retard
retard 12" retard
12"
5.3
4.9
2.7
2.3
14.0
10.6
1.7
1.4
4.4
4.3
4.6
4.6
Standard
Standard
2.4
1.o
11.0
2.0
3.4
3.4
Standard
Standard
HC+NO,
TypeBBelliptical
ellipticalcross-section
cross-section
Type
Type L circular cross-section; catalyst volume approximately 14 per cent smaller than Type B
molecule are higher than for hydrocarbons

at corresponding temperature. Overall performance for hydrocarbon and carbon monoxide oxidation is demonstrated by emission
measurements on exhaust gas samples taken
before and after the catalyst installation
during operation of the engine through the
CARB 13-mode cycle referred to previously.
Table I1 shows values for the 4.236 engine
using a standard Honeycat catalyst. Table
I11 summarises the CARB cycle specific
emission data for DI and ID1 engines using
two catalysts of identical composition but
with slightly different volumes chosen as
convenient to fit commonly used round and
elliptical cross section silencer boxes.
Control of Nitrogen Oxides

Table I11 shows that the catalyst has no
significant effect on NO, emissions. Any
small apparent increase across the catalyst
is not a real effect but is due solely to experimental error in sampling and analysis. It
also shows that the NO, value is a major
contributor to the combined HC +NO, limit
value specified in certain American legislation.
(Although NO is used as a convenient method
for expressing total NO, emission, it should
be noted that NO is the major component.)
However, it is known that retarding injection
timing will reduce NO, formation. Unfortunately, as mentioned earlier, and shown
in Fig 5, the conditions which help to prevent
NO, synthesis will lead to decreased combustion efficiency and, therefore, to an increase in the amounts of oxidisable components in the exhaust.
This technique of altering timing therefore
suggests a method of NO, emission control
provided that catalytic systems are used to
control the increased quantities of hydrocarbons and CO. Although a minimum value
for HC 4 NO, occurred at about 8' retard the
value of 12' retard, corresponding to minimum NO, formation, was chosen to evaluate
the catalyst system because this could only
affect HC and CO. Comparison of the CARB
cycle data of Table I11 for the diesel engine
in standard and retarded timing shows that

the catalyst will cope very efficiently with the
increased emissions.
Odour Control
Accurate quantitative data on odour control
is difficult to obtain as it is usually necessary
to use organoleptic methods of assessment.
The use of odour panels is expensive and
time consuming but independent measurement of the efficiency of the Johnson Matthey
catalyst using specially constructed air sampling cells and a trained panel of observers has
demonstrated that the catalyst is an extremely
effective method of odour control. Similar
work, using successive dilution of exhaust
samples taken by hypodermic syringe to
determine odour threshold values (4), was
done in our own research programme.
EXHAU
V0LUI.I
GAS
ftyrnin
300
1 oc
?
.
a
w
n
0 0
m a
I
w w
n n
100
200
STANDARD CATALYST BOX SIZE
E NG I N
300
400
500 I N 3
DISPLACE M E N 1
Fig. 6 Chart used to estimate the size of catalytic exhaust purijier required for a particular
application. Most engines operate within the range shaded on the right-hand side. Reading
across, the y axis gives the exhaust gas volume and the lejbhand shaded portion gives the
size of catalyst system from the x axis
Measurements of odour threshold were made

during runs arranged as a 2 x2 factorial
experimental design (s), with centre point, in
order to determine the amount of odour
control possible for various load/speed engine
conditions. These confirmed that the catalyst
made a significant contribution to odour
control at all times when exhaust gas temperature was above about zooPC. Even at
engine idle, when temperatures were too low
for catalytic ignition, some observers reported
an improvement in odour. Further work on
this topic is planned in which organoleptic
and instrumental methods of odour measurement will be used simultaneously.
Application to Diesel Engined

Plant or Vehicles
Thus we have shown that by combining the
measured properties of catalysts with the
relevant engine emission data (exhaust gas
volume, composition, and temperature) it is

possible to predict the emission control
capabilities of commercially available units
for specific applications. Honeycat Diesel
Exhaust Purifiers are available in standard
sizes (DEP 60, DEP 90, DEP 145) in which
catalyst volumes are progressively increased.
Choice of purifier will depend on both geometrical constraints for the particular engine
installation and on the emission standards
required. In general, it is convenient to use
charts of the type shown in Fig. 6 to estimate
the size of purifier required for the application
under consideration. Most engines operate in
the speed range shown on the shaded righthand portion of the diagram and estimates
of exhaust gas volume can be read directly
on the y-axis for a given engine displacement
size. By reference to the appropriate space
velocity line, chosen on the basis of known
performance and required emission target,
10
it is possible to choose the appropriate DEP.

This is then installed on the automobile,
fork lift truck or other equipment as near to
the engine exhaust manifold as practicable.
I
2
References
G. J. K. Acres and B. J. Cooper, Platinum
Metals Rev., 1972, 16,(3), 74-86

G. J. K. Acres, Platinum Metals Rev., I970,14,
(31, 78-85
3 California Exhaust Emission Standards, Test
and Approval Procedures for Diesel Engines in

1973 and Subsequent Model Year, Vehicles
over 6,001 Ib. gross Weight, Proposed Nov.
18th, 1970, State of California Air Resources
Board
4 D. P. Potter, J. Wignall, and M. L. Windsor,
J . Environmental Planning Pollution Control,
1972, 2, (2),47-52
5 See any standard textbook on statistical design
of experiments, e.g. Experimental Designs,
W. G. Cochran and G. M. Cox, 2nd edn., publ.
John Wiley Ltd.
Acknowledgement
The majority of results reported in this article
were obtained during a Johnson Matthey research
programme undertaken at Ricardo and Co.
Engineers (1927) Ltd. Supplementary confirmatory data has been obtained during confidential
projects in cooperation with various Johnson
Matthey Chemicals Ltd. customers and with
other research laboratories. The author wishes to
thank the staff of Ricardo Ltd. for helpful discussions during the course of this work.
Organometallic Chemistry of Platinum

ORGANOMETALLIC AND COORDINATION CHEMISTRY OF PLATINUM BY UMERTO
BELLUCO, Academic Press, London and New York, 1974,701 pp. k17.50
This volume is a recent addition to the There is also a very brief comparison with the
series of monographs on Organometallic reactivities found in other dB square planar
Chemistry which includes P. M. Maitlis systems.
The organometallic chemistry of the
The Organic Chemistry of Palladium. It
is the first hook to be devoted entirely to the
chemistry of platinum complexes and supplements F. R. Hartleys The Chemistry of
Platinum and Palladium.
Dr Belluco and his colleagues do not claim
to have comprehensively covered the literature, especially in the section on coordination
complexes. They have, however, provided
the most up-to-date compilation of information necessary for a full appreciation of
reactivity and bonding in the organometallic
chemistry of platinum. A total of 1400
references, up to August 1973, are quoted in
the text, in addition to a list of reviews on the
subjects covered by each chapter.
The book opens with a chapter on coordination compounds which is sub-divided
into the chemistry of platinum in its various
oxidation states.
Each section contains
details of the physical and spectral properties
of the relevant complexes. Specific descriptions of preparative methods have been
omitted for the sake of brevity and the discussion is limited to general procedures and
selected compounds. There is an additional
section on oxidative addition to platinum(I1)
complexes.
There follows a discussion on the
mechanism of substitution reactions with
particular reference to the effect on reactivity
of entering and leaving groups, cis and
trans ligands, and the nature of the solvent.
Platinum Metals Rev., 1975, 19, (l), 11-1 1
element is treated according to the nature of

the ligands, with chapters on hydride complexes, metal-Group IV 0-bonded complexes,
and compounds formed with unsaturated
hydrocarbons. Each chapter is sub-divided
as for the coordination compounds of a
given oxidation state, but with particular
emphasis on the preparative chemistry. In
the five chapters on the complexes of platinum,
extensive use has been made of tabulated
nuclear magnetic resonance, infrared and
Raman spectral data, and there are numerous
illustrations of the molecular structures of
significant complexes.
The final chapter is on homogeneous
catalysis, where the emphasis is on the hydrogenation and isomerisation of olefins by
platinum(I1) complexes.
However, the
inclusion of short sections on homogeneous
catalysis by other ds metal complexes appears
rather incongruous when details of the industrially viable homogeneous hydrosilation
catalyst, trans-Pt(Et,S),Cl,,
have been
omitted.
There is an adequate subject index, but the
reviewer regrets the absence of author and
formula indices which are found most useful
in W. P. Griffiths The Chemistry of the
Rarer Platinum Metals.
Overall, the book is a welcome addition to
the literature and will be valued by students
P. C. H.
and practical chemists alike.
11
The Production of Acetic Acid

RHODIUM CATALYSED CARBONYLATION OF METHANOL
By James F. Roth
Monsanto Co., St. Louis, Missouri
The new Monsanto Company acetic acid process employs a rhodiumbased homogeneous liquid-phase catalyst which promotes methanol
carbonylation in high selectivity and at low pressures. This article describes some of the chemistry involved in this process, with particular
emphasis on the role played by rhodium complexes in the catalytic cycle.
The new acetic acid plant built by the
Monsanto Company at Texas City is designed
to operate at lower pressures than previous
plants. The output of 300 million pounds
per year of acetic acid derived from methanol
is the result of the successful development
of a homogeneous catalyst based on rhodium.
This new catalyst was reported recently
( I , 2) for the low pressure liquid-phase
synthesis of acetic acid from methanol and
carbon monoxide.
Previously, workers at B.A.S.F. described
a commercial acetic acid process, based on
methanol carbonylation and an iodinepromoted cobalt catalyst, that employs
carbon monoxide pressures of about 7500
lb/in2 and gives a molar selectivity to acetic
acid of about go per cent (3). The new
rhodium catalyst can be used at much lower
pressures and affords reaction rates essentially
independent of carbon monoxide partial
pressure in the range between 200 and 1800
lb/in2. It effects methanol carbonylation
in 99 per cent selectivity and displays similar
selectivity even when the carbon monoxide
feed contains as much as 50 per cent hydrogen.
Catalyst Composition
The carbonylation catalyst is comprised of
two components, a soluble rhodium complex
and an iodide promoter. The catalytic species
is believed to consist of a coordination complex of rhodium with carbon monoxide and
halogen ligands. A wide variety of rhodium

compounds and iodine compounds have been
found to give similar reaction rates and
product distribution. This suggests that
these tend to form the same active catalytic
species. Solvent effects, e.g. faster rates in
more polar solvents, indicate that the active
species may be ionic.
Kinetics of Methanol Carbonylation

The overall stoichiometry of the acetic
acid synthesis is represented simply by
CH,OH 1 CO-rCH,COOH
The results of kinetics studies of the

rhodium-catalysed homogeneous reaction
have been reported (2) and have several
interesting and unusual features. The reaction
was found to be zero order with respect to
both reactants-methanol and carbon monoxide. An obvious consequence of the zero
order dependence on carbon monoxide
pressure is the ability to obtain high reaction
rates at low reaction pressures. With respect
to catalyst components, it was found that
reaction rate was directly proportional to
both the rhodium and iodide concentrations.
Another key observation made relates to the
fate of the methyl iodide (formed via reaction
of CH,OH+HI) concentration during the
reaction. This was determined by analysis of
timed liquid samples removed during the
course of the reaction. It was observed that
12
The Monsantu Co. acetic

acid plant at Texas City uses
a new proress bused on a
rhodium homogeneons liquidphase catalyst which g i m s
higher selectivity ,for the carbonylation of methanol ut
lower pressures than earlier
processes
methyl iodide reached a

steady-state concentration
very rapidly, that this concentration remained constant over most of the
reaction, and that the rate
of formation of acetic acid
was constant during the
same period.
Mechanism
of the Reaction
All of the kinetics results
can be rationalised by assuming that the reaction
proceeds in a stepwise
manner, as follows :
The initial step in the
catalytic cycle consists of a
rapid conversion of methanol to methyl iodide, for
example, via :
CH,OH+HI%CH,I +H,O
the rhodium-alkyl bond occurs to yield an

acyl-rhodium(II1) complex. This is accompanied by subsequent or simultaneous
replacement of co in the rhodium coordination sphere.
(1)
Then, an oxidative addition of methyl

iodide to a Rh(1) complex (d8 square planar)
occurs [Equation (z)]. This results in formation of a six-coordinate alkyl-rhodium(I1I)
(d6)complex.
CH,I + [Rh complex]
slow
Rapid insertion of carbon monoxide,

present as a ligand in the Rh complex, into
Finally, the d6 acyl-rhodium(II1) complex

reacts to produce acetic acid and to regenerate
13
the original d8 rhodium(1) complex. Several

different reaction modes can be proposed to
describe this step. These include a direct
hydrolysis of the acyl-rhodium(II1) complex
by water, a specific methanol-assisted solvolysis of this complex, or reductive elimination of acetyl iodide from the complex
followed by immediate hydrolysis of the
acetyl iodide to yield acetic acid, the: starting
Of these
rhodium(1) complex and HI.
possibilities, we favour the latter, as shown:
1
CH,
+[Rh complex]
I
Rh complex
I
.i
_I
I1
+ CH,C-I
(4)
Hzo
CH,COOH +HI
This overall reaction scheme is cclnsistent

with the observed reaction order dependencies and with the observed conslancy of
CHJ concentration during most of the
reaction, if one assumes that reaction (2)
is the rate-determining step. Accoxding to
this scheme, the role played by rhodium
complexes is threefold, consisting of the ratedetermining oxidative addition step, which
results in introduction of the methyl group

into the coordination sphere and two subsequent rapid steps involving first an exceptionally facile carbon monoxide insertion
reaction and then a facile reductive elimination step. This sequence leads to the establishment of a catalytic cycle. This multiple
step process all occurs with a degree of
selectivity that is remarkable even for a
homogeneous catalytic reaction.
It has been shown (4) that a heterogeneous
analogue of the homogeneous catalyst can be
prepared and that the kinetics of methanol
carbonylation are identical for the solid
supported rhodium complex and the homogeneous liquid-phase catalyst systems. This
suggests that, in spite of the obvious physical
differences between these catalysts, a similar
reaction mechanism is probzbly operative.
References
I
F. E. Paulik and J. F. Roth, J. Cherrr. SOC.,
Chem. Commwz., 1968, 1578

J- F. Roth, J. H. Craddock, A. Hershman and
F. E. Paulik, Chem. Techno!., 1971,600-605
3 H. Hohenschultz, N. von Kutepow and W.
Himmele, Hydrocarbon Proces., 1966, 45, 141
4 K. K. Robinson, A. Hershman, J. H. Craddock
and J. F. Roth, J. Caralysis, 1972,27, ( 3 ) , 389
2
Superconductivity in Palladium-Hydrogen Alloys

Superconducting properties have not generally been associated with the platinum
group metals.
However, in I972 T.
Skoskiewicz of the Polish Academy of
Sciences reported that palladium enriched
with hydrogen possesses superconductivity,
with a transition temperature T, of -5 K
when H:Pd=o.g.
Recent research in this field has been
briefly summarised by R. Taylor (New
Scientist, 1974, 64, (923, Nov. 14), 473), who
comments on work by B. Stritzker et al. of
the Nuclear Research Centre at Julich aimed
at raising T, ( Z . Physik, 1974, 268, (z),
261-264) and by C. A. Mackliet et al. at the
Naval Research Laboratory at Washington,
D.C., on the specific heat of superconducting
Pd-H alloys (Solid State Commun., 1974, 15,
(t),207-210).
The Julich team, which had first raised T,

to 9.4 K by H+ion bombardment to increase
the H:Pd ratio on the surface of palladium

foils to more than I, had also shown that the
substitution of deuterium for hydrogen can
raise T, to 11 I<. It is suggested that these
additions may be modifying the lattice
vibrations, or phonons, in the solids, thereby
changing their coupling to the electrons,
since it is the electron-phonon interaction
which is believed to lead to superconductivity.
Stritzker has now shown that alloying of
suitable amounts of copper, silver or gold to
Pd-H can raise T, still more (to 16.6 K for
45 per cent Cu-Pd when H:Pd-0.7; the
optimum silver and gold concentrations are
smaller).
Mackliet and his co-workers have discovered that, whereas the peaks in the specific
heat of superconductors usually drop sharply
above T, to the normal state, i.e. the superconducting state is more ordered, in Pd-H the
drop is less marked.
F. J. S.
14
Heavv Platinum Plating from a

Molten Salt Bath
J
The electroplating of platinum from conventional aqueous electrolytes is readily

achieved on to a number of basis metals but,
as with other coatings, is extremely difficult
on to refractory metals owing to the presence
of oxide layers. Some success has been
achieved with metals such as titanium but the
maximum thickness of deposit has usually
been of the order of 2.5 microns and a complicated sequence of pre-treatment operations
has been necessary.
A molten salt electrolytic process has now
been developed in the Metals Research
Department of Degussa at Wolfgang near
Frankfurt for the deposition of highly adherent and ductile coatings
of platinum on to a range
of refractory metals such
as titanium, tantalum,
niobium,
molybdenum,
and tungsten, and even on
to graphite.
The process uses a bath
of molten cyanides, operating at a temperature of
around 55o"C, and thick-
nesses of roo or 150 microns can be achieved.

High tensile and shear strength values
have been determined on these deposits,
ranging from four to eight times the values
obtained with normal electrodeposits, together with high ductility, with fracture
occurring under test in the basis metal rather
than at the interface.
The process offers the possibility of obtaining the desirable electrochemical properties
of platinum on refractory metals in such
applications as anodes for cathodic protection,
for chlorine production, for the purification
of toxic waste water, and for insoluble anodes
in electroplating baths.
Examples of the applications

of platinum deposition from
the Degussu molten salt electrolytic process, including expanded metal anodes, tubes,
rods, andJinished components.
The rod in the lower right hand
corner of the illustration was
bent over a radius of 20 m m
after deposition without failure
15
The Production of Heavy Water

HYDROGEN-WATER DEUTERIUM EXCHANGE OVER
PLATINUM METALS ON CARBON SUPPORTS
By N. H. Sagert and R. M. L. Pouteau

Atomic Energy of Canada Limited, Pinawa, Manitoba
Catalysts using suitably supported platinum show promise for the

commercial production of heavy water. Carbons are potential primary
supports for the platinum and metal-support interactions have been
observed in this system.
These interactions lower the chemical
activation energy and increase the rate of reaction under conditions
where it seems likely that the support donates electrons to the metal.
The Canadian nuclear power system, the
so-called CANDU system, is based on the
use of natural uranium oxide fuel. To use
this fuel, a very efficient moderator is required, and the only practical moderator is
heavy water, D,O. The present generation
of heavy water-moderated, pressurised, heavy
water-cooled reactors use about I Mg of
D,O per MW (electrical). Thus, at current
prices, the heavy water in a 400 MW(e)
unit costs L1.3 x IO', so there is considerable
incentive to produce it more cheaply.
The current commercial process for making
heavy water uses a dual temperature exchange
between the deuterium in water and hydrogen
sulphide, H,S. The process i s highly developed but suffers from a number of shortcomings including the inability to extract
more than 20 per cent of the deuterium from
water of natural deuterium abundance, and
the necessity of dealing with Mg quantities
of H,S at pressures of 2 MPa. An alternative
process is the dual temperature exchange
between hydrogen and water. However,
this exchange reaction requires an efficient
catalyst. Supported platinum and chromiapromoted nickel are good catalysts in the
vapour phase but lose their activity rapidly
in the liquid phase. Fortunately, Stevens
(2, 3) recently demonstrated that supported
platinum catalysts would retain their activity

in the presence of liquid water if they were
protected from wetting by a permeable
hydrophobic film. The exchange reaction
then takes place in the vapour state in the
interior of the catalyst, which is surrounded
by liquid water. This process is much more
likely to be economic.
Various charcoals have often been used
as primary supports for the platinum, and
vapour phase rates over carbon-supported
catalysts have often been higher than over
alumina- or silica-supported platinum (I).
However, it is only recently that methods
have been developed for measuring metal
surface areas in the presence of a support
(4). Therefore it is not clear from the earlier
work whether there is a true metal support
interaction with the carbon supports or
whether the platinum is merely better dispersed on these supports. It seemed desirable to learn whether the specific rates (rates
per unit metal surface area) were, in fact,
higher with the carbon supports. Also, since
the electronic properties of carbon are easily
altered by heat treating ( 5 ) , it might be possible to find optimum electronic properties
for the support and at the same time to
learn something about the mechanism of the
exchange reaction.
16
Fig. 1 Research workers at Atomic Energy of Canada Limited have found that the mass
spectrometer is an indispensable tool for the study of isotopic exchange reactions. This
instrument monitors the deuterium content of hydrogen from the catalytic reactor
Support Effects
Rates for the H,-HDO exchange were
measured in the vapour phase using platinum
black and platinum on carbon catalysts (6).
The carbon was graphitised at various heat
treatment temperatures before the platinum
was deposited on it. The results are shown in
Fig. 2, where the specific rate, r,, is thenumber
of moles of HD that would be initially produced if static experiments could be done
using pure HDO and H,. In actual fact,
rates were measured in a flow system using
H, with its natural abundance of deuterium
and water containing about 4 per cent
deuterium (8 per cent HDO). Rates are given
in terms of the platinum surface area.
Obviously, graphitising the support lowers
the apparent activation energy (makes it
more negative) and increases the rate at
lower temperatures. Since the rates are
calculated from plots of the logarithm of the
conversion against reciprocal flow, we do
17
not think that external diffusion is important.

Since varying the particle size did not change
the rates, neither do we think that pore
diffusion is causing these effects.
Over a relatively small range of pressures,
the rate of a catalytic reaction may often be
adequately represented by a power law
Under these conditions, and with surface

exchange rate controlling (7), the true activation energy for the surface exchange (8)
is given by:
E, i E a p p
+ a AH,O
t b AH,
(2)
where Eappis the apparent activation energy,

and the As are the heats of desorption of
water and hydrogen. Since a and b can be
obtained experimentally and values of A are
available, then E, can be calculated, and E,
values are shown in the Table overleaf.
Clearly, graphitisation of the support leads to
a considerable lowering of E,. Since the work

function of well graphitised carbon is less
than that of platinum, it was suggested that

electron transfer to the platinum might be
responsible for this effect.
Activation Energies for Hydrogemwater

Deuterium Exchange over Platinum
Catalysts
Support
Noble Metals on Graphon

In the above section, we suggest that
electron transfer from the graphitised carbon
might be responsible for the lowering of E,
as the graphitising temperature of the support
is changed. Since all the Group VIII noble
metals catalyse the hydrogen-water exchange,
we measured specific rates, orders and
apparent activation energies over all six
platinum group metals, supported on Graphon
(8). For comparison, data were obtained over
unsupported metal powders (10). The work
Reference
A1&a'
SiOI
None
Thermax
Graphon
Thermax (2100)
18
Figure 3 shows the ratio of E, over supported

catalysts to E, over unsupported powders,
plotted as a function of the themionic work
functions selected by Bouwman and Sachtler
(I I). A good correlation was obtained and the
slope suggests that for each kJ/mol that the
work function is raised, E, is lowered by
0.67 kJ/mol. The quantitative aspect of the
correlation may be somewhat suspect, as
the reported values of work functions vary
considerably. However, we did use a consistent set measured recently.
The observed orders of reaction were best
explained by a mechanism involving exchange between chemisorbed hydrogen atoms
functions of these metals cover the range

4.5 to 5.7 eV whereas the work function for
Graphon is probably somewhere above that
for well crystallised graphite (4.4 eV).
Therefore we would expect electron transfer
effects to be minimal with metals of lower
work function and to become more pronounced as the work function of the metal
increases.
Over the unsupported powders, the true
activation energies (E,) were within the
range 61 f 6 kJ/mol for all six metals. However, when the same metals were supported
on Graphon, the E, values varied from 103
kJ/mol for Ru to 36 kJ/mol for platinum.
19
and physically adsorbed water (6, 7). Since

hydrogcn chemisorption is not hindered by
the presence of water vapour (IZ), it is
thought that hydrogen and water are adsorbed on separate types of sites and do not
interfere with each other. This leads to a
rate expression of the form
r =k, OH,O
@H
(3)
If a Freundlich isotherm is assumed, k,

can be identified with the k, of equation (I).
Thus, writing k, in its Arrhenius form,
(4)
where C, and CH2, are the surface concentrations in molim? which can be calculated
from the reaction orders. Relative frequency
factors for supported and unsupported
catalysts are shown in Fig. 3b. There seems
to be some compensation between the
frequency factor and the activation energy,
but fortunately this compensation is not
complete and the actual specific rates at
433K are always increased by supporting
the metal on Graphon.
If our proposed mechanism holds, the
observed lowering of E, is associated with
a lowering of the activation energy for the
exchange step where a deuterium atom is
exchanged between physically adsorbed water
and a chemistorbed hydrogen atom. Since
the water is weakly bonded, it is most reasonable to assume that the major way in which the
activation energy can be lowered is by a
change in the Pt-H bonding.
With platinum on Graphon, electron
donation from the Graphon to the metal
occurs because of the difference in work
function. Because both phases are conductors, complete equilibrium should be
achieved. Now at room temperature and
above, the polarisation of the platinumhydrogen bond is Pts'--HS- (13). Thus,
charging the platinum negatively will weaken
the platinum-hydrogen bonds. Indeed, in
hydride-platinum complexes, it has been
shown that adding ligands which withdraw
electrons from the platinum strengthens
20
the platinum-hydrogen bond (14). Adding

electrons to the platinum should therefore
weaken this bond. Weakening the platinumhydrogen bond should lead to a lower
activation energy. In the case of metals
with lower work functions, the bonding
seems to be changed in the opposite direction,
leading to higher E, values. Figure 3 suggests that the effective work function of
Graphon is about 5.2 eV.
We think that the donation of electrons to
the metal affects the platinum-hydrogen
bond but other explanations are possible.
Levy and Boudart (IS) suggested recently
that the following equilibrium may exist
on the platinum surface in the presence of
hydrogen and water
PtH
H,O+iPt-
+ H,O+
(5)
This reaction provides a mechanism for

exchange between chemisorbed hydrogen
and physically adsorbed water. The work
function of the metal would be involved
directly in the thermochemistry of this
exchange.
The frequency factor for supported platinum divided by the frequency factor for
platinum black is less than unity. This
suggests that there are relatively fewer active
sites produced by electron transfer to the
metal than were present in its absence.
Similarly, the ratios of frequency factors for
the other metals are greater than unity,
suggesting that more of the metal surface
participates in the reaction.
In summary, we have noted a metal support interaction in the hydrogen-water
deuterium exchange. The evidence suggests
that the activation energy for surface exchange is lowered when the work functions
of the metal and the support are such as to
allow electrons to be donated to the metal.
This evidence may be sumrnarised as follows :
(i) Graphitising the carbon support lowers
the chemical activation energy for
hydrogen-water exchange.
(ii) When different noble metals are used
on graphitised carbon supports, a
correlation is obtained between the

chemical activation energies and the
work functions of the metals. Metals
with lower work functions have the
highest chemical activation energies.
(iii) When these noble metals are not
supported, the chemical activation
energies are constant, which means
that the correlation observed in (ii)
is not a property of the metals themselves.
This type of chemical, or electronic, promotion may well be of more importance than
is generally realised. It has already been
noted in the alkali metal promotion of
supported ruthenium catalysts for the synthesis of ammonia (16).
References
I
Production of Heavy Water, ed. 6.M.

Murphy, hlcGraw-Hill, New York, 1955,
145-260
W. H. Stevens, Canadian Patent 907,292,
I972
3 Can. Chem. Process., 1972, 56, ( I Z ) , 22
4 M. Boudart, Adw. Catal. Rel. Subj., 1969,
20, I53
5 S. Mrozowski, Carbon, 1971, 9,97
6 N. H. Sagert and R. M. L. Pouteau, Can. J.
Chenz., 1972, 50, 3686
7 J. H. Rolston and J. W. Goodale, Can. J .
Chem., 1972, 50, 1900
8 N. H. Sagert and R. M. L. Pouteau, Can. J .
Chem., 197% 51, 4031
g N. H. Sagert and R. M. L. Pouteau, Can. J .
Chem., 1971, 49, 3411
N. H. Sagert and R. M. L. Pouteau, Can. J.

Chem., 1974,52,2960
r r R. Bouwman and W. M. H. Sachtler, Surface
Sci., 1971, 24, r4o
12 E. S. J. Tomezsko and G. T. Furukawa,J.
10
Cuta2ysis, 1967, 8, 386

13 J. C. P. Mignolet, J . Chim. Phy., 1957, 54,
I9
14 A. P. Ginsberg, Transition Metal Chemistry, Vol. I, ed. R. L. Carlin, Marcel

Dekker, New York, 1965, 21.5
15 R. B. Levy and M. Boudan, J . Catalysis,
1974, 32, 304
16 K. I. Aika, H. Hori and A. Ozaki,J. Catalysis,
1972~27,424
Photocatalytic Properties of Materials

THE PHOTOREDUCTION OF PALLADIUM IONS ON TITANIUM DIOXIDE
The predominant position occupied by the
metal silver in photographic processes often
obscures the fact that other metals and
materials possess photographic properties.
Both scientific and economic reasons have
prompted recent studies of these alternatives
with varying degrees of success.
It has been known since 1920 that titanium
dioxide TiO, exhibits photocatalytic properties, since it is darkened by ultra-violet
radiation. Both electrons and holes produced
by light excitation may be involved. More
recently, the photoreduction of palladium
ions Pd+ at TiO, has been studied as an
initial step towards a photographic process
with TiO,. Photoreduction of a few metal
ions forms the initial image in a photographic
process and this image has subsequently to be
developed during a second stage to make it
visible and to retain it. Any photocatalytic
reduction of Pd+ ions on TiO, is, of course,
accompanied by a corresponding oxidation
process at the TiO,.
Simultaneous studies of the photocatalytic
reduction of Pdf and of the electrochemical
21
properties of TiO, have now been reported

by F. Mollers, H. J. Tolle and R. Memming
of Philips Forschungslaboratorium Hamburg
G.m.b.H. ( J . Electrochem. Soc., 1974, 121,
(9), I 160-1 167). They carried out electrochemical and photocurrent measurements on
vapour-deposited TiO, films on conducting
substrates (SnO, on glass, or titanium sheet).
It was shown that the primary step in this
process is the generation of an anodic
photocurrent, i.e. evolution of oxygen, which
catalyses the cathodic deposition (reduction)
of palladium under open-circuit conditions.
The nature of the photocatalytic deposition of palladium on TiO, was interpreted
on the basis of the photovoltaic effect of the
semiconducting TiO,. Further studies included an examination of the various parameters affecting the phenomenon, e.g. space
charge effects, film thickness and doping.
The results are clearly illustrated by a series
of graphs depicting the various electrochemical data and the whole is presented as
a useful and stimulating paper.
F. J. S.
Trifluorophosphine Complexes
of the Platinum Metals
A REVIEW OF RECENT DEVELOPMENTS
By John F. Nixon and J. Richard Swain

School of Molecular Sciences, University of Sussex, Brighton
The chemistry of the trijluorophosphine complexes of the transition metals,

and of the platinum metals in particular, is of increasing importance.
This article describes some of the more recent developments in trifluorophosphine complexes of the platinum metals, including their syntheses,
structures, reactions, and potential as homogeneous catalysts.
The rapid development of transition metal considered to operate in the same synergic
carbonyl chemistry originated with the dis- fashion as that already suggested for the
covery of Ni(CO), in 1890. About the same analogous metal carbonyls. The n-comtime the first trifluorophosphine coordina- ponent was expected to be favoured in
tion complex [PtF,(PF,)], was synthesised trifluorophosphine-metal complexes because
by Moissan, but its true identity was not of the presence of the highly electronegative
recognised at the time. It was only following fluorine atoms attached to phosphorus (I).
the synthesis of the complexes cis-PtC1, A large number of trifluorophosphine(PF,), and [PtCI,(PF,)], by Chatt and transition metal complexes are now known
Williams in 1950 that attention was drawn and their chemistry has been extensively
to the similarity of trifluorophosphine and studied (2, 3, 4).
carbon monoxide as ligands towards transition metals. It was proposed that the dative Binary Compounds
Pl.atinum metal complexes in which trisigma bond formed by donation of the lonepair of electrons on phosphorus to the metal fluorophosphine is the only ligand present are
was supplemented by a symmetry allowed listed in Table I. It is interesting to note
x-bond involving back donation of transition that the corresponding carbonyl complexes
metal d-electrons into empty phosphorus M(CO)4, (M =Pd, Pt) and MB(CO)B,(M=
#-orbitals. The 0- and x-components were Rh, Ir) are unstab1,e. As yet there is no
Table I
Platinum Metal
RU(PF3)5
(colourless, m.p. 30C)
OS(PF3,
(colourless crystals)
- Trifluorophosphine Complexes
Rh*(PF3)8
(yellow, m.p. 92.5C)
Pd(PF,),
(colourless, rn.p. -4OC,
dec -20C)
[Rh(PF3),], (x=3 or4)

(red crystals)
IrdPF3h
yellow, m.p. 113-116C)
22
Pt(PFJ4
(colourless,
Pt(PF3L
m.p. -15OC)
(colourless, m.p. -15C)
b.p.
b.p.86"C/730
86C/730dec
dec130C)
130C)
extensive chemistry of polynuclear metal

trifluorophosphine complexes.
Methods of Preparation
The main synthetic route developed by Th.
Kruck and co-workers in Germany involves
reductive fluorophosphination.
In this
method the platinum metal halide is heated
in an autoclave with copper or zinc in the
presence of high pressures (5c-500 atm)
of trifluorophosphine ( 2, 5, 6).
Other synthetic routes using milder reaction conditions involve displacement of

ligands (e.g. CO, x-allyl) already coordinated
to the platinum metal (13, 14), e.g.
PF,
Rua(C0),zw
RuPFXCO),
( x - 5 4, 3:
ally1 chloride
Pd(PF,), can also be obtained by the direct

reaction between palladium powder and
trifluorophosphine at high temperature and
pressure (15).
;
400 atm
(PP,) 3CuCl
MCI, 3Cu 5PF,-M
150-250C
(M-Ru, 0 s )
250 am
2RhC1, I GCu I BPI.,-Rh,(PF,),
Structures
Vibrational spectroscopic studies suggested
that the M(PF,), complexes, (M=Pd, Pt),
have perfectly tetrahedral structures and this
has been subsequently confirmed in the case
of the platinum complex (16). In contrast
to the very short metal-phosphorus bond
length found for Ni(PF,), (2.116A), the
platinum-phosphorus distance in Pt(PF,),
(2.230 A) is not substantially different from
that in other platinum-phosphine complexes.
This may reflect the decreased importance of
metal-phosphorus =-bonding for the heavier
platinum metals.
T h e pentakis(trifluorophosphine)ruthenium and osmium complexes, M(PF,),,
almost certainly have trigonal bipyramid
structures. Detailed 19F and 31P nuclear
magnetic resonance studies show that these
molecules are fluxional even at temperatures as low as - 160C, the barrier to intramolecular ligand exchange between equatorial
and axial positions being less than 5 kcal/mole
(17) (Fig. 1).
GCuCI
> 150C
Interestingly, when IrC1, is heated with

PF, and copper only small amounts of the
orange red crystalline p,-phosphido-nonaks
-(trifluorophosphine)tri-iridium
Ir,P(PF,)
are formedrather than Ir,(PFJ8 (7). The latter
can be obtained in good yield from the reaction between K[Ir(PF,),] and IrCl(I?F,), (8)
or by U.V. irradiation of IrH(PF,), (9). It
is thermally stable up to 200C.The rhodium
analogue, on the other hand, evolves two
moles of PF, per dimer at 170C to afford a
red volatile solid, [Rh(PF,),],, whose identity
is not yet fully established (8).
The platinum and palladium complexes
M(PF,),, which are readily available by
reductive fluorophosphination of the appropriate metal halide (10) can also be
obtained in the absence of any reducing metal
since PF, can act as its own reducing agent
(11, ~z),viz.
100-150 am
PtCI, : jPF,-Pt(PF,),
: PF,CI,
100C
Fig. 1 Possible intramolecular ligand exchange mechanism in M( PF3)5complexes
23
The structures of the M,(PF& complexes

(M=Rh, Ir), are not yet known, but presumably consist of two staggered trigonal
bipyramid M(PF,), units held together by a
metal-metal bond. Ir,P(PF,), is thought to
have the structure shown below (7).
All the trifluorophosphine metal hydrides

exhibit acidic properties, readily forming the
(M -Rh,
Ir),
metallates [M(PF,),]-,
[MH(PF,),]- and [M(PF,),]2-, (M=Ru,
Os), with bases or potassium amalgam (IS,
IS).
Table I I
Trifluorophosphine Platinum Metal

Hydrides
Ru HdPF3,
(colourless, m.p.
m.p.
(colourless,
- 76T)
OsHAPF,),
(colourless, m.p.
-72C)
RWPF,),
(colourless, m.p.
-40C,
89Ti725)
-40C,
b.p.b.p.
89Ti725)
IrH(PF3,
(colourless,
m.p.
(colourless,
m.p.
-39C.
95C/730)
-39C.
b.p.b.p.
95"C/730)
Hydrides
The hydrides MH(PF,), (M=Rh, Ir)
and MH,(PF,), (MN=Ru, 0 s ) listed in
Table I1 are obtained in high yields by
heating a mixture of the metal chloride and
copper under high pressures of trifluorophosphine and hydrogen (IS, IS).
RhCI,+SCu+ 4PF, iH, ---+RhH(PF,),
The MH(PF,), complexes react with

triphenylphosphine to produce the salts
[Ph,PH]+[M(PF,),]- while the substituted
products RhH(PF,)(PPh,), and &H(PF,),
(PPhJ2 have recently been obtained by
reaction of the stoichiometric quantities of
PF, and RhH(PPh,), (20). The complexes
RhH(PF,)(PPh,), and RhH(PF,),(PPh,),
exhibit high activity as homogeneous catalysts. For example, RhH(PE3)(PPh,), catalyses
the hydrogenation of terminal olefins (at
25C,I atm H,) while RhH$F,),(PPh,),
has been found to bring about rapid isomerisation of terminal olefins (20). The
ruthenium complexes RuH,(PPh,), (PF,) and
RuH,(PPh,),(PF,)2 have been obtained very
recently from RuH,(PPh,),, but are not as
catalytically active as their rhodium counterparts (21).
3CuCI
The rhodium and iridium hydrides can also

be obtained by acidification of the metallates
[M(PF,),]- which are available from alternative low pressure synthetic routes. All
the hydrides are very volatile liquids and,
except for RhH(PF,),, exhibit considerable
thermal stability.
The binuclear complex Rh,(PF,), is
readily cleaved by hydrogen gas to yield
RhH(PF,), quantitatively, while Ir,(PF,)*
forms IrH(PF,), in the presence of moisture
( 2 ) . When a mixture of HIr(PF,), and
HCo(PF,), is subjected to U.V. irradiation,
the interesting bridged complex shown
below is obtained as a red oil (7).
Fig. 2 The struetiire of R h H ( P F , ) , US

determined i n the gas phase by electron
diffraction
24
Structures
The structure of RhH(PF,), (Fig. 2),
which has recently been determined by
electron diffraction (22), may be considered
to be pseudo-tetrahedral, i.e. based on a
distorted trigonal bipyramid in which the
hydrogen atom occupies an axial position.
The rhodium-phosphorus distance is shorter
than that in RhH(PPh,),and of the same order
of magnitude as that found for Rh(NO)
(PF3), (Rh-P-2.245 A) (23). It is not,
however, the shortest rhodium-phosphorus
bond length known. In the analogous cobalt
complex, CoH(PFJ,, the cobdt-phosphorus
bond is exceptionally short (24).
Variable temperature n.m.r. studies on
MH(PFJ4 (M=Co, Rh, Ir) establish that
all these complexes are stereochemically
non-rigid (fluxional) and it has been proposed
that the phosphorus environments are
interchanged by a tetrahedral tunnelling
rearrangement mechanism (17).
A recent X-ray crystallographic study (25)
of the catalytically active complex RhH
(PF3)(PPh3),has confirmed the basic trigonal

bipyramidal structure proposed earlier on
the basis of its IH, lDF, and 31P n.m.r.
spectra (20) (Fig. 3). The rhodium-triis very
fluorophosphine distance (2.15
much shorter than the rhodium-triphenylphosphine distances (average 2.33 A), which
is consistent with the stronger n-bonding
ability of PF,.
There is n.m.r. evidence that in complexes
of the type MH,(PF,)~ (M=RU, 0 s )
(191, RuHz(PF,)(PPhJ, and RuHdFd,
(PPh,), (21), the hydrides occupy cispositions in a distorted octahedron,
a)
Halides
The colourless complex cis-PtGl,(PF,),
and the orange dimeric compound [PtCl,
(PF3)I2 mentioned above are both obtained
by passing PF, through a plug of platinous
chloride at 200-220C.
Passage of PFz over heated rhodium
trichloride in the presence of copper powder
gives very low yields of the red crystalline,
volatile, chlorine bridged
dimer, [RhCI(PF,),I, (2)J
but this complex has subsequently been conveniently
synthesised in high yield
by reaction of PF, with
[RhCI(L,)]
(L =ethylene,
cyclo-octene, CO,
etc.)
under mild conditions (8,
26, 27).
The complexes [RhX

(PF3)Jt (X=Br, I) have
been prepared similarly and
are also obtained from
halogen exchange reactions
of [RhCl(PF,),], with LiBr
or NaI (27). Treatment of
Fig. 3 The structure of RhH(PF,)(PPh,), (inner coordination sphere only). The H position i s not shown
(Rh-H distance -1.6 A)
25
~ M W 8 H I J 2 l 2GH14 =
cyclo-octene) with trifluorophosphine yields the rather
Fig.4 Scheme showing some of the reactions of
the haEide compound [RhCI( PF,),]
formed by treating the dimer with an excess

of triphenylphosphine has been shown to
undergo fast ligand exchange reactions with
traces of trifluorophosphine or triphenylphosphine (26).
No structural data are available at present
on any of the above halide complexes, but
[RhCl(PF,),], probably has a similar structure
to that found for [RhCl(CO),], with two
chlorine bridges between the metal atoms
and possibly some degree of metal-metal
interaction in the solid state.
unstable IrCl(PF,), which readily decomposes

to the dimeric [IrCl(PF,),], on warming (8).
It is interesting that the corresponding
carbonyl complex has the composition
IrCl(CO),. The very volatile IrI(PF3)4has
been made by treating the metallate salt
KJr(PF,), with iodine at -80C (28).
The
yellow
crystalline
complexes
RhX(PF,), (X-Cl, Er, I) are stable at room
temperature only under a pressure of PF,,
rapidly reverting to the red [RhX(PF,),],
compounds on removal of the trifluorophosphine pressure (27).
-lJP3
Organometallic Compounds
RhX(PFd,,Z====3 [RhX(PF&],
ycllow
-1 PF,
red
Some typical complexes are listed in

Table 111. Rh,(PF,), reacts with a variety of
acetylenes to give volatile compounds of the
type Rh,(PF,),(acetylene).
The structural
The synthetic utility of the dimeric

[RhC1(PF,)J2 complex is summarised in
Fig. 4. The complex trans-RhCl(PPh,),(PF,)
Table 111
Some OrganometallicCompounds of the Platinum Metals Containing Trifluorophosphine
26
analogy between these

compounds and the
better known, related
Co,(CO) ,(acetylene)
complexes has been confirmed by an X-ray
diffraction study of
Rh,(PF,),(PPh,),(PhC
r C P h ) (29) (Fig. 5).
The rhodium-trifluorophosphine distances
(average 2.216 8) are
again significantly
shorter than the rhodium triphenylphosphine distances (average
2.391 8).
A series of volatile,
ii-allylic complexes
Rh(x-allylic)(PF,), have
been obtained by insertion of various dienes
into the metal-hydride
bond of RhH(PF,), (30,
31). These complexes
react with hydrogen
chloride to produce ultimately [RhCl(PF,),],
and an olefin, e.g.
Fig. 5 The structure of Rh,( PF,)c(PPh,),(PhC_CPh).

l h e Ph,P ligands have been deleted for clarity
The intermediate x-ally1 rhodium(II1)

hydride complex has been detected by a
low temperature n.m.r. study and this
observation is important in providing support
for the involvement of this type of intermediate during the isomerisation of olefins
catalysed by transition metal complexes
(32).
A novel thermal isomerisation of
Rh(i-t-I,r-dimethylaUyl)O,
to the 1,2H
hlc / A ,. p e
isomer has been observed (33) and a diene
metal-hydride intermediate postulated (Fig.
6).
The x-ally1 group in IUZ(X-C~H~)(PF~)~
is
Fig. 6 Thermal isomerisationof Rh(r-C,H,)
readily displaced by hydrogen and trifluoro(PF,), by way of a diene metal-hydride
intermediate
phosphine to yield RhH(PF,), quantitatively
27
Fig. 7 The structure of the

complex RuCZ2(Cl,H,,)(PF,)
References
(34), and treatment with nitric oxide affords
I
J.
Chatt,
Mature
(London), 1950, 165, 637;
the volatile liquid nitrosyl Rh(NO)(PF,),,
J. Chatt and A. A. Williams, J. Chem. SOC.,
(2, 34), whose structure has been determined
1951, 3061
by electron diffraction (23).
2 Th. Kruck, Angew. Chem., International
Ed. En., 1967, 6, 53
The structure of the unusual bis-Tc-allylic
3 J. F. Nixon, Advances Inorg. Chem. Radioruthenium complex dichloro-2,7-dimethylchern., 1970, 13, 363
octa-2,6-diene-1,8-diyl(trifluorophosphine) 4 J. F. Nixon, Endeavour, 1973,32, 19
5 Th. Kruck and A. Prasch, 2. Anorg. Allgem.
ruthenium, RUCI,(C,~H,,)(PF,), (35) i s shown
Chem., 1968,356, 118
in Fig. 7. This represents the first structural
6 Th. Kruck, N. Derner and W. Lang, Z.
Naturforsch., 1966, zIb, 1020
study of a trifluorophosphine complex of a
7 Th. Kruck, G. Sylvester and I.-P. Kunau,
metal in an oxidation state greater than
Z. ATaturforxch., 1973, 28b, 38
one (25). It is interesting to note that the
8 M. A. Bennett and D. J. Patmore, Inorg.
Chem., 1971, 10, 2387
ruthenium-phosphorus bond length (2.237 8)
g Th. Kruck, G. Sylvester and 1.2. Kunau,
is still considerably shorter than in other
Angew. Chem., International Ed. En., 1971,
rutheniuim phosphine complexes (typically
10, 725
10 Th. Kruck, and K. Baur, Angezu. Chem.,
2.30-2.37 8).
International Ed. En., 1965, 4, 521
A new synthetic method which promises 11 Th. Kruck and K. Baur, 2. Anorg. Allgem.
Chem., 1969, 364,192
to have considerable general application
12 J. F. Nixon and M. D. Sexton,J. Chem. Soc.,
involvcs transfer of PF, initially coordinated
A, Inorg. Phys. Theor., 1970, 321
to nickel to other transition metals. Thus 13 C. A. Udovich and R. J. Clark, J. Organometal. Chem., 1972, 36, 355
treatment of the pentamethylcyclopenta14
H.
T. Dodd and J. F. Nixon,J. Organometal.
dienyl complexes (Me,C,MCl,), (M=Rh,
Chem., I971,32, C67
Ir) with an excess of the commercially avail- 15 Th. Kruck, K. Baur and W. Lang, Chem.
Ber., 1961, 101, 138
able complex Ni(PF,), in boiling toluene
16
J. C. Marriott, J. A. Salthouse, M. J. Ware
gives good yields of the complexes z-(Me5C,)
and J. M. Freeman, Chem. Commun., 1970,
595
M(PF,), (36).
2
17 P. Meakin, E. L. Muetterties and J. P.

Jesson, J . Am. Chem. SOC.,1972,95, 527r
18
19
20
21
22
23
24
25
26
27
28 Th. Kruck, A. Engelmann and W. Lang,

Chem. Bm.,1966, 99, 2473
Th. Kruck, W. Lang, N. Derner and M. 29 M. A. Bennett, R. N. Johnson, G. B.
Stadler, Chem. Ber., 1968, 101, 3816
Robertson, T. W. Turney and P. 0. Whimp,
Th. Kruck and A. Prasch, Z. Anorg. Al2gem.
3. Am. Chem. SOC.,1972, 94,6540
Chem., 1969, 371, I
30 D. A. Clement, J. F. Nixon and B. Wilkins,
J. F. Nixon and J. R. Swain,J. Organometal.
J . Organometal. Chem., 1972, 37, C43
Chem., 1974, 72, C I ~ - C I ~
31 J. F. Nixon, B. Wilkins and D. A. Clement,
R. A. Head and J. F. Nixon, to be published
J . Chem. SOC.,Dalton Trans., 1974, 1993
D. W. H. Rankin, personal communication
32 J. F. Nixon and B. Wilkins, J . Organometal.
D. M. Bridges, D. A. Clement, J. F. Nixon
Chem., 1972, 44, C25
and D. W. H. Rankin, Acta Cryst. A, 1972,
33 M. A. Cairns, J. F. Nixon and B. Wilkins,
318, 1130
Chem. Commzm., 1973, 86
B. A. Frenz and J. A. Ihers, Inorg. Chem.,
34 J. F. Nixon and B. Wilkins, J. Organometal.
1970, 33 2403
Chem., 1974,80,129
P. Hitchcock, J. F. Nixon and J. Sinclair,
submitted for publication
35 R. A. Head, J. F. Nixon, J. R. Swain and
D. A. Clement and J. F. Nixon, 3. Chem.
C. M. Woodard, J . Organometal. Chem.,
SOC.,Dalton Trans., 1972,2553
19741 76,393
J. F. Nixon and J. R. Swain, J . Chem. SOC., 36 R. B. King and A. Efraty, J . Am. Chem.
Dalton Trans., 1972, I044
S0c.J 1971, 931 5260
An Age-hardenable Palladium Based Spring Alloy

Strong, light and rigid structural components are frequently produced by incorporating strong fibres of high elastic modulus
into a lighter and weaker matrix. Glass or
graphite fibres can thus be used to reinforce
synthetic resin matrices, while other types of
glass fibres are being employed to strengthen
fine concrete mixes. With metals, however,
fibre reinforcement has met with little
success because at high temperatures the
matrix tends inevitably to react with the
strengthening phase, which is either dissolved
or seriously weakened.
D r K. H. Reiff of the Carl Haas spring
factory has recently described (Metall, 1974,
28, (7), 686-690) an attempt to develop a
fibre-strengthened spring alloy in which no
degradation of the strengthening phase occurs
because it is always in thermodynamic
equilibrium with its weaker matrix. With
this object in mind he selected eutectic alloys
based on the ternary system palladiumcopper-gallium, in which the lamellar phase
was an intermetallic compound, strong but
ductile enough to allow the alloy as a whole
to be heavily cold worked. T h e working and
annealing procedure adopted produced a
highly aligned fibre structure in the wires
drawn from chill cast ingots. The proportion
of the reinforcing fibres appeared to vary
with the copper rather than with the gallium
content of the alloys, and similar considerations applied to the hardness and tensile
strength.
Wires having an initial diameter of 1.75 m m

were cold drawn without annealing to a
diameter of 50 pn, the area reduction ratio
being approximately 1000:I. The heavily
cold worked wires were then aged, and tensile
values peaking at 260 kp/mm2 or) rather
more than 165 ton/in2) were obtained after
one hour at 425C. Such tensile values are
remarkably high for a ductile non-ferrous
alloy and are comparable to those of maraging
steels or of hard drawn wires of tungsten or
rhenium. The high tensile strength was,
however, due simply to age-hardening, and
over-ageing reduced strength values catastrophically to the 80 ton/in' level, which was
much below that of the hard drawn, un-aged
wire.
These results, coupled with the fact that the
elastic modulus of the fibrous wires was only
marginally higher than that of pure palladium,
show that the high strengths attained were a
consequence of precipitation hardening alone
and could not be attributed to fibre strengthening. Whatever the mechanism involved,
however, a tensile strength approximately
twice that of fully heat treated berylliumcopper is still impressive, and the heat treatment procedures required would seem well
suited to the setting of hair springs. Certain
applications might therefore be envisaged
where economic justification could be found
for the use of this strong but expensive
palladium-based spring alloy.
A. S. D.
29
ABSTRACTS
of current literature on the platinum metals and their alloys
PROPERTIES
formations, the hysteresis revealed by electrical

resistance/temperature plots, the thermoelastic
growth and the reappearance of an identical
microstructure after thermal cycling were studied
as a function of the ordering of the y-phase.
The Heat of Adsorption of Hydrogen on

Platinum
and P. J. RICHARDS, Surface Sci.,
1974 44, (I), 129-140
UHV adiabatic calorimetric studies of the heat
of adsorption (9) of H on clean polycrystalline Pt
determined as a function of the coverage (0) and
temperature showed that adsorption at 273 K
resulted in a stepped shape q-0 curve with
q (0=0)-24.7 kcal/mole. At 77 K the form of
the curve depends on the temperature of preadsorption.
P. R. NORTON
Localised Enhancement Effects in Pd-Ag

Alloys
A. P. AIURANI, Phys. Rev.Lett., 1974,33, (2), 91-94
Low-temperature electrical resistivities of Pd-Ag
alloys show a positive T 2temperature dependence
in the concentration range above 60 at.O,:Ag.
This behaviour supplements the well-known
resistivity minima observed in alloys with lower
concentrations of Ag, and strongly favours the
model of scattering from localised exchangeenhanced Pd d states, as against s+d scattering
in the rigid- or collective-band description of
the alloys.
Temperature-dependence of Resistivity of
PtCr Alloys
Phys. Rev. B,1974,
9, (111, 4945-4953
Studies of the electrical resistivity of s-Iz%Cr-Pt
alloys at 1.4-300 K showed that the spin-fluctuation temperature increased from 52.5 to 85 K as
Cr concentration increased from 5 to 12 at.:!;. No
magnetic ordering occurs above 1.4 K for concentration <12 at.?(,; a rough calculation is
performed which qualitatively accounts for the
decreasing magnetic-ordering temperature across
the series AuCr, PdCr and PtCr.
R. M. ROSHKO and G . WILLIAMS,
Surface Area Effects on the Sorption of

Hydrogen by Palladium
M. J. B. EVANS,
1205
1200-
Pressure-composition isotherms for dilute solutions of H, in Pd were measured at 100-240C

and at up to 1000Torr. For Pd foil the isotherms
are consistent with data at lower temperatures, and
with existing theoretical isotherms. With samples
of appreciable surface area a higher sorptive
capacity is found which may be due to the formation of a layer of adsorbed H, on the metal
surface; appropriate correction may be made for
this. The variation of partial molar enthalpy of
adsorbed H2 with H,-content is also affected by
this surface phenomenon.
Magnetic Structure of Ordered IronPlatinum Alloys

A. z. MEN'SHIKOV, YU. A. DOROFEEV, v . A. KAZANTSEV
and S. K. SIDOROV, Fiz. Metal. Metalloved., 1974,
38, (31, 505-518
Elastic scattering of neutrons and magnetic
measurements on 10-75 at.O/,Fe-Pt alloys revealed
five magnetic structures corresponding to Pt,Fe,
Pt, ,5Fel.2SJ
Pt,.,Fe,.,, PtFe, and Fe,Pt. Their
magnetic properties vary from antiferromagnetic
ordering in Pt,Fe and Pt2.75Fel2 5 to ferroFePt is
magnetic in Pt, 5Fe,.j and Fe,Pt.
believed to possess uncompensated antiferromagnetism, i.e. ferrimagnetism. Experimental
and theoretical values are in best agreement for
atomic moments of Fe (3.O-2.75)pB and Pt (0.20.3)VB.
Electrical Resistivity of Some PalladiumSilver Alloys Containing Hydrogen at

4.2 K
R. J. SMITH and D. A. OTTERSON, N A S A
Note 0-7672, 1974, (May), 11 pp.
Tech.
The resistivities of the alloys of 50-900/oPd and

go-roc)/Ag measured as a function of absorbed
H at 4.2 K showed minimum and maximum
values, except for IoO(,Ag-Pd,which had only a
maximum, and so*GAg-Pd with only a minimum.
The Reversible Martensite Transformation

in Iron-Platinum Alloys near Fe,Pt
s. KAJIWARA and w . s. OWEN, Metall. Trans., 1974,
Effect of Pressure on the Curie Temperatures

of PdFe, PdCo, PtFe and PtCo Alloys
s. MEIER, c. w . CHRISTOE and G. WORTMANN,
Solid State Commun., 1974, Is, (3), 485-488
The Curie temperatures of PdFe, PdCo, PtFe,
and PtCo alloys with Fe or Co concentration of
1-10 at.o/, have been measured by thermal
5, (91,2047-2061
A series of 25-27 at.q/,Pt-Fe alloys with ordering
of the y phase varying from substantial disorder
to nearly complete order were thermally cycled
at 25-196C. The kinetics of the y%cc trans-
Platinum Metals Rev.,1975, 19, (l), 30-37
Can.J. Chem., 1974, 52, (7),
J.
30
scanning of the 67FeMossbauer resonance under

pressures up to 170 kbar. The data are compared
with models, which relate the variation of T,
under pressure to changes in the impurity spinconduction electron coupling parameter Ji and
to changes of the pure host susceptibility Xh.
The differences between the experimental data
and these models are discussed.
structure of Dy,Pd, show that this compound is

cubic with a=13.529& space group Fdjrn, and
the elementary cell containing 68 D y and 28 I'd
atoms. The R.E.,Pd, compounds, where R.E. =
Tb, Ho, Er, Tm, Lu, and Y , are isotypic with
Dy,Pd,, and their lattice values are reported.
High Pressure Magnetic Behaviour of Low

Nickel Content Pd-Ni Alloys
R. F. MILLER and J. KOSHY,
Phys. Lett. A, 1974, 49, (I), 63-64

The magnetic properties of disordered Pd-Ni
alloys, with low Ni content were studied at high
magnetic fields and at high pressures. T h e
variation of the saturation magnetisation and
Curie temperature with the concentration and
pressure are described.
J . BEILLE,
The Growth and Structure of Epitaxial

Rhodium Films
J . Phys. D: Appl. Phys.,
1974,7, (10, 1472-1474
Single-crystal Rh films were epitaxially grown by
vacuum evaporation on the cubic, octahedral and
dodecahedra1 planes of rock salt, and also on Ag.
The structure of the films was investigated by
electron microscopy as a function of substrate
temperature and thickness of 28-600"C and
10-600 A, respectively.
Defects in Glassy Pd-Si Alloys
Oxidation of Iridium
J. LOGAN,
Scripta Metal., 1974, 8, (6), 727-732

X-ray diffraction and density studies on asquenched and rolled Pd,,Si,, showed that X-ray
diffracted intensities were identical for both asquenched and rolled foils but the density of the
as-quenched foils is -5% while the rolled foils
vary by -0.3%. The increase in the density upon
rolling is 0.5-5.8%.
R. T. WIMBER
The Glass Transition Temperature in Glassy

Alloys: Effect of Atomic Sizes and the Heats
of Mixing
Phase Diagram of the Iridium-Zirconium
and H. G. KRAUS, Metall. Trans.,

197455, (71, 1565-1.572
Ir wires heated by self resistance at r675-2260JC
were oxidised in naturally convected O 2 at
0.00132-1.32 atm. The experimental results were
correlated by a theoretical rate equation based on
control of the oxidation rates by diffusion of
Ir(g), IrO,(g) and IrO,(g) through the gaseous
boundary layer. Standard-state free-energies of
IrO,(g) and Ir03(g) formation were obtained.
System
Acta Metall., 1974, 22, (7), 897-900
The glass transition temperature T, of glassy v. v. KUPRINA and G. I. KUPYACHAYA, Vest.
systems (Pd,-,Mx)o B3jSio165 for M=Cu, Ag, Moskov. Univ., Ser. II, Khim., 1974~15, (3),
Au, Rh, Ni, Co and Fe and (Pd,-,Nx), ,,Po 2o 371-373
for N-Ni, Co and Fe was studied. The lowering Studies of the Zr-Ir system detected the interof Tg on admixture of metals with different mediate phases ZrIrs, ZrIr,, ZrIr, Zr,Ir, and
atomic radii results in the non-linearity in T,
ZrJr.
ZrIr3, ZrIr, and ZrJr are formed by
vs x curves (for small x) for (Pd1-,Mx), 835Sio.165 peritectic reactions. ZrIr is formed directly and
alloys and in the shift in peak positions of T, vs undergoes the polymorphic conversion p-tr.
x curves of (Pdl-xNx)n.80Po.,, alloys.
H. S. CHEN,
Investigation of the Character of the

Effect of Palladium on the Oxidation Interatomic Interaction in Alloys of the
Behaviour of Sintered Tungsten-Chromium- Ruthenium-Vanadium System
Palladium Alloys
v. K. YURTAEVA, G. P. MURAV'EVA, M. v. RAEVSKAYA,
Nippon Icinzoku Gokkaishi,
1974, 38, (6), 486-492
The effect of Pd on sintering and oxidation
behaviour of W-Cr alloys was studied on specimens containing ro-zoU/,Cr, 0.1-2%Pd and
0.1-2xNi and compared with that of Ni which
is an effective activator for sintering of W. Both
Pd and Ni accelerated the sintering of W-Cr as
well as the sintering of W but P d was more
effective in activating the sintering than Ni.
T. ITAGAKI and R. YODA,
I. G. SOKOLOVA and E. M. SOKOLOVSKAYA, Vest.

Moskov. Univ., Ser. 11, Khim., 1974, (4), 464-466
The probability of stacking fault formation in
Ru-V alloys in the V solid solution range was
studied and a relation between stacking faults
and alloy hardness was detected.
Density of Molten Palladium, Platinum, and

Iridium at the Melting Point
P. S. MARTSENYUK and YU. N. IVASHCH~NKO, Ukr.
Khim. Zh., 1974, 40, (41,431-433
Densities of molten Pd, Pt and I r measured at the
melting point were found to be 10.52, 18.81 and
19.39 Mg/m3 for Pd, Pt and Ir, respectively. The
impurity contents of the metals were o.ojo0,,Pd,
o.02r0/,Pt and o.030/,Ir.
Crystal Structure of the So-called R.E.,Pd,

Compounds
and A. PALENZONA,J. Less-common
Metals, 1974, 38, (I), 77-82
Single-crystal photographic data of the crystal
M. L. FORNASINI
31
CHEMICAL COMPOUNDS
observation results directly from the existence of

large dielectric constants; values for the
longtitudinal and transverse dielectric constants at
4 K are q l ~ 3 0 0 0and ~ 1 ~ 4 .
Structure-Activity Relationships for Antituniour Active Platinum(I1) Complexes

Abstr. Papers, 168th Nut. Mtg.,
Am. Ckem. SOC.,1974, (Sept.), INOR 16
J. D. HOESCHELE,
On Fluoropalladates(I1) KPdF,, RbPdF,,

TlPdF, and K,PdF,
At least three new major classes of antitumour

active Pt(I1) complexes analogous to cis-Pt
(NH,),C12 have been identified; [Pt(amine),X,],
X,rmalonates, oxalate; cis-(PtA,Cl,], A =
aliLyclic amines; and the Platinum Blues - an
uncharacterised class of PtjNH,) ,-pyrimide
complexes.
and R. HOPPE, 2. Anorg. Allgem. Chem.,

1974,408, (21, I I ~ - J Z O
RbPdF,, TlPdF, and KIdF, were obtained by
heating the binary fluorides in a closed system;
lattice parameters and the colour of the compound
in each case are given.
E. ALTER
Composition and Stability of Osmium(1V)Amino Acids Complexes

0. FAROOQ and N. AHMAD, J . Electroanal. Chem.
Chemistry and Antitumour Activity of

Platinum Blue Complexes
and H. T. PERESIE, Abstr. PaDers,
168th Nut. Mtg., Am. Chem. SOC.,1974, (Sept.);
INOR 17
The reaction of cis-diaquodiammine Pt(IX) with
2,4-dihydroxypyrimidines and primary amides
leads to the formation of highly coloured complexes of Pt which are different in type from the
classic Platinum Blue complexes. The results
of chemical and spectral studies on these complexes are given and are related to possible structures for these complexes.
R. G. FISCHER
461-464
Interfac. Electrochem., 1974, 53, (9,
The interaction of Os(1V) with some amino acids
using sodium chlaroosmate in an aqueous medium
was studied. p H measurement and potentiometric
titrations were used to calculate the successive
equilibrium constants, the overall stability constants, and the compositions.
ELECTROCHEMISTRY
Effect nf Chemisorbed Carbon Monoxide on
Hydrogen Adsorption at Platinum Electrodes
Potential Anti-cancer Activity of Platinum

and Palladium Amine Complexes
M. W. BREITER, Extended Abstr., 14gk Mtg.,

1974, 74-1, (May), 730-731,
Electrochem. SOC.,
abstr. 303
Studies of the effect of chemisorbcd CO on H adsorption on Pt electrodes at room temperature
showed that the potential-H coverage plots did
not change their shape much on the three electrodes at CO coverages below 0.4. Theoretical
predictions require a larger effect than that observed at 8,,<0.4.
s. KIKSCHNER and A. MAURER, Abstr. Papers, 168th

Nut. Mtg., Am. Chem. SOC., 1974, (Sept.),
INOR 94
The preparation of Pd and Pt complexes with
morpholine, piperazine and piperidine ligands,
which show some biological activity but which do
not exhibit anti-tumour activity in their own right,
is reported. Complexes containing hydrazine as a
ligand were also prepared and characterised
before screening for anti-cancer activity.
Clad Metal Anodes

R. BABOIAN, Extended Abstr. 145th Mtg., Electro-
Evidence for Ordered Layers of K+ in KCP
ckenz. SOC.,1974, 74-1, (May), 601-602, abstr. 256

Studies of the anodic polarisation behaviour and
the stability of the clad metal electrodes (consisting mainly of Pt coatings on Ta, Nb and Ti) using
Pt group metals and some of their alloys were
conducted in HC1.
(K,[P~(cN),IC~,.,.~H,~)
and H. SCHULZ, Pkys. Reu. Lett.,

1974, 33, (I6), g63-$5
The crystal structure of K,[Pt(CN),] Cla.3.3H,0
was determined. It crystallises in space group
P4mm, contrary to earlier assignments. The
K t ions occupy ordered positions in layers with
a periodicity of c=5.77 A which are perpendicular
to the c axis. The same kind of superstructure
was found for K,[Pt(CN),] BrO.,.3H,O.
H. J. DEISEROTH
Chemisorptive and Catalytic Properties of

Platinum-RhodiumAlloys
D. A. J. RANDand R. WOODS, Extended Abstr., 145th

Mtg., Electrochem. SOC. 1974, 74-1, (May),
Observation of Electromagnetic Resonances 734-735
Studies of the electrocatalytic activity of Pt-Rh
in Crystals of K,Pt(CN),Br, ,.3H,O at electrodes
during methanol oxidation showed that
Microwave Frequencies
at 0.58V the activity versus composition curve
R. C. JAKLEVIC and R. B. SAILLANT, Solid State
passes through a maximum at 347Rh-R. T h e
Commun., 1974, 15,(2),307-m
catalytic behaviour is interpreted as a mechanism
Electromagnetic dielectric resonances in the involving reaction between organic intermediates
range 8-11 GHz have been observed in I mm and hydroxyl radicals adsorbed on the alloy
sized crystals of K,Pt(CN)IBr,.,.3H20.
This surface.
32
dealuminisation and reaches its maximum when

Si0,:A1,0a=7.3. Increased dealuminisation of
these zeolites leads to a decrease in the dehydrogenation activity of the Pt catalysts.
ELECTRODEPOSITION AND
SURFACE COATINGS
Refractory IntermetallicCompound Coatings
v. SRIKRISHNAN and L. PECORA,

U.S. Rept. AD $$4893/zGA, 1974,zopp
Crystal structure, electronic configuration and
thermodynamics of HfPt, and ZrPt, were studied.
Films of HfPt, and ZrPt, are suitable for coatings
for components subjected to high temperature
oxidising atmospheres.
P. J. FICAI.ORA,
Conversion of Cyclic Hydrocarbons on

Platinum/Alumina Catalyst
Electron Microscope Investigation of Mixed

Stannous Chloride/Palladium Chloride Catalysts for Plating Dielectric Substrates
N. FELDSTEIN, M. SCHLESINGER, N. E. HEDGECOCK
and S. L. CHOW,
Electrochem. Soc., 1974, 121,
3.
738-744
Electron microscopy and electron diffraction
studies of surfaces treated by the catalysing
system (SnCl,/PdCl,/HCl) in conjunction with
various accelerating solutions show that the best
plating results are obtained when Pd,Sn is
present on the treated surface prior to the
metallisation step.
Kinetics of
Palladium
the
Electrodeposition
Effect of Pore Diameter of Aluminium Oxide

on the Activity, Stability and Selectivity of
Platinum/Alurnina Catalysts
v. G. DYRIN, M. E. LEVINTER, A. N. LOGINOVA and
of
Neftekhimiya, 1974, 14, (s), 7i4-719

Fine-pore catalysts have greater activity and
stability for aromatisation, hydrocracking and
coke formation of petroleum fractions but less
selectivity because of increased Pt dispersion and
filling of the pores by molecules of the reactants.
Fine-pore catalysts have less selectivity than wideport catalysts because of secondary aromatisation,
transposition of H,, hydrocracking, and destructive polycondensation with coke formation.
L. I. VLASOVA,
and J. THOMPSON,
J . Electroanal. Chem. Interfacial Electrochem.,
1974, 53, (I), 145-150
Surface area changes which occur when Pd is
deposited on to Pd from chloro-complexes were
studied electrochemically. A three-dimensional
nucleation and growth model is used to evaluate
the kinetics of the process.
J. A. HARRISON, H. B. S . ALCAZAR
HETEROGENEOUS CATALYSIS
On a New Platinum on Alumina Catalyst. I.

Preparation and Composition of the Catalyst
C. HOANG-VAN, P. A. COMPAGNON and s. J. TEICHNER,
Effect of Addition of Iridium on the Activity

of Platinum/Alumina Catalysts in the
Dehydrogenation of Cyclohexane
N. s. KOZLOV, L. YA. MOSTOVAYA and G. A.
Bull. SOC.Chim. Fr., 1974, (7-8 pt.I), 1225-1228

Finely divided Pt was deposited on N , O , without
any change in the amorphous state of the support.
The amounts of Pt and C1 contained in the
samples were determined, as was their specific
surface area by the adsorption of N,.
Neftekhimiya, 1974, 14, (4), 591-594

Studies of the effects of Ir additions to Pt/Al,O,
on catalyst activity, thermal stability and resistance to S poisoning during cyclohexane dehydrogenation showed that Pt-Ir/Al,O, possesses
greater thermal stability and resistance to the
action of S compounds than does Pt/Al,O,.
ZHIZHENKO,
On the Activity of the Platinurn Group

Metals in the Demethylation of Toluene
with Water Vapour
G. L. RABINOVICH, G. V. DYDYKINA, G. N.
MASLYANSKII and M. I. DEMENTEVA,
Kinet. Kataliz,
Activity of Platinum Catalysts, Prepared on

Supports of Type L Dealuminised Zeolites,
in the Reactions of Isomerisation and
Dehydroisomerisation
1974, 159 (41, 949-953

Pt metals on y-Al,O, catalyse demethylation of
toluene with H,O vapour.
Catalyst activity
decreases in the order Rh>Pt>Pd>Ir, Ru, Os,
as for demethylation in He. T h e catalysts are
considered to be bifunctional, the metal possessing
destructive activity and the support possessing
hydrophilic properties.
L. P. SHIRINSKAYA, V. S. KOMAROV, I. I. URANOVICH,

M. F. RUSAK and N. S. KOZLOV, Neftekhimiya, 1974,
14, (411 568-571

Isomerisation activity of Pt!type L dealuminised
zeolites rises with increases in the amount of
and F. G. UNGER,
Neftekhimiya, 1974, 14,(9,707713
Diene condensation products tend to form on
Pt/Al,O, for diene, cyclo-olefin, indene, acenaphthalene, phenanthrene, and anthracene
hydrocarbons. Indane, indene, acenaphthalene,
phenanthrene, anthracene, and more condensed
structures appear to form by C,- and C,dehydrocyclisation of paraffins, aIkylaromatic
hydrocarbons and diene condensates of intermediate dienes and cyclo-olefins. Coke formation
on Pt/A1,0, tends to occur in the order: cyclopentadiene > indene > indane > methylcyclopentane > bis- butylbenzene > hexene > decalin
> hexane > d-methylnaphthalene > styrene >
tetralin.
R. A. BAKULIN, M. E. LEVINTER
33
Determination of the Surface of Dispersed

Platinum Catalysts on Electrically Condncting Supports
N. A. URISSON, L. N. MOKROUSOV, G. V. SHTEINBERG,
z. I. KUDRYAVTSEVA, I. I. ASTAKHOV and v. s.
BAGOTSKII, Kinet. Kataliz, 1974, 15, (4), 1 0 0 9
1014
T h e specific surface u in m2/g for Pt supported
on active C, graphite and C black was determined
by four independent methods. Supported Pt has
2-4 times the surface of Pt black; a tends to
increase as the Pt concentration decreases.
Adsorption of Hydrogen on Pt/Zeolite

Catalysts
T. G. MARTYNYUK, v. I. SHEKHOBALOVA and V. s.
Vest. Maskov. Univ., Ser. I I , Khim.,
19741 (41, 450-454
Studies of the mechanism of H, chemisorption on
various Pt/zeolite catalysts with respect to Pt
content, zeolite type and method of application
of Pi to the zeolites showed complexity of adsorption isotherms.
BORONIN,
Crystallite Size Effects in the Low-temperature Oxidation of Ammonia over Supported

Platinum
J. J. OSTEFXAIER, J. R. KATZER and W. H . MANOGUE,
J . Catalysis, 1974, 33, (3), 457-473

The effect of crystallite size on the specific
catalytic activity of supported Pt catalysts in NH,
oxidation with 0, was determined. Rates of NH,
oxidation were measured in a differential, fixed
bed, flow reactor at 393-473 K and catalysts with
crystallite size of 20, 27 and 155 A were used.
The initial specific catalytic activity of the 155 A
catalyst was higher than those of the 20 and 27 A
catalysts by factors of 5.7 and 3.7, respectively.
Deactivation of a Platinum Monolithic

Carbon Monoxide/Hydrocarbon Oxidation
Catalyst
D. LIEDERMAN, s. E. VOLTZ and P. w. SNYDER, Ind.
Engng. Chem., Prod. Res. Dev., 1974, 13, (3),
166-172
The effects of ageing on the CO/hydrocarbon
oxidation activity and important physical properties of a P t monolithic catalyst were determined.
Catalyst samples were aged to 25,000 equivalent
miles at a maximum temperature of 1450'F with
unleaded fuel on an engine dynamometer. The
activity for the oxidation of CO, C,H,, and engine
exhaust gas hydrocarbons decreased rapidly during the first 1000-5000 miles with very little
additional deactivation during further ageing. A
large decrease in C,H, oxidation activity continued
through the 25,000 miles of ageing. The growth
of very large Pt crystallites appeared to be a
primary cause of catalyst deactivation. No significant changes in surface area or solid-state phase
composition were noted. Small amounts of P b
were detected on aged catalyst samples.
Heats of Adsorption of Hydrogen on

Skeleton Platinum, Rhodium and Platinum
-Rhodium Catalysts in Hydrochloric Acid
Solutions
T. M. CRISHINA, L. I. LOGACHEVA, T. V. SHESTAKOVA
and G. D. VOVCHENKO, Zh. FizKhim., 1974, 48,
(8),2093--2096
The heats of adsorption of Hz on skeleton Pt, Rh
and Rh-Pt catalysts in INHCI solutions were
determined and the bonding energies between the
adsorbed H , and the surfaces were calculated.
Effect of Temperature on the Adsorption of

Hydrogen by Skeleton Platinum-Rhodium
Catalysts in Hydrochloric Acid Solutions
T. M. GRISHINA, L. I. LOGACHEVA, T. V. SHESTAKOVA
and G. D. VOVCHENKO, Zh. %z. Khim., 1974, 48,
(9192330-2332
Galvanostatic and potentiodynamic studies of H,
adsorption on Pt, Rh and Rh-Pt skeleton catalysts
in rNHCl at 10-70C showed that the adsorption
capacity for H, on heating is significantly diminished on Rh and Rh-rich alloys.
Effect of the Composition and Conditions of

Heat Treatment of Palladium-Rhodium
Alloys on Their Catalytic Activity in the
Dehydrogenation of Cyclobexane
E. V. KHRAFOVA, V. M. GRYAZNOV, R. 0. MZEE,
N. R. ROSHAN and B. DZHUNTINI, Izv. Akad. Nauk
S.S.S.R., Sw.I<him., 1974, (IO), 2182-2188

Catalytic activity for cyclohexane dehydrogenation of 7-209/~Rh-Pd alloys decreases as H, is
removed from them and is completely reduced
after treatment by H,. The activity increases with
the temperature for treatment in air from 350
to 750C. Activity increased after tests at 450470C in a stream of Ar, prcsumably due to the
removal of firmly adsorbed H,.
The Catalytic Chemistry of Nitric Oxide. 11.

Reduction of Nitric Oxide over Noble Metal
Catalysts
T. P. KOBYLINSKI and B. w. T A Y L O R , ~ .Catalysis,
1974, 33> (3h 376-384
The reduction studies of NO with H2,
CO, and
equimolar mixture of H,/CO over supported
Pt, Pd, Rh, and Ru catalysts showed that when
H, was used the activity of the catalyst was
Pd>Pt,Rh>Ru.
When CO or CO/H, mixtures were used, this activity sequence was reversed. The results show that CO inhibits NO
reduction strongly over Pt and Pd, the presence
of CO over Ru catalyst accelerates the reaction
and the reduction of NO in the presence of Pt and
Pd gives NH, as major product.
Hydrogenation of Ally1 Alcohol on Rhodium

A. M. SOKOL'SKAYA, K. KH. NURGOZHAEV and T.
O&IARKULOV, z h . Fix. Khim., 1974, 48, (i),
1740-
1742
T h e rate of hydrogenation of ally1 alcohol on Rh
34
black is high because of weakly adsorbed H, on

the Rh surface. Greatest yield (93%) of propanol
occurred at 20C, 20 atm HP; greatest yield of
propanol occurred at 20C and 80C, 60 atm.
Hydrogenation of Aliphatic Ketones under

Pressure of Hydrogen
and A. K.
zh. Fiz-Khirn., 1974, 48, (8),
A. M. SOKOL'SKAYA, A. I. LYASHENKO
ZHARMALAMBETOVA,
2 I 16-2 I 18
a m H,
supports a high rate of conversion of acetone and
methylethylketone to saturated secondary alcohols.
T o increase the rate of ketone hydrogenation the
H , is stabilised by Ru using an alkaline solvent.
Hydrogenation takes place by the formation of
free radicals not exposed to condensation.
I
wt.% Ru/y-Al,O, in H,O at
20-100
is closely connected with catalyst concentration

and with the pressure of Ha. Monoalkylacetylenes
and phenylacetylene are hydrogenated in stages,
and diphenylacetylene adds two moles of H z via
the intermediate stage of diphenylethylene.
Tetrakis(triphenylphosphine)palladium(O)
-Homogeneous Catalyst for the Hydrogenation of Acetylene and Ethylene
G. K. SHESTAKOV, A. M. VASIL'EV, L. M. TISHCHENKO,
0. N. TEMKIN and R. M. FLID, Kinet. Kataliz, 1974,
15, (41, 1070--I072

Tetrakis(triphenylphosphine)palladium(O) in oxylene effectively catalyses hydrogenation of
C,H, and C,H, at IOO'C, I atm. Butene in the
product is formed by hydrodimerisation of C,H,
and C,H,. The reducing agent may be toluene
sulphate and formamide.
Hydrogenation of Epoxycyclododecadiene
over Group W I Metals
Polymerisation of Some Cycloolefins with
F. A. CHERNYSHKOVA, D. V. MUSHENKO, E. G.
Palladiuni-5;-complexes
LEBEDEVA and v.
v. SEMENOVA, Neftekhimiya, 1974,
141 (51, 677-681

Hydrogenation of epoxycyclododecadiene (transepoxy-cis,tram-cyclododecadiene) on Group
VIII metals takes place at the double bonds in
two stages; first to the cis and tram forms of
epoxycyclododecene, which is then reduced to
epoxycyclododecane. Yield of the latter is 879696 on Pd, Ru, Rh, or Pt. Oxirane rings are
not reduced on these catalysts. Hydrogenation
of the cis and tram double bonds of epoxyclododecadiene and epoxycyclodecene on Pd and Rh
proceeds at similar rates.
F. HOJABRI, Abstr. Papers, 168th Nat. Mtg., Am.

Chem. SOC.,1974, (Scpt.), INDE 44
Studies of the Pd z-allylic complexes prepared by
the reaction of PdC1, with pinenes at high
temperature showed them to be very active
catalysts for the polymerisation of bicyclohepta(2,5)-diene at 130-2oo0C. The polymerisation
pattern revealed that only one double bond of the
diene was opened by this reaction.
Catalysis by Supported Transition Metal

Complexes. 11. Hydrogenation of Ally1
Alcohol on a Palladium Resin
R. L. LAZCANO, M. P. PEDROSA, J. SABADIE
J.-E. GERMAN, Bull. soc. Chim. Fr., 1974,
Catalytic Transfer Hydrogenation

and T. J. NESTRICK, Chem. Rev., 1974,
74, t5)l 567-5x0
Studies of the catalytic transfer hydrogenation
with an organic molecule as H donor, using Pd
but occasionally also Raney Ni showed that this
reaction permits the reduction of olefins, nitriles
and nitro compounds, as well as hydrogenolysis
of benzylic and allylic functional groups and the
replacement of aromatic halogen. The reaction
is more selective than regular hydrogenation and
in special cases, such as the reduction of polyunsaturated steroids, has proved superior.
G . BRIEGER
pt.II), 1129-1132
The liquid phase hydrogenation of ally1 alcohol
in the presence of a catalyst obtained by ion
exchange with a basic resin having a PdCla2anion gives a mixturc of propanol and the corresponding aldehyde. The activity and selectivity
of the catalyst was studied as a function of solvent,
temperature (25--28OC), H, pressure (1-100 bar),
and was compared with those of the usual Pd
catalysts. Differences in results indicate the
presence on the resin of active centres, with
markedly different properties to highly dispersed
Pd.
HOMOGENEOUS CATALYSIS
Investigation of the Catalytic Action of
Pt-Sn(I1) Complexes in Hydrogenations of
Acetylene Hydrocarbons
The Selectivity of Palladium(I1) in Substitution Reactions of Their Chloro-complexes with Diamines

Chirnia, 197428, (7), 347349
The rate constants of the substitution reactions of
C1- and HzO by various diamines in Pd(I1)
chloro-complexes were determined spectrophotometrically.
The substitution mechanism is
associative, and comparison with the corresponding Pt (11) complexes shows the selectivity of
Pd(I1) to be smaller than that of Pt(I1).
R. ERNST and R. ROULET,
N. V. BORUNOVA, L. KH. FREIDLIN, YA. G .

MUKHTAROV and N. I. MALOPEEV, Nefzekhirniya,
1974, 14, (4), 572-57s

Pt-Sn complexes catalyse a higher rate of hydrogenation for mono-substituted C =C bonds
than for disubstituted, irrespective of the length
of the substitutcd alkyl chain. The amount of
hydrogenation of pentyne-1 and phenylacetylene
and
(5-6
35
Rhodium Carbonyl Chloride Anion, [Rh exchange suggests that this effect originates from
(CO)2C12]-: a True Catalyst in the Reduction the relative stabilities of the D,, H D and H,
adducts with RhCl(Ph,P),, or by control of the
of NO by CO
H D and H, product distribution by the H2-Dn

equilibrium reaction.
MEYEK, J. REED and R. EISENBERG, Abstr.

Papers, 168th Nat. Mtg., Am. Chem. SOL,1974,
(Sept.), INOR 116
Studies of the RhCl,/EtOH catalyst during
reduction of NO by CO showed that addition
of HCl to the catalyst system shortens an induction
period, during which Rh(CO),Cl,- is formed,
and acid accelerates the reaction between NO and
CO. The interaction of Rh(CO),Cl,- with NO
has been examined and i.r. spectroscopy reveals
the presence of several nitrosyl species.
C. D.
Homogeneous Catalysis of Hydrogen Isotope

Exchange between D, and Ethanol by
Chlorotris(triphenylphosphine)rhodium(I),
11. In Chloroform-Ethanol
Ibid., 2226-2235
The kinetics and mechanism of D , exchange
catalysed by RhCl(Ph,P), was studied in CHCI,
-C,H,OH solutions. T h e D P exchange reaction
rate is strongly dependent on solvent composition
and decreased 30 times between 6-$)6mol.0/,
C,H,OH. The activation energy for D 2exchange
=101fgkJ/mol at 58 mol.:/o C,H,OH, and
86 8kJ/rnol at 6 mol.O/,C,H,OH. Results thus
indicate solvent-catalyst bonding interactions to
be important in this respect.
Preparation of Hydridometallocarboranes
and Their Use as Homogeneous Catalysts
T. E. PAXSON
and M.
F. HAWTHORNE,J.
Ant. Chetn.
SOL.,
19749 96, (I4)i 4674-4676
Methanol solution of the tris(tripheny1phoshine)
rhodium(1) cation was reacted at 60C with a
methanolic solution of either (CH,),NHT[7,8C,B ,HI 2]- or (CH,),NH+[7,9-CPB,H,,]- and high
yields of 3,3-[(C6H,),P],-3-H-3,~,2-RhC,BJI,
and
2.2-[(CsHs),P] ,-2-H-z,r,7-RhC,B
sH1l,
respectively, were obtained. These compounds
catalyse the deuterium exchange of terminal
{BH) groups in boranes, carboranes and
metalloboranes, and the hydrosilation of ketones.
Transition Metal Catalysed Exchange of

Deuterium Gas with Terminal BoronHydrogen Bonds in Carboranes, Metallocarboranes, and Other Boron Compounds
and M. F. HAWTHORNE, Zbid., 4676-4677
I n the presence of catalytic amounts of (PPh,),,
RuHCl which is an effective catalyst for the
specific ortho deuteration of triphenylphosphine,
carboranylphosphine was found to exchange H
atoms for deuterium gas at B atoms but not at
Ca atoms. The nucleophilic character of transition
metal complexes in ortho metallation and other
oxidative additions was discussed.
E. L. HOEL
Homogeneous Catalysis of Hydrogen Isotope

Exchange between D, and Ethanol by
Chlorotris(triphenylphosphine)rhoclium(I).I.
In Benzene-Ethanol
G. STRATIIDEE
and
R. GIVEN,
Can. J . Chem., 1974,
52, (IZ), 2216-2225
The kinetics and mechanism of D,-C,H,OH

exchange catalysed by RhCI(Ph,P), was studied
in 50 vol.%C,H,-C,H,50H. The exchange rate
was low and was limited by the D , transfer rate
from dideuteridochlorotris(tripheny1phosphine)
rhodium(II1) to the solvent, and not by the rate
of activation of D,. T h e activation energy for the
overall process=3gkJ/mol. New data is given
for the catalysis of H2-D, exchange in C,H, by
RhCl(Ph,P),. Analysis of the apparent HD:D,
isotope effect observed during D ,-C,H,OH
Homogeneous Catalysis of Olefin Isomerisation. Part IV. The Isomerisation of Pent-lene Catalysed by Solutions of IrH(CO)
(PPh,) ,, IrHCI,(PEt,Ph) 3, IrCI(CO)(PPh,)
IrCI(O,)(CO)(PPh,),, and of PtH(SnC1,)
(PPh,) 2
D. BINGHAM, D. E. WEBSTER
and
P. B.
WELLS,
J . Chem. SOC.,Dalton Trans., 1974, (14), 15141518

The isomerisation of pent-1-ene to pent-a-ene
at 80C is catalysed by solutions of ( I ) IrH(C0)
(PPh,),, (2) IrHCl,(PEt,Ph),, (3) IrCl(C0j
(PPh,), or IrCl(O,)(CO)(PPh,), each in the
presence of 0 source, and (4) PtH(SnCl,)(PPh,),
in benzene. System (I), (2) and (4) catalyse the
preferential formation of cis-pent-2-ene where as
(3) provides preferential formation of transpent-2-ene.
Bart V. Pent-1-ene Isomerisation Catalysed

by Solutions of RuHCl(PPh,), and of
RuHCI(CO)(PPh,),; Variation of the Isomeric Composition of Pent-2-ene and Its
Attribution to Steric Factors
Zbid., 1519-1521
Isomerisation of pent-I-ene to pent-2-ene at
3 5 4 0 C is catalysed by solutions of RuHCl
(PPh,), and RuHCl(CO)(PPh,), in benzene.
Preferential formation of cis-olefin occurs at
higher catalyst concentrations but a change to
preferential trans-olefin formation is observed
as catalyst concentration is reduced.
Part VI. Pent-1-ene Isomeration Catalysed

by Solutions of Dodecacarbonyltri-iron(0)
and of Bis(benzonitrile)dichloropalladium
(11) in Benzene
D. BINGHAM, B. HUDSON, D. E. WEBSTER
WELLS, Ibid., 1521-1524
and P.
B.
Isomerisation of pent-1-ene to cis- and transpent-a-ene is catalysed at 50C and above by

solutions in benzene of Fe,(C0)12 and of PdC1,
36
(C,H,CN),. In both cases, preferential formation

of trans-pent-2-ene occurs. The reaction mechanisms involve z-allylic intermediates; for the Pdcatalysed reaction bis-n-ally1 complexes may also
participate.
Homogeneous Hydrogenation of Buta-1,3diene and Ethylene Catalysed by Carbonylhydridotris(triphenylphosphine)iridium(I)

and by Carbonyltrihydridobis(triphenylphosphine)iridium(III)
M. G. BURNETT, R. J. MORRISON and c. J. STRUGNELL,
J . Chem. Sac., Dalton Trans., 1974,(16), 1663-1671
Spectrophotometric and kinetic studies of the
individual steps in the catalytic cycle of buta-1,3diene hydrogenated to a mixture of butenes and
butane by IrH(CO)(PPh,), and IrH,(CO)(PPh,),
at 50C in dimethylformamide, were quantitatively interpreted in terms of a mechanism based
on the reductive elimination of butenes by
Ir(a-C,H,)Hz(CO)(PPh,)2.
The intermediate
Ir(T;-C,H,)(CO)(PPh,), was also isolated and
characterised.
Complex Metal-Polymer Catalysts for Benzene Hydrogenation

E. N. RASADKINA, T. V. KUZNETSOVA, A. T. TELESHEV,
I. D. ROZHDESTVENSKAYA and I. V. KALECHITS,
Kinet. Kataliz, 1974, 15, (4), 969-973

Studies of Rh, Ir and Pd catalysts complexed with
nylon showed how conditions of their preparation
affect their properties in C,H, hydrogenation.
Cyclohexene is formed as well as cyclohexane.
T h e order of activity of these complexes is
Ir>Pt>Rh>Pd.
CHEMICAL TECHIYOLQGY
Morphology of Dimensionally Stable Anodes
K. J. O'LEARY and T. J. NAVIN, Extended Abstr.,
145th Mtg., Electmchem. SOC.,r974, 74-1, (May),

603-608, abstr. 257
X-ray studies of 2:1 molar ratio solutions of Ti
and Ru painted on a clean T i substrate and fired
at 10oyoo"C showed that below 300C they are
amorphous and above 700C they are fully
crystalline with extremely small crystals of
roo-5008.
Electrical conductivity of fully
crystalline solid solutions falls between the
insulator T i 0 and metallic conductor RuO 2.
ELECTRICAL AND
ELECTRONIC ENGINEERING
Reliability Studies of the PtSi-Ta-Au Metallisation System for Microwave Power Transistors
H. M. DAY, A. CHRISTOU, w. WEISENBERGER and
J. K. HIRVONEN, Extended Abstr., Iqjth Mtg.,
Electrochem. SOC., 1974, 74-1, (May), 188-189,

abstr. 75
X-ray and electron diffractometry studies of the
Si-Ta-Pt-Au and Si-Pt layers showed formation
of TaAu, TaBSiand Ta,Pt compounds at >450"cJ
while PtSi formed at the Si-Pt interface at 200C
in 20 min. The ion backscattering data indicate
that no further reaction takes place at the Si-Pt
interface when annealed in vacuum at 700C.
Auger electron data on the Si-Ta-Pt-Au system
are also obtained and discussed.
NEW PATENTS
ELECTRODEPOSITION AND
SURFACE COATINGS
METALS AND ALLOYS

Palladium Alloy for Hydrogen Membranes
Ruthenium Dioxide Electrode Coating
URALSKY ORDENA TRUDORAGA KRASNOGO ZNAMEI

POLITEKHNICHESKY INSTITUT
British Patent 1,370,529

Finely-divided RuO, having a particulate size of
0.1 p or less dispersed in an organic polymer,
resistant to degradation in an electrolytic process
exhibits a low oxygen overvoltage for a surprisingly long period of time. Also a combination of
finely-divided RuO, and organic polymer on an
electrically-conductive substrate provides an
efficient electrode for many electrochemical
reactions.
ELECTRONOR CORP.
Britzsh Patent i,365,271

Alloys for H diffusion contain 1-26?" Ag, I - 2 6 O 0
Au, o.r-o.go/, Ru, 0.1-2;; A1 and 0.1-2.5O1, Pt,
remainder Pd. In one example an alloy contains
75% Pd, 2076 Ag, 2.57" Au, 0 . 5 ~ 6Ru, I"/, A1
and 1% Pt.
CHEMICAL COMPOUNDS
Synthesis of Silyl Metal Complexes
HETEROGENEOUS CATALYSIS

Silyl Pt and Pd complexes are formed by reacting
disilanes or hydrosilanes with Pt or Pd phosphine
complexes. Thus Si,Cl, with Pd(PPhzMe),C1,
gives Pd(PPh,Me) ,(SiCl,)Cl.
DOW CORNING CQRP.
Platinum Metals Rev., 1975, 19, (l), 3 7 4 0
Aromatic Hydrogenation
TEXACO DEVELOPMENT CORP.

The hydrogenation of aromatic hydrocarbons in
37
the presence of S may be achieved by adding CO

to the feedstock before it passes over a fiuorided
Pt/AI,O,.
duced by contact with a fluorohalohydrocarbon,

e.g. CHC1,F.
Epoxy Spirolactones
Deuterium from Hydrogen-containingCompounds
S. D. SEARLE & CO.

Spirolactones are produced in a process where an
epoxy androstene furandione is hydrogenated
over Pd jC to give the corresponding androstane
derivative.
GULF RESEARCIi & DEVELOPMENT CO.

A vapour of a deuterium-containing hydrocarbon
undergoes deuterium transfer to another hydrocarbon at high temperature in the presence of a
hydrogenation-dehydrogenation catalyst, especially Pt.
Platinum-Cobalt Catalyst Bed for Flameless

Catalytic Heater
U S . Patent 3,802,856
A catalyst bed unit employing a measured amount
of cobalt in conjunction with P t forms the fuelreactive catalyst of the unit to render the heater
capable of operation at low CO emission levels.
The catalyst is applied to its support by dissolving
chloroplatinic acid and cobalt nitrate in a solution
of methanol and water, spraying the mixture on to
the support and heating the unit to reduce the
H,PtCl, and Co nitrite to Pt and Co metals.
BRUEST INDUSTRIES INC.
Reforming Catalyst
STE. FRANCAIS DES PRODUITS POUR CATALYSE
British Patent r,364,744

Hydrocarbon reforming is catalysed by an A1,03
support carrying o.oo5-r0/, Pt, O.OOS-I~,,I r
and 0.05-3'b T1 and,'or In.
Combination Reforming Process

ESSO RESEARCH & ENGINEERING CO.
Catalyst of Zinc Lanthanide Exchanged

Zeolite

The naphthene content of a paraffininaptha
feedstock is increased in contact with a Pt group
metal and then the product stream is mixed with
H and contacted with a support mixture of Pt with
either Ir, Rh or Ru. Suitably, 0.01-2q:, of both
metals are present on an A1,0, support.
U S . Patent 3,804,780
Pt and Pd catalysts may be supported on a
crystalline zeolite having 6-13 yo lanthanide
cations and less than 2.5"/0 Zn cations.
MOBIL OIL CORP.
NO, Abatement
Trimethyl Hydroquinone Production
& CO. LTD.

U.S. Patent 3,806,582
A process is described for the purification of gases
containing NO, formed in the manufacture of
HNO ,. A gas containing the oxides and including
0 and a gaseous reducing fuel, is passed at a
temperature above the ignition temperature of
the gas and the fuel through a catalyst comprising
an inert ceramic material impregnated or coated
with a mixture or alloy of Pt and Rh metals in
which Rh ranges from 20-507'0 by weight but is
preferably present to the extent of 35?/0by weight
of the catalytic metal content of the catalyst.
JOHNSON MATTHEY

2,3,6-Trimethyl-p-benzoquinone is reduced to
the corresponding hydroquinone using H in the
presence of a P d catalyst and an aliphatic ketone
solvent, e.g. Pd/C plus MIBK.
KURARAY CO. LTD.
Isopropylaniline Production
ESZAKMAGYARORSZAGI VEGYIONUK

N-Isopropylaniline is obtained when aniline and
acetone are reacted in a hydrogen atmosphere at
elevated temperatures and pressures using a Pt
catalyst, for example, 126 Pt/A1,0,.
Preparing Amino-substituted Phosphonates

Hydrocarbon Conversion Catalyst
THE GATES RUBBER CO.

U.S. Patent 3,813,456
T h e preparation of amino-substituted phosphonates from their corresponding cyanosubstituted phophonate precursors, consists of
hydrogenating the cyano-substituted phosphonates in the presence of NH, and Rh catalyst.
UNIVERSAL OIL PRODUCTS CO.

A reforming catalyst is obtained by impregnating
a support (Al,Os) with a complex Sn-Pt group
metal anionic species and calcining in the usual
way. An acidic SnCl solution mixed with a
H,PtCI, solution supplies a suitable impregnating
solution.
Ruthenium NO, Removal Catalyst

FORD 'MOTOR CO.
Saturated Hydrocarbon Isomerisation

co. LTD.
Brirish Patea 1,366,784

The isomerisation of hydrocarbons, e.g. straight
chain paraffins, is catalysed by a mixture of
0.013% Pt or Pd and 0.01-150/~
halogen on a
mordenite support where the halogen is introNIPPON OIL
U.S. Patent 3,819,536
A fixing compound, selected from an alkaline
38
earth material or a rare earth material which

decomposes to an oxide of the material, is
deposited on a catalytic support. A hydrated,
halogenated Ru compound which reduces to
R u is also deposited on the catalytic support. T h e
materials on the support are heated in a reducing
New Rhodium Complex
atmosphere to form the Ru metal. After the

reducing step the materials are fixed by heating
them to a ruthenate-forming temperature.
JQHNSQN MATTHEY
& CO.
LTD.

New complexes of Rh(1) for use in catalysing
hydrogenation, oxidation, decarbonylation, isomerisation, hydroformylation and other reactions
are obtained by adding excess of an arsine,
phosphine, stibine, sulphide or amine stabilising
ligand (susceptible to oxidation) to a Rh(I1)
carboxylate solution protonated by an acid. T h e
complexes are of the type Rh(CO)(PPh:,),BF,,
e.g. prepared from a rhodium acetate (HBF,)
phosphine solution by bubbling through carbon
monoxide.
Platinum Reforming Catalyst

STE. FRANCAIS DE PRODUITS POUR CATALYSE
French Appl. 2,196,192

The catalyst, for use in hydrocarbon reforming,
has an A1,0, support, O.OOS-I.O~( Pt, o.ooS-I.o%
Ir and O . O O S - ~ . O ? ~ Nb.
Acetic Acid Production

German Offen.2,303,271
Acetic acid, optionally with methyl acetate, is
obtained by the reaction of methanol with CO in
the presence of Co catalysts promoted with Br
and/or I and Pd, Pt, Ru, I r or Cu.
BASF A.G.
Palladium Complex in Oligomer Production

MITSUBISHI CHEMICAL INDUSTRIES LTD.

A chain oligomer is produced from a vinyl or
vinylidene aromatic compound in the presence of
a Pd compound, a compound containing a fluoro
complex or perchlorate anion and a trivalent
organic P compound, e.g. methallyl Pd chloride,
tributyl phosphine and Ag chlorate or borofluoride.
HOMOGENEOUS CATALYSIS
Carbon Monoxide Copolymerisation Catalyst
SHELL INTERNATIONALE RESEARCH MIJ. B.V.

High molecular weight polymers are produced
from CO and other monomers, e.g. C,H,, in the
presence of an aryl phosphine-palladium halide
complex, e.g. (PPh,),PdCl, or Pd(PR,),.
Producing Oligomers of Unsaturated Compounds

MITSUBISHI CHEMICAL INDUSTRIES LTD.
Cationic Platinum Catalysts
U.S. Patent 3,803,254
BP CHEMICALS INTERNATIONAL LTD.
Pd phosphine, arsine and stibine complexes, e.g.
[PdL,(PPh,)][BF,] ,, where L is benzonitrile, are

used to oligomerise styrene and other unsaturated
compounds.

New catalysts for alcohol carbonylation and other
reactions are complexes of univalent or trivalent
Rh or Ir with acetonitrile, benzonitrile, butyl
isocyanate, benzene, toluene, phosphite or phosphine; the anion must be a phosphate, sulphate,
perchlorate, borate, iodate or bromate. A typical
catalyst is Rh(P(OPh),),BPh,.
Ruthenium Complexes
RHONE-POULENC S.A.
U.S. Patents 3,804,868 & 3,804,869

New R u complexes of the formula Ru(diket),L,
in which (diket) represents a bidentate ligand
Silane Production
derived from a P-diketone and L is a tertiary
DOW CORNING CORP.
British Patent 1,363,157 phosphine ligand, are useful as catalysts in, for
Pt, Pd and Ni phosphine complexes are used to example, isomerisations (such as the REPPE
catalyse the rcaction of a Si,Cl, and a halide to synthesis), hydrogenations and dimerisations
form mixed substituted silanes. For example, (such as the hydrodimerisation of acrylonitrile to
adiponitrile).
PhSiC1, is prepared by the reaction of Si,CI,
and PhCl in the presence of Pd(PPhMe,),Cl,.
Ruthenium(I1) Complexes as Selective

Hydrogenation Catalysts
PHILLIPS PETROLEUM CO.
U.S.Patent 3,804,914
Unsaturated Organosilicon Compounds

CESKOSLOVENSKA AKADEMIE VED

Silane addition to a diene is catalysed by an
inorganic P d compound or organic complex.
For example, the addition of triethoxysilane to
butadiene is catalysed by bis(ally1)Pd chloride.
Cyclic polyenes are selectively hydrogenated to

cyclic monoenes in the presence of a Ru(I1)
catalyst complex having the general formula
LnRUXm where L is a ligand, X is a halogen or
hydrogen, n is 2,3 or 4, m is 2 or 3 and the sum of
n f m is 4, 5 or 6, e.g. (Ph,),(CO),RuCl,.
Cyanobenzoic Acid Hydrogenation

p-Aminomethyl benzoic acid is produced in one
step by the reaction of an alkyl ester of p-cyanobenzoic acid in aqueous alkaline medium containing a catalyst, e.g. Rh, Ru, RuO,, Rho,, etc.
ASAHI KASEI K.K.K.
39
Platinum Catalyst for Siloxane Curing

WACKER-CHEMIE A.G.
U.S.Patent 3,814,731
Polyorganosiloxanes in non-stick coatings are
cured with a reaction product of H,PtCl, and a
ketone.
Production of Carboxylic Acids

MONSANTO CO.
U.S. Patents 3,816,488 & 3,816,489

An improved process for the production of
carboxylic acids by the reaction of ethylenically
unsaturated compounds with CO and water
uses catalyst compositions consisting of Rh
compounds and complexes together with an
iodide promoter in critical proportions, e.g.
RhCl, promoted with HI, and I r compounds
and complexes together with an iodide promoter
in critical proportions, e.g. IrCl, and HI.
Preparing Linear Fatty Acids

TEXACO INC.
U.S. Patent 3,819,669
A process for preparing linear fatty acids and
esters from alpha olefins and CO uses homogeneous Pt complexes, e.g. a Pt(AsPh,),-SnC12
system.
CHEMICAL TECHNOLOGY
Electrolysis Electrodes
British Patent ~,366,429
A new design of electrode has a sandwich structure in which the outer layers consist of slotted
plates of a valve metal, e.g. Ti, coated with a Pt
group metal or metal oxide (except 0 s ) .
HOOKER CHEMICAL CORP.
when they contain Pd as a component. A preferred Pb alloy contains 0.05 to o.i5O/O of CU,
0.05 to 0.15~6 of Sn and 0.05 to 0.276 of Pd.
I n one example 0.i "/o of each of these was used.
Bilevel Thin Film Integrated Circuit

BELL TELEPHONE LABORATORIES INC.
U.S. Patent 3,s i i,973

Bilevel thin film circuits having Au metallised
through holes require protection from attack by
Au conductor etchants. A new procedure for this
involves plating an etch stop such as Rh or Pt
on the walls of the through holes and around the
entrance and exit ports. Since Rh plating is
normally required in the fabrication of such circuits for solderable components, the through hole
protection and Rh plating may be performed
simultaneously.
Gold Alloy Metallisation for Capacitor
Electrodes
E. I. DU PONT DE NEMOURS & GO.
US.Patent 3,817,758
Powder compositions useful in making ceramic
capacitors electrodes and capacitors contain
specific alloys of 5-15U/o Pt, 15-3oyh Pd and
60-807; Au.
GLASS TECHNOLOGY
TEMPERATURE
MEASUREMENT
Ceramic Inductor
Implantable Thermopiles
U.S. Patent 3,812,442

An inductor consists of a tape of ceramic material
carrying a helical path of metal film, e.g. a Pt-Auglass paste film.
W. L. MUCKELROY
ELECTRICAL AND ELECTRONIC

ENGINEERING
Electrodes for Acid Electrolytes
BADISCHE ANJLIN-
& SODA-FABRIK A.G.

Two electrically conducting bodies, e.g. Pt foil
and a metal electrode base, are cemented together
by an ethylene-unsaturated acid copolymer filled
with an electrically conducting medium, e.g. Au,
Pt, silvered Ti, gilded Ti, platinised Ti, etc.
Electron Discharge Heater

G.T.E. SYLVANIA INC.
British Patent i,366,007
A dark heater coating consists of Al, Zr or Be
oxide coated with 2-2.546 W which is protected
from oxidation by Pt or Ir.
Lead-based Alloys for Electrode

BADISCHE ANILIN-
& SODA-FABRIK A.G.

Pb-based alloys used for solid or grid electrodes
are further improved in their efficiency and life
NUCLEAR BATTERY CORP.
British Patents 1,370,382-1,370,386

Thermopiles for use in human bodies contain a
semiconductor thermoelectric wired up using a
wire made of Au, Ag, Pt or their alloys.
Temperature Measurement
& STEEL RESEARCH ASSOCIATION
Temperatures in steelmaking furnaces, for
example, are measured by a couple formed by
dissimilar metal conductors placed side-by-side
in a refractory insulating matrix with a conducting
path between their ends in the furnace. I n one
example, P t and Pt-Rh conductors are embedded
in magnesia.
BRITISH IRON
High Temperature Thermocouple Alloy

Systems
t
U.S. ATOMIC ENERGY COMMISSION
U.S. Patent 3,817,793

A thermocouple system capable of delivering a
substantially linear EMF response as a function
of temperature up to 1800C in a thermal neutron
environment has a positive leg and a negative leg
consisting of a Cr-base binary alloy having
sufficient ductility to be drawn into wire form;
the alloy contains 15-25 at.?; Ru, 15-20
at.% 0 s and the balance Cr.
40

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UK ISSN 0032-1400

PLATINUM METALS REVIEW

Organometallic Chemistry of Platinum

The Production of Acetic Acid

Superconductivity in Palladium-Hydrogen Alloys

Heavy Platinum Plating from a Molten Salt Bath

The Production of Heavy Water

Photocatalytic Properties of Materials

Trifluorophosphine Complexes of the Platinum Metals

An Age-hardenable Palladium Based Spring Alloy

Communications should be addressed to

Exhaust Purifiers for Compression

systcm in order to give acceptable efficiencies

A new platinum catalyst system has

Platinum Metals Rev., 1975, 19, (l), 2-11

concentration of individual components in

lem for petrol fuelled engines. Therefore the

Engine Exhaust Emissions

Platinum Metals Rev., 1975, 19, (l),

incomplete combustion, and smoke formation

The distinctive obnoxious odour of diesel

American Legislation for Exhaust Emissions

California, light duty vehicles

California, light duty trucks

California, heavy duty vehicles

U.S. Federal, heavy duty vehicles

U.S. Federal, light duty vehicles

U.S. Federal, light duty trucks

* Some of these regulations are n o t yet finalised

Platinum Metals Rev., 1975, 19, (l),

but have been proposed for the dates shown

The elimination of noxious emissions from equipment used in tunnel construction i s

Platinum Metals Rev., 1975, 19, (l),

diesel and petrol powered vehicles over 6000

cedures (3). The essential properties of the

Properties of Oxidation Catalysts

Diesel Exhaust Gas Temperatures

*Johnson Matthey Chemicals registered trade name

Platinum Metals Rev., 1975, 19, (l),

Control of Carbon Monoxide

Thc volume and compositiun of

the engine in the ex-works con-

Platinum Metals Rev., 1975, 19, (l),

Catalytic Oxidation of Hydrocarbons and Carbon Monoxide during CARB Cycle

,efore Catalyst 4fter Catalyst

Brake specific emissions, g/bhp/h

proportional to speed. There is only a limited

Brake Specific Emissions, CARB Cycle, g/bhp/h

Before After IBefore After

Before After Before After

Platinum Metals Rev., 1975, 19, (l),

molecule are higher than for hydrocarbons

Control of Nitrogen Oxides

Platinum Metals Rev., 1975, 19, (l),

in standard and retarded timing shows that

STANDARD CATALYST BOX SIZE

Measurements of odour threshold were made

Application to Diesel Engined

Platinum Metals Rev., 1975, 19, (l),

volume, composition, and temperature) it is

it is possible to choose the appropriate DEP.

Metals Rev., 1972, 16,(3), 74-86

3 California Exhaust Emission Standards, Test