INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA.1966 - IAEA

539 Pages·2011·13.49 MB·English

PROCEEDINGS
OF A
SYMPOSIUM,
VIENNA,
22 — 27 JULY 1965
ORGANIZED
Ф BY THE IAEA
IN CO-OPERATION
W I TH
THE IUPAC
THERMODYNAMICS
INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA.1966

THE RMOD YNAM ICS
Vol.1

PROCEEDINGS SERIES
THERMODYNAMICS
PROCEEDINGS OF THE SYMPOSIUM ON
THERMODYNAMICS
WITH EMPHASIS ON NUCLEAR MATERIALS
AND ATOMIC TRANSPORT IN SOLIDS
ORGANIZED BY THE
INTERNATIONAL ATOMIC ENERGY AGENCY
IN CO-OPERATION WITH THE
COMMISSION ON THERMODYNAMICS AND THERMOCHEMISTRY
OF THE
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
AND HELD IN VIENNA, 22-27 JULY 1965
VOL.1
In two volumes
INTERNATIONAL ATOMIC ENERGY AGENCY
VIENNA, 1966
Symposium on Thermodynamics with Emphasis on
Nuclear Materials and Atomic Transport in
Solids, Vienna, 22 -27 July, 1965.
Proceedings ... organized by the International
Atomic Energy Agency in co-operation with the
Commission on Thermodynamics and Thermo-
chemistry of the International Union of Pure and
Applied Chemistry . . . Vienna, the Agency, 1966.
2 vols. (IAEA, Proceedings series)
541.11
621.039.517
536.7
THERMODYNAMICS, IAEA, VIENNA, 1966
STI/PUB/109
Printed by the IAEA in Austria
January 1966
FOREWORD
Knowledge of the thermodynamics of nuclear materials is vital to the
design of reactor fuels and moderating and cooling systems, in fact all facets
of nuclear plant operation that involve mixtures of, or contact between, two
or more elements in single- or multi-phase systems. The steep thermal
gradients and the high temperatures involved in nuclear technology pose
special problems for engineers and thermodynamicists, who have found that
extrapolation of low-temperature data to high temperatures very often proves
invalid. For this reason, standard thermodynamic techniques such as
calorimetry and EMF-methods have been extended into high-temperature
regions.
Since the Agency's last conference on this subject, also held in Vienna
(Thermodynamics of Nuclear Materials, 1962), there have been notable ad-
vances in calorimetry performed at temperatures greater than 1000°C, and
in the use of EMF cells with solid electrolytes operated at similar tempera-
tures. Significant advances have also been made in measuring diffusion
parameters at the higher temperatures.
An important field covered in this Symposium was the correlation of
such atomic transport data with thermodynamic data, a prerequisite if the
nuclear engineer is to incorporate diffusion results into his normal process-
assessment techniques.
Finally the Symposium suggested the requirements for good critical
tables. The mere compiling of such data is no longer sufficient; the com-
piler must have free access to all the data of a particular experiment, he
must have an intimate knowledge of experimental work in this field and he
must weight every figure quoted in the light of his experience. As a step
in this direction, the Agency has called on the services of many well-known
experts and is preparing a number of monographs giving critical assess-
ments of thermodynamic data and phase-diagrams for many of the elements
of interest in reactor design.
Most of the countries engaged in research in thermodynamics were
represented at the meeting, which was held in co-operation with the Commission
on Thermodynamics and Thermochemistry of the International Union of Pure
and Applied Chemistry.
EDITORIAL NOTE
The papers and discussions incorporated in the proceedings published
by the International Atomic Energy Agency are edited by the Agency's edi-
torial staff to the extent considered necessary for the reader's assistance.
The views expressed and the general style adopted remain, however, the
responsibility of the named authors or participants.
For the sake of speed of publication the present Proceedings have been
printed by composition typing and photo-offset lithography. Within the limi-
tations imposed by this method, every effort has been made to maintain a
high editorial standard; in particular, the units and symbols employed are
to the fullest practicable extent those standardized or recommended by the
competent international scientific bodies.
The affiliations of authors are those given at the time of nomination.
The use in these Proceedings of particular designations of countries or
territories does not imply any judgement by the Agency as to the legal status
of such countries or territories, of their authorities and institutions or of
the delimitation of their boundaries.
The mention of specific companies or of their products or brand-names
does not imply any endorsement or recommendation on the part of the Inter-
national Atomic Energy Agency.
CONTENTS OF VOLЛ
INTRODUCTORY LECTURE
Thermochemistry and.nuclear engineering (SM-66/29) 3
M.H. Rand and L.E.J. Roberts
CALORIMETRY AT HIGH TEMPERATURES (Session 1)
Calorimetry at high temperatures (SM-66/93) 35
F. Grtfnvold
A high température isothermal calorimeter (SM-66/90) 53
J.R. Lacher, H. Gottlieb, P. Fowell andJ.D. Park
Les chaleurs de mélange dans les systèmes binaires de sels
fondus (SM-66/20) . . 67
I. G. Murgulescu et D. I. Marchidan
Emploi d'un calorimètre sous vide pour la mesure des chaleurs
de dissolution de Ge, Al et Ag dans Sn à 700°C;
mesures des enthalpies de Sn, ZrB2, BN et
TÍB2, B4C
(SM-66/55) 75
J. -C. Mathieu, F. Durand et E. Bonnier
Discussion to Session 1: Calorimetry at high temperatures 89
EMF METHODS, INCLUDING SOLID ELECTROLYTES (Session 2)
The EMF method in studying thermodynamic and kinetic
properties of compounds at elevated temperatures (SM-66/,98) . . . . 97
i:
H. Schmalzried
The application of oxygen concentration cells with the solid
electrolyte Zr02- CaO to thermodynamic research (SM-66/15) .. . Ill
Y. Matsushita and K. Goto
Measurements of the thermodynamic stabilities of thé
niobium and tantalum oxides using a high-temperature
galvanic cell (SM-66/66) . 131
W.L. Worrell
Thermodynamic data for plutonium oxides (SM-66/32)- ¡ 145
•T.L. Markin and M.H. Rand
Solid-state EMF techniques: the free energies of formation
of NiCl, and several double salts of KCl (SM-66/62) 157
2 C0CI2
J. J. Egan !
The free energies of formation of thorium borides from. .
measurements on solid EMF. cells (SM-66/61) - 165
S. Aronson and A. Auskern
Термодинамические свойства сплавов железа с кремнием
(SM-66/38) . 171
P. A. Вечер, В. А. Гейдерих и Я .И. Герасимов
Discussion to Session 2: EMF methods, including solid electrolytes . 181
VAPORIZATION (Session 3)
Thermodynamics of vaporization of nuclear materials at
high temperatures (SM-66/72) 191
P. W. Gilles
Knudsen effusion studies of compounds of uranium and thorium
with elements of Groups Illb anb IVb (SM-66/35) 211
С. B. Alcock, J. B. Cornish and P. Grieveson
The vapour pressure of plutonium (SM-66/75) 231
R.N.R. Mulford
The evaporation behaviour, thermodynamic properties
and systematic trends of actinide metal-oxygen systems
(SM-66/80) 243
R.J. Ackermann and R.J. Thorn
Vaporization in the lithium fluoride-beryllium fluoride system
(SM-66/26) ' 271
A. Büchler and J. L. Stauf fer
The preparation and thermodynamics of europium dicarbide
(SM-66/58) ;.. 291
R.E. Gebelt and H.A. Eick
A mass spectrometric study of the vapour pressure of U(g)
and UC(g) over various compositions in the uranium-carbon
2
system (SM-66/70) 309
E;K. Storms
Les préssions de vapeur et l'association moléculaire des
vapeurs du chlorure et du bromure de potassium fondus
(SM-66/19) 345
I. G. Murgulescu et Letitia Marta
Изучение упругости пара монокарбида урана (SM-66/107) 359
B. В. Хромоножкин и Р. А .Андриевский
Discussion to Session 3: Vaporization 367
THERMODYNAMICS OF THE LIQUID STATE (Session IV)
Thermodynamics of fused salts and fused salt mixtures
(SM-66/89) .. 383
O. J. Kleppa
The chemistry and thermodynamics of molten-salt-reactor
fluoride solutions (SM-66/60) ; 409
C.F. Baes, Jr.
Cation-exchange equilibria with fused salts (SM-66/86) 435
E. С. Freiling
Practical application of thermodynamics to plutonium process
reactions at high temperature (SM-66/69) 459
J.A. Leary and L. J. Mullins
Densities of some low melting plutonium alloys (SM-66/73) 473
R.H. Perkins, L.A. Geoffrion and J. С. Biery