NATL INST. OF STAND & TECH

AlllDt 2 0 1 A

7

NIST D-A-DITAi/ifis

PUBLICATIONS

NBSIR 74-600

AFOSR SCIENTIFIC REPORT

AFOSR-TR-75-0596

Thermodynamics of Chemical Species

Important to Rocket Technology

Various authors

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

1 October 1974

Final Report for Agreement No. AFOSR-ISSA-74-0001

July 1973- June 1974

Approved for public release; distribution unlimited.

Prepared for Air Force Office of Scientific Research

1400 Wilson Boulevard

n, Virginia 22209

QC

/oo

my
Qualified requestors may obtain additional copies from the Defense

Documentation Center, all others should apply to the National Technical

Information Service.

Conditions for Reproduction

Reproduction, translation, publication, use and disposal in whole or in

part by or for the United States Covernment is permitted.

Previous reports describing related work have the NBS Report Nos

.

6297, 6484. 6645, 6928, 7093, 7192, 7437, 7587, 7796, 8033, 8186,

8504, 8628, 8919, 9028, 9389, 9500, 9601, 9803, 9905, 10004, 10074,

10326, 10481, 10904, and NBSIR 73-280, 73-281.
NBSIR 74-600

AFOSR SCIENTIFIC REPORT

AFOSR-TR-75-0596

THERMODYNAMICS OF CHEMICAL SPECIES

IMPORTANT TO ROCKET TECHNOLOGY

Various authors

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

1 October 1974

Final Report for Agreement No. AFOSR-ISSA-74-0001

July 1973 -June 1974

Approved for public release; distribution unlimited.

Prepared for Air Force Office of Scientific Research

1400 Wilson Boulevard

Arlington, Virginia 22209

a * p - m'

U. S. DEPARTMENT OF COMMERCE, Frederick B. Dent. Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts. Director

UNCLASSIFIED

SECURITY CLASSIFICATION OK THIS PAGE (When Date Entered) REPORT DOCUMENTATION PAGE READ INSTRUCTIONS

BEFORE COMPLETING FORM

1. REPORT NUMBER j 2 GOVT ACCESSION NO. AROSR-TR-75-0596

j

3 RECIPIENT'S CATALOG NUMBER

4. TITLE (and Subtitle) THERMODYNAMICS OF CHEMICAL SPECIES IMPORTANT TO

5. TYPE OF REPORT A PERIOD COVERED

FINAL

l July 1973-30 June 19 74

6 PERFORMING ORG REPORT NUMBER

7. AUTHORS)

CHARLES W BECKETT

8. CONTRACT OR GRANT NUMBERS)

ISSA- 74-0001

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

INSTITUTE FOR MATERIALS RESEARCH

WASHINGTON, DC 20234

10. PROGRAM ELEMENT. PROJECT TASK

AREA a WORK UNIT NUMBERS

681308

9750-01

" CONTROLLING OFFICE NAME AND ADDRESS

AIR FORCE OFFICE OF SCIENTIFIC RESEARCH/NA

1400 WILSON BOULEVARD

ARLINGTON, VIRGINIA 22209

12. REPORT DATE

Oct 1974

13. NUMBER OF PAGES

200

U. MONITORING AGENCv NAME & ADDRESS^// different Irom Controlling Office) 15. SECURITY CLASS (of this report)

UNCLASSIFIED

15a. DECLASSIFICATION DOWNGRADING

SCHEDULE

16. DISTRIBUTION STATEMENT (of this Report)

Approved for public release; distribution unlimited.

17. DISTRIBUTION STATEMENT (of the abstract entered In Block 20, it different from Report)

18. SUPPLEMENTARY NOTES

'9. KEY WORDS 'Continue on reverse side If necessary and Identify by block number)

graphite electrical resistivity infrared matrix isolation

vanadium radiance temperature spectroscopy

zirconium enthalpy of transition reaction of Fe(g) and oxygen

melting point specific heat total emittance

20. ABST RA ~ T (Continue, on reverse side If necessary and Identify by block number)

Using a subsecond-duration transient technique the specific heat,

electrical resistivity, and hemispherical total emittance were simultaneously

measured over the temperature range 1500-3000 K for some grades of graphite.

Similar measurements were made on vanadium, and zirconium in the temperature

range of 1500-2100 K. Melting points and radiance temperature (at 650 nm) are reported for zirconium and molybdenum. The temperature of the (continued)

I jAN^a 1473 EDITION OF 1 NOV 65 IS OBSOLETE

UNCLASSIFIED

SECURITY CLASSIFICATION OF THIS PAGE (When Drta Entrrrd)
UNCLASSIFIED

SECURITY CLASSIFICATION OF THIS PAGEftWien Dmf Entered)

19. reaction of Ba(g) and excited ozone scandium group and rare-earth gaseous monoxides

calculation of dissociation energies

review of literature on rate of effusion and mass-spectrometric data

bibliography on spectroscopy of fluorides and oxides of the

lanthanide series

20. transition from the a-B phase of zirconium and the energy difference of

these phases has also been measured using the subsecond duration

transient technique.

The products of the reaction of Fe(g) and 0£ have been investigated

and identified using the methods of infrared matrix isolation spectroscopy. A preliminary report on the study of the reaction of Ba(g) with

vibrationally excited ozone is also presented.

The dissociation energies of the scandium group and rare-earth gaseous

monoxides are evaluated by reviewing the literature available on Knudsen

effusion rates and mass-spectrometric data. Criteria are discussed for

choosing data for evaluation of dissociation energies. A bibliography

of the available literature on the spectroscopy of fluorides, oxides,

and oxy fluorides belonging to the lanthanide series is given.

UNCLASSIFIED

SECURITY CLASSIFICATION OF THIS PAGEOWien Data Entered)
FOREWORD

Structure, propulsion, and guidance of new or improved weapons

delivery systems are dependent in crucial areas of design on the

availability of accurate thermodynamic data. Data on high-temperature

materials, new rocket propellant ingredients, and combustion products

(including exhaust ions) are, in many cases, lacking or unreliable.

A broad integrated research program at the National Bureau of Standards

has supplied new or more reliable thermodynamic properties essential

in several major phases of current propulsion development and application.

Measured were compounds of those several chemical elements important

in efficient propulsion fuels; those substances most affecting ion

concentrations in such advanced propulsion concepts as ion propulsion;

and the transition and other refractory metals (and their pertinent

compounds) which may be suitable as construction materials for rocket

motors, rocket nozzles, and nose cones that will be durable under

extreme conditions of high temperature and corrosive environment. The

properties determined extend in temperature up to 6000 degrees

Kelvin. The principal research activities were experimental, and

involved developing new measurement techniques and apparatus, as well

as measuring heats of reaction, of fusion, and of vaporization;

specific heats; equilibria involving gases; several properties from fast

processes at very high temperatures; spectra of the infrared, matrixisolation, microwave, and electronic types; and mass spectra. Some

of these techniques, by relating thermodynamic properties to molecular

or crystal structures, make it possible to tabulate reliably these

properties over far wider ranges of temperature and pressure than those

actually employed in the basic investigations. Additional research

activities of the program have involved the critical review of published

chemical-thermodynamic (and some chemical-kinetic) data, and the

generation of new thermo chemical tables important in current chemicallaser research.

i

ABSTRACT

This report (covering July 1973 -June 1974) gives accounts on

the determination of the thermo physical properties of conductors

by high speed techniques, studies of reaction intermediates of

possible interest to chemical laser systems by the methods of matrix

isolation infrared spectroscopy, preliminary report on the reaction

kinetics of Ba(g) with vibrational ly excited ozone, a survey of the

dissociation energies of the scandium group and rare-earth oxides,

and a bibliography on spectroscopy of fluorides and oxides belonging

to the lanthanide series.

Using a subsecond -duration transient technique the specific

heat, electrical resistivity, and hemispherical total emittance were

simultaneously measured over the temperature range 1500-3000 K for some grades of graphite. Similar measurements were made on vanadium,

and zirconium in the temperature range of 1500-2100 K. Melting

points and radiance temperatures (at 650 nm) are reported for zirconium

and molybdenum. The temperature of the transition from the o/-(3 phase

of zirconium and the energy difference of these phases has also been

measured using the subsecond duration transient technique.

The products of the reaction of Fe(g) and O2 have been investigated

and identified using the methods of infrared matrix isolation

spectroscopy. A preliminary report on the study of the reaction of

Ba(g) with vibrationally excited ozone is also presented.

The dissociation energies of the scandium group and rare-earth

gaseous monoxides are evaluated by reviewing the literature available on Knudsen effusion rates and mass-spectrometric data. Criteria are discussed

for choosing data for evaluation of dissociation energies. A bibliography

of the available literature on the spectroscopy of fluorides, oxides,

and oxy fluorides belonging to the lanthanide series is given.

Charles W. Beckett

iii

TABLE OF CONTENTS

Foreword * Abstract • •• iii

Chap. 1. MEASUREMENTS OF HEAT CAPACITY f EJJEGEKLCAL

RE.STSTTVTTV AMD HRMTRPHFRTP.AT. TOTAT. EMTTTANr.E CiV TWO GRADES OF GRAPHITE IN THE RANGE 1500 TO

3000 K BY A PULSE HEATING TECHNIQUE

(by Ared Cezairliyan and V. Righini) 1

Abstract 1

1. Introduction 2

2. Method 3

3. Measurements 4

Table 1. Characteristics of the Graphite

Specimens 5 4. Experimental Results 6

Heat Capacity 6

Table 2. Operational Characteristic of

the Measurement System During

Experiments of Graphite Specimens ' Table 3. Heat Capacity of Poco and

Pyro lytic Graphites 9

Figure 1. Deviation of Heat Capacity Results

of Poco Graphite 1°

Figure 2. Deviation of Heat Capacity Results

of Pyro lytic Graphite ..... H

Electrical Resistivity 12

Table 4. Electrical Resistivity of Poco

and Pyrolytic Graphites .... 14

Figure 3. Electrical Resistivity of Poco

and Pyrolytic Graphites .... 15

Hemispherical Total Emittance 16

Table 5. Hemispherical Total Emittance of

Poco and Pyrolytic Graphites • . 17

Figure 4. Hemispherical Total Emittance of

Poco and Pyrolytic Graphites . 18

5. Estimate of Errors 19

6 . Discussion 19

Heat capacity 19

Figure 5. Heat Capacity of Graphite Reported

in the Literature 20

Electrical Resistivity 23

Figure 6. Electrical Resistivity of Poco

and Pyrolytic Graphite .... 24

Hemispherical Total Emittance 25

Acknowledgement 26

7. References 27

v
Chap. 2. SIMULTANEOUS MEASUREMENTS OF HEAT CAPACITY. ELECTRICAL

RESISTIVITY AND HEMISPHERICAL TOTAL EMITTANCE BY A

PULSE HEATING TECHNIQUE: VANADIUM. 1500 TO 2100 K

(by A. Cezairliyan, F. Righinl and J. L. McClure) 30

Abstract 30

1. Introduction 31

Table 1. Specimen Information 32

2. Measurements ..... 33

Table la 33

Table 2. Measurement Technique and System

Characteristics 34

Table 3. Functional Representation of

Results on Vanadium 35

Table 4. Results on Properties of Vanadium 35

Table 5. Error Analysis 36

3. Discussion 37

Figure 1. Heat Capacity of Vanadium Reported

in the Literature 38

Figure 2. Electrical Resistivity of Vanadium

Reported in the Literature .... 39

Figure 3. Hemispherical Total Emittance of

Vanadium Reported in the Literature 40

Acknowledgement 42

4. Appendix 43

Table A-l Experimental Results on Heat

Capacity and Electrical Resistivity

of Vanadium 43

Table A-2 Experimental Results on Hemispherical

Total Emittance of Vanadium . . . 44

5. References 45

Chap. 3. SIMULTANEOUS MEASUREMENTS OF HEAT CAPACITY. ELECTRICAL

RESISTIVITY AND HEMISPHERICAL TOTAL EMITTANCE BY A

PULSE HEATING TECHNIQUE

(A. Cezairliyan and F. Righini) 47

Abstract 47

1. Introduction 48

Table 1. Specimen Information 49

2. Measurements 50

Table la Impurities in the Specimen .... 50

Table 2. Measurement Technique and System

Characteristics 51

Table 3. Functional Representation of

Results on Zirconium 52

Table 4. Results on Properties of

Zirconium 52

Table 5. Error Analysis 5 3

3. Discussion 54

Acknowledgement 55

vi
Figure 1. Heat Capacity of Zirconium

Reported in the Literature ... 56

Figure 2. Electrical Resistivity of

Zirconium Reported in the

Literature 57

Figure 3. Hemispherical Total Emittance of

Zirconium Reported in the Literature 58

4. Appendix 59

Table A-l Experimental Results on Heat

Capacity of Zirconium 59

Table A-2 Experimental Results on Resistivity of Zirconium .... 60

Table A- 3 Experimental Results on Hemispherical Total Emittance of

Zirconium 61

5. References 62

Chap. 4. MEASUREMENT OF MELTING POINTS, RADIANCE TEMPERATURE

(AT MELTING POINT) , AND ELECTRICAL RESISTIVITY OF

ZIRCONIUM BY A PULSE HEATING METHOD

(A. Cezairliyan and F. Righini) 64

Abstract 64

1. Introduction 65

2. Measurements 66

3. Experimentsl Results 67

Melting Point 67

Figure 1. Variation of Temperature of

Zirzonium as a Function of Time

Near and at the Melting Point. . 68

Table 1. Experimental Results of the

Melting Point of Tubular

Zirconium Samples ....... 69

Radiance Temperature at the Melting Point ... 70

Figure 2. Variation of Radiance Temperature

(at 650 nm) of Zirconium as a function of time near and at its

melting point for three typical

experiments 71

Table 2. Summary of Experiments for the

Measurement of Radiance Temperature of Zirconium During

Melting 72

Electrical Resistivity 74

Figure 3. Difference of Radiance Temperature (at the melting point

of zirconium, at 650 nm) for

Individual Experiments from their

Average Value of 1940.5 K. . . . 75

Figure 4. Typical Variation of Radiance

Temperature (at 650 nm) of

Zirconium (with oxide coating)

as a Function of Time near and

at its Mleting Point 76

vii
4. Estimate of Errors 77

Figure 5. Variation of Electrical

Resistivity of Zirconium

(Specimen II) as a Function

of Temperature Near and at

its Melting Point 78

5. Discussion 79

Table 3. Imprecision and Inaccuracy of

Measured and Computed Quantities 80

Table 4. Values of the Melting Points

of Zirconium Reported in the

Literature 81

Acknowledgement 83

6. References 84

Chap. 5. THERMODYNAMIC STUDIES OF THE a-^> PHASE TRANSFORMATION IN

ZIRCONIUM USING A SUBS ECOND PULSE HEATING TECHNIQUE

(A. Cezairliyan and F. Righini) 88

Abstract 88

1. Introduction 89

2. Measurements 90

3. Experimental Results 91

Table 1. Results for the oh$ Transformation

Temperature and Transformation

Energy of Zirconium 92

Figure 1. Variation of Temperature as a Function of Time, Near and at the

Transformation Point of Zirconium 94

Figure 2. Variation of Resistivity as a Function of Time Near and at the

Transformation Point of Zirconium 95

Figure 3. Variation of Resistivity as a Function of Temperature Near and

at the Transformation Point of

Zirconium 96

4. Discussion 97

Table 2. Values of the 0^3 Transformation

Temperature of Zirconium Reported

in the Literature 99

Acknowledgement 100

Table 3. Change of the Electrical Resistivity

of Zirconium During the a-3 Transformation Reported in the LiteratuE 101

5. References 102

viii
Chap. 6. RADIANCE TEMPERATURE (AT 650 nm) OF MOLYBDENUM AT ITS

MELTING POINT

(A. Cezairliyan) 105

Figure 1. Variation of Radiance Temperature (at 650 nm) of Molybdenum

as a Function of Time Near and

at its Melting Point for Three

Typical Experiments 107

Table 1. Symmary of Experiments for the

Measurement of Radiance Temperature (at 650 nm) of Molybdenum

during Melting ........ 108

Figure 2. Difference of Radiance Temperature (at the Melting Point)

of Molybdenum at 650 nm) for

Individual Experiments from

their Average Value of

2530.4 K . 110

1. References 112

Chap. 7. MATRIX ISOLATION STUDIES ON THE REACTION OF IRON VAPOR

WITH OXYGEN

(S. Abramowitz and N. Acquista) 113

1. Introduction 113

2. Experimental 113

3. Reeults 114

4. Discussion 115

5 . Conclusion 118

Table 1. Observed Fundamental Modes for

Fe0

2 118

Figure 1. The Infrared Spectrum of Matrix

Isolated Fe0

2 119

6. References . . . 120

Chap. 8. STUDIES OF THE REACTIONS OF Ra(g) WITH 0

^ (W. Braun, M. Kurylo, S. Abramowitz) 122

Capt. 9. DISSOCIATION ENERGIES OF THE SCANDIUM GROUP AND RARE-EARTH

GASEOUS MONOXIDES

(Ralph F. Krause, Jr.) 12 3

Abstract 123

I. Introduction 124

Table 1. Compilations of Dissociation

Energies for the Gaseous Monoxides 125

II. Weight-Loss Vaporization of Sesquioxides . . . 126

Table 2. Some Equilibria Involved with

the Vaporization of Sesquioxides 128

Table 3. Ratio of Mass-Spectrometric Ion

Intensities from Vaporization

of the Sesquioxides 128

III. Auxiliary Data 130

Table 4. Selected Values of Chemical

Thermodynamic Properties for the

Solid Sesquioxides 131

ix
Table 5. Selected Values of Chemical , Thermodynamic Properties of

the Atomic Metals and Atomic

Oxygen 132

Table 6. Values of the Gibbs Free

Energy Functions for the Gaseous

Monoxides 134

Table 7. Differences in Dissociation

Energies from Different Values

of the Gibbs Free Energy

Functions for the Gaseous

Monoxides 134

IV. Errors in Vapor Composition 135

Table 8. Effect of the Uncertainty of

Forming Neodynium Dioxide Gas

on Calculations Using Sesquioxide

Rate of Effusion Data .... 136

Table 9. Effects of Correcting for

Gaseous Tantalum Oxides on Calculations Using Sesquioxide

Rate of Effusion Data .... 136

Table 10. Effects of Other Assumptions on Calculations Using Sesquioxide

Rate of Effusion Data .... 138

V. Equilibria Data by Mass Spectroscopy 139

Table 11. Mass-Spectrometrically Determined

Enthalpy Changes of Isomolecular

Exchange Reactions 140

VI. Recalculated Results 141

Table 12. Dissociation Energies Recalculated

from Published Weight-Loss and

Mass Spectrometric Data . . . 142

VII. References 144

Acknowledgement 147

Chap. 10. BIBLIOGRAPHY ON SPECTROSCOPY OF FLUORIDES AND OXIDES

BELONGING TO LANTHANIDE SERIES

(Francis Westley) 148

I. Cerium 151

II. Dysprosium 153

III. Erbium 155

IV. Europium 158

V. Gadolinium 162

VI. Holmium 165

VII. Lanthanum 167

VIII. Lutetium 171

IX. Neodymium 173

X. Promethium 176

XI. Praseodymium 176

XII. Samarium 179

XIII. Terbium 182

XIV. Thulium 184

XV. Ytterbium 186

x
Chapter 1

MEASUREMENTS OF HEAT CAPACITY, ELECTRICAL

RESISTIVITY AND HEMISPHERICAL TOTAL EMITTANCE

OF TWO GRADES OF GRAPHITE IN THE

RANGE 1500 TO 3000 K BY A PULSE

HEATING TECHNIQUE*

A. Cezairliyan and F. Righini

National Bureau of Standards

Washington, D. C. 20234, U.S.A.

Abstract

Measurements of heat capacity, electrical resistivity and

hemispherical total emittance of Poco and pyrolytic graphites in the

temperature range 1500 to 3000 K by a subsecond duration pulse heating

technique are described. For a given graphite grade, heat capacities

of different specimens were in agreement within 0.5%. The difference

between the results for the two different grades was about 1.8%; the

results of Poco being higher than those of pyrolytic. Electrical

resistivity of the Poco graphite was about four times greater than that

of pyrolytic graphite (parallel to basal planes). Hemispherical total

emittance of Poco graphite was almost twice that of pyrolytic graphite.

This work was supported in part by the U. S. Air Force Office of

Scientific Research.

Guest scientist from the Istituto di Metrologia "G. Colonnetti" in

Torino, under a fellowship from the Consiglio Nazionale delle Ricerche

of Italy.

I
1. Introduction

Disagreements exist between the limited number of experimental

results for the properties of graphite above 1500 K reported in the

literature. Most of the reported measurements were performed on

different grades of graphite, which complicates their evaluation and

poses the question whether the differences were due to measurement

errors or were really indicative of differences in the graphite grades.

As an attempt to elucidate this, a program was initiated for the

systematic and accurate measurement of selected properties of various

grades of graphite at high temperatures. The results of the first

phase, namely the measurement of heat capacity of a grade of graphite

(Poco, AXM-5Q) in the temperature range 1500 to 3000 K, were presented

in an earlier publication [1]. The objective of this paper is to report

the results of the measurements of heat capacity, electrical resistivity

and hemispherical total emittance of two grades of graphite (Poco and

pyrolytic) in the range 1500 to 3000 K. The Poco graphite used in this

-fro too work (Poco, DFP-2) is differentiae one. used in the earlier study. For

a. completeness and for ease of comparison, the results of the earlier study

on Poco graphite are also included in this paper,.

^Commercial identification of graphites is made in this paper in order

to specify adequately the grade of the graphite specimens whose properties

were determined experimentally. In no case does such identification

imply recommendation or endorsement by the National Bureau of Standards.
2. Method

The method is based on rapid resistive self-heating of the tubular

specimen from room temperature to high temperatures (above 1500 K) in

less t;han one second by the passage of an electrical current pulse

through it; and on measuring, with millisecond resolution, such

experimental quantities as current through the specimen, potential drop

across the specimen, and specimen temperature.

The current through the specimen is determined from the measurement of the potential difference across a standard resistance placed in

series with the specimen. The potential difference across the middle

one third of the specimen is measured between spring-loaded, knife-edge

probes. The specimen temperature is measured at the rate of 1200 times

per second with a high-speed photoelectric pyrometer [2], The small

hole in the wall at the middle of the tubular specimen provides an

approximation to blackbody conditions for optical temperature measurements. All these data are recorded with a digital data acquisition

system, which has a time resolution of 0.4 millisecond and a full-scale

signal resolution of one part in 8000.

Details regarding the construction and operation of the measurement

system, the methods of measuring experimental quantities, and other

pertinent information, such as the formulation of relations for

properties, etc. are given in earlier publications [3, 4],

3
3. Measurements

The new measurements reported in this paper were performed on

one Poco graphite (DFP-2) specimen and two pyro lytic graphite specimens.

The characteristics of these specimens, as well as those of the Poco

graphite (AXM-5Q) specimen used in the earlier study, are given in

Table 1. In the rest of this paper, the specimens are referred to by

their designated numbers as listed in Table 1. The pyro lytic graphite

specimens were fabricated in a way to allow the pulse current to flow

in the direction parallel to the basal planes. Before the start of

the measurements, the specimens were heat treated by subjecting them

to 15-20 heating pulses (up to 2800 K) . All the experiments were

conducted with the specimen in a vacuum environment at approximately

10"5

torr.

To study possible effects that might be attributable to the rate

with which the specimen heats, two ranges of heating rates, designated as

"fast" and "slow", were used in the experiments on specimens-l, 2 and 3.

To optimize the operation of the high-speed pyrometer, the temperature

interval (1500 to 3000 K) was divided into six ranges. A "fast" and

a "slow" experiment were performed in each temperature range. These

yielded a total of 12 experiments for each of the specimens-l, 2 and 3.

In the case of specimen-4, only a "slow" heating rate was used yielding

a total of 6 experiments for the specimen.

4
Table 1

Characteristics of the Graphite Specimens

Specimen ru l x l y UC 1 1 o L L

y

Nominal Dimensions, mm

Designation Grade

-3

g • cm length O.D. thickness

Specimen-1 Poco (AXM-5Q)* 99.

9

+

1.755 76 6.3 0.5

Specimen-2 Poco (DFP-2) 99.99+

1.791 76 6.3 0.5

Specimen-3

*** Pyrolytic 99.99+

2.19 76 7.2 0.5

Specimen -4

•kick Pyrolytic 99 . 99+

2.19 76 7.2 0.5

The graphite block was kindly furnished by the U.S. Air Force Materials

Laboratory, Wright-Patterson Air Force Base, Ohio.

"kThe graphite block was purchased from the Poco Graphite, Inc.

The graphite in the form of tubes was kindly furnished by the Union

Carbide Corporation through Dr. A. W. Moore. Deposition temperature:

2400 K.

5
To optimize the operation of the measurement system, the heating

rate of the specimen (in both "fast" and "slow" experiments) was varied

depending on the desired temperature range by adjusting the value of

the resistance in series with the specimen. Duration of the current

pulses ranged from 210 to 330 ms for the "fast" experiments, and 280 to

520 ms for the "slow experiments. Other typical operational

characteristics of the measurement system during the experiments on

the two different-grade graphite specimens, such as specimen heating

rate, and heat loss from specimen by thermal radiation, are summarized

in Table 2.

Optical checks performed on the experiment chamber window after

the pulse experiments did not indicate any graphite deposition. Also,

weight measurements before and after the entire set of pulse experiments

did not show any change in specimen weight.

4. Experimental Results

This section presents the properties determined from the measured

quantities. All values are based on the International Practical

Temperature Scale of 1968 [5]. In all computations, the geometrical

quantities are based on their room temperature (298 K) dimensions.

4.1. Heat Capacity

The heat capacity data were determined from the measurements of

current, voltage, and temperature obtained during the heating period.

A correction for heat loss due to thermal radiation was made using the

results on hemispherical total emittance.

6
Table 2

Operational Characteristics of the Measurement

System During Experiments on Graphite Specimens

Graphite Temperature Specimen Heating Rate Radiative Heat Loss

Grade K K's"

i from Specimen

% of input power

"Fast" "Slow" "Fast" "Slow"

1500 6000 4400 2 3

Poco

(Specimen^!)

2000 6000 4000 7 10

2500 6900 3800 13 22

3000 6200 2700 26 45

1500 3800 2900 2 3

Py rolytic 2000 5100 3600 4 6

(Specimen-3) 2500 6600 5200 7 9

3000 7500 5700 12 15

7
The heat capacity results obtained for the "fast" and "slow"

experiments were fitted separately for each specimen by polynomial

functions of temperature using the least squares method. The best fits

were quadratic for Poco graphite and linear for pyrolytic graphite,

with standard deviations (of an individual point) in the range 0.4 to

0.67o. A study of the results indicated the following: (a) the

difference in the results corresponding to "fast" and slow experiments

for a given specimen (in the range 0.2 to 0.6%) is less than or

comparable to the measurement resolution, and (b) the difference in

the results corresponding to the two specimens of the same graphite grade

(0.37, for Poco and 0.57, for pyrolytic) is less than or comparable to

the measurement resolution. It may be concluded that for a given

graphite grade, two different specimens and two different heating rates

yielded the same value for heat capacity. However, the average absolute

difference between the results of Poco and pyrolytic graphites was 1.87,;

the results of Poco being higher than those of pyrolytic.

The functions for heat capacity that represent the combined results

of the two specimens and the two heating rates for each graphite grade in

the range 1500 to 3000 K are:

For Poco graphite (standard deviation, 0.57,)

C

p = 19.84 + 3.490 x 10"3

T-4.119 x lO'V (I)

For pyrolytic graphite (standard deviation, 0.67.)

C = 21.60 + 1.534 x 10"3T ) P where T is in K and C is in J.mol"«K . In the computations of heat

P capacity, the atomic weight of graphite was taken as 12.011. The heat

8
Table 3

Heat Capacity of Poco and Pyrolytic

Graphites According to Equations (1) and (2)

Temperature

K

Heat Capacity, J-mol »K

Poco Pyrolytic

1500 24.15 23.90

1600 24.37 24.05

1700 24.58 24.21

1800 24.79 24.36

1900 24.98 24.51

2000 25.17 24.67

2100 25.35 24.82

2200 25.52 24.97

2300 25.69 25.13

2400 25.84 25.28

2500 25.99 25.44

2600 26.13 25.59

2700 26.26 25.74

2800 26.38 25.90

2900 26.50 26.05

3000 26.60 26.20

9


capacity for the two grades of graphite computed using the Equations

(1) and (2) is presented in Table 3. Figures 1 and 2 show the

deviation of the measured heat capacity values of Poco and pyrolytic

graphite specimens from the values calculated from Equations (1) and

(2) , respectively.

4.2. Electrical Resistivity

Electrical resistivity of the graphite specimens was determined

from the same experiments that were used to calculate heat capacity.

In the case of pyrolytic graphite, the results correspond to the

measurements in the direction parallel to the basal planes. The differences

in the results between "fast" and "slow" experiments for a given

specimen were within the measurement resolution. However, unlike heat

capacity, there were differences in the electrical resistivity of the

two specimens belonging to the same graphite grade. The average absolute

difference between the two specimens was about 7% for Poco graphite and

1.57o for pyrolytic graphite. It should be noted, however, that the Poco

graphite specimens represented two different types, therefore, a

difference in their electrical resistivity may be expected. The

difference in the case of pyrolytic graphite may largely be attributed to

the differences in the fabrication of the specimens. The electrical

resistivity of Poco graphite at temperatures above 1500 K was about four

times greater than that of pyrolytic graphite.

12
The functions for electrical resistivity that represent the

average of the results corresponding to two different heating rates for

the two types of Poco graphite specimens in the range 1500 to 3000 K

are

Poco (AXM-5Q) graphite (standard deviation, 0.07 % )

p = 908.56-1.4324 x lO^T + 1.4766 x 10

_A

T

2 -2 .2603 x 10

_8

T

3

(3)

Poco (DFP-2) graphite (standard deviation, 0.05%)

D = 808.97-1.0082 x 10

-1

T + 1.2824 x lO^I2 -1 . 9763 x 10"8

T

3

(4)

The function for electrical resistivity that represents the

average of the results for the two pyrolytic graphite specimens

corresponding to two different heating rates in the range 1500 to

3000 K is:

Pyrolytic graphite (standard deviation, 0.9%)

P = 190.21-1.3574 x 10" 3

T + 1.6492 x lO'V (5)

-8

where T is in K and p is in 10 Q«m. The electrical resistivity of

the graphites computed using Equations (3), (4) and (5) is presented in

Table 4. The measured electrical resistivity values of the graphite

specimens are shown in Figure 3. The data on both Poco graphite specimens

indicate the presence of an inflection point in the function of electrical

resistivity versus temperature in the vicinity of 2170 K (2178 K for

specimen -1 and 2163 K for specimen-2) . The data on pyrolytic graphite

do not indicate any inflection point in the present temperature range.

Electrical resistance measurements at 283 K with a Kelvin bridge

before and after the pulse experiments were in agreement within 0.1% for

the Poco graphite specimens and 0.5% for the pyrolytic graphite specimens.

This indicates that no significant irreversible structural or chemical

changes had taken place in the specimens as the result of

13
Table 4

Electrical Resistivity of Poco and Pyrolytic

Graphites According to Equations (3), (4) and (5)

Temperature

K

-8

Electrical Resistivity, 10 Q-m

Poco Pyrolytic

Specimens

3 and 4

AXM-5Q

(Specimen-1)

DFP-2

(Specimen-2)

1 DUU 949.7 879.6 225.3

i £aa 964.8 895.0 230.3

i ir\f\ i /UU 980.7 911.1 235.6

i qaa loUU 997.3 927.7 241.2

1014.4 944 .8 247.2

o aaa 1031.9 962.2 253.5

1 1 AA 2 100 1049.6 979.8 260.

1

1 1 AA zzUO 1067.4 997.4 267.0

O O AA 1085.2 1015.0 274.3

O/. AA 1 inn o

1 102 .

8

1032 .

5

281.9

0 £ AA 1120.2 1049.6 289.9

2600 1137.1 1066.4 298.2

2700 1153.4 1082.6 306.8

2800 1169.0 1098.2 315.7

2900 1183.7 1113.1 325.0

3000 1197.5 1127.1 334.6

14
1200

1100

1000

C3

COO

| 900

i—GO

CO

"J= 340

<o

BC

300

260

220

P0C0 GRAPHITE

SPECIMEN 1

+ SPECIMEN-2

5% -

• FAST HEATING

+ SLOW HEATING

PYR0LYTIC GRAPHITE

SPECIMEN-3-

L_SPECIMEN-4 5

o

/o

+ •o

•o

+ •o • FAST HEATING

SLOW HEATING

i

400

JL 1800 2200 2600 3000

TEMPERATURE, K

Figure 3. Electrical resistivity of Poco and pyrolytic graphites

15
their having been heated to high temperatures. The average values of the

-8

electrical resistivity (in 10 Q'To) for the graphites at 283 K were

as follows: 1475 for Poco (AXM-5Q), 1338 for Poco (DFP-2) and 511

for pyro lytic graphite.

4.3. Hemispherical Total Quittance

Hemispherical total emittance was computed for each specimen

using data taken during both heating and cooling periods. In the

case of pyrolytic graphite, the results correspond to radiation emitted

from the surface parallel to the basal planes. The differences between

the "fast" and "slow" experiments for a given specimen were within

the measurement resolution. However, the results were different for

different specimens. The functions for hemispherical total emittance

that represent the results of the graphites are:

Poco (AXM-5Q) graphite, 1800 to 2900 K (standard deviation, 0.7%)

e = 0.679 + 6.00 x 10" 5

T (6)

Poco (DFP - 2) graphite, 1700 to 2900 K (standard deviation, 0.7%)

e = 0.794 + 2.28 x

10"5 T (7)

Pyrolytic graphite, 2300 to 3000 K (standard deviation, 1.2%)

e = 0.641-5.70 x 10" 5 T (8)

where T is in K. The hemispherical total emittance of the graphites

computed using Equations (6), (7) and (8) is presented in Table 5. The

measured values of the hemispherical total emittance of the graphite

specimens are shown in Figure 4.

16
Table 5

Hemispherical Total Emittance of Poco

and Pyrolytic Graphites According to

Equations (6), (7) and (8)

Hemispherical Total Emittance

Temperature Poco Pyrolytic

K AXM-5Q DFP- 2

(Specimen -1) (Specimen-2) (Specimen-3)

1700 0.833

1800 0.787 0.835

1900 0.793 0.837

2000 0.799 0.840

2100 0.805 0.842

2200 0.811 0.844

2300 0.817 0.846 U . J IV

2400 0.823 0.849 U . JUH

2500 0.829 0.851 0.499

2600 0.835 0.853 0.493

2700 0.841 0.856 0.487

2800 0.847 0.858 0.481

2900 0.853 0.860 0.476

3000 0.470

17

5. Estimate of Errors

Estimates of errors in measured and computed quantities lead to

the following estimates of errors in the properties: heat capacity,

3%; electrical resistivity, 1% (Poco) and 3% (pyrolytic) ; hemispherical

total emittance, 5%. Details regarding the estimates of errors and

their combination in experiments using the present measurement system

are given in a previous publication [4]. Specific items in the error

analyses were recomputed whenever the present conditions differed from

those in the earlier publication.

Because of the high value of the hemispherical total emittance

of graphite (especially Poco grades), heat loss from the specimen due

to thermal radiation constitutes a substantial fraction of the input

power, especially at temperatures above 2500 K (Table 2). However,

as a result of data taken during the cooling period, an accurate account

of its magnitude in correcting heat capacity was possible. This is

demonstrated by the rather closely agreeing results (within measurement resolution) of the two sets of experiments performed on the same

specimen at two different heating rates.

6. Discussion

6.1. Heat Capacity

Only a limited number of experimental heat capacity results for

graphite at temperatures above 1500 K was found in the literature.

Since most of them are for different grades of graphite, it is questionable whether one has a common ground for comparison. As it may be seen

in Figure 5, considerable differences exist between the results of

various investigators. , Q
1000 1500 2000 2500 3000

TEMPERATURE, K

Figure 5. Heat capacity of graphite reported in the literature.

The measurements, with the exception of those of Rasor

and McClelland and the present work, were performed

using drop calorimetric techniques.
The heat capacity results of the present work agree best with

those reported by West and Ishihara [6] on grade CCH graphite. In the

overlapping temperature region (1500 to 2600 K), the results of West

and Ishihara are, on the average, about 0.6% lower than the Poco

graphite results and about 1.2% higher than the pyro lytic graphite

results. This rather close agreement is even more significant if

one considers that different measurement techniques (drop and pulse)

were employed in the two cases.

The smoothed results of Rasor and McClelland [7] are average

values, as given by the authors, representing data on four grades of

graphite ^3474D, 7087, GBH, and GBE) . Their actual data have a scatter

of approximately 5% about their smooth curve. The difference between

the results of Rasor and McClelland and those of the present work is,

on the average, about 3% (Poco) and 5% (pyrolytic).

Lucks et al. [8] have reported results for two grades of graphite.

The upper and lower curves (in Figure 5) represent the results for the

grades 7087 and GBH, respectively. The disagreement between the results

of Lucks et al. and Rasor and McClelland for the same grades of graphite

is more than 10%, suggesting serious experimental errors.

In the temperature region of overlap with the present work (1500 to

1800 K), the results for ATJ graphite reported by Fieldhouse et al. [9]

agree, within 3%, with those of the present work. However, the slope of

the curve representing the results of Fieldhouse et al. is considerably

greater than the slopes of the curves representing the present work.

21
The results reported recently by Sheindlin et al. [10] on a

number of different graphites fall between the present work results on

the two graphite grades in the range 1500 to 2300 K. However, above

2300 K, their results indicate a sharp increase in heat capacity

which reaches a value of 29.55 J'mol"

1 ^"1

at 3000 K, which is 11% higher

than the present work result on Poco graphite.

In addition to the present measurements, the only other known

measurements on Poco (AXM-5Q) graphite were those reported in the AGARD

Report [11] covering the temperature range 373 to 1273 K. Since these

data have no overlapping region with the present results it is difficult

to estimate the differences in the two results. However, from Figure

5 it may be seen that an extrapolation of the literature results to

1500 K is likely to yield a value approximately 2% lower than that of

the present work on Poco graphite.

The rather closely agreeing results of West and Ishihara [6] and

those of the present work were obtained on different grades of graphite

using different measurement techniques indicating that the heat

capacity of graphite may not be very sensitive to differences in certain

grades. Therefore, the differences in the literature results should not

be entirely attributed to grade differences, and the foregoing observation

suggests that these differences might have been partly due to experimental

errors. In addition, the state of the specimen (purity, degree of

graphitization and annealing) have undoubtedly played an important role

in the results. Sheindlin et al. [10] have also arrived to a similar

conclusion as a result of their measurements on several graphites. They

22
have observed that the values obtained for different graphites did

not differ by more than their experimental error (1.5 to 2.5% in

enthalpy) .

It may be seen that heat capacity of graphite reaches the Dulong

and Petit value of 3R at a temperature in the vicinity of 2000 K, and

continues to increase above that temperature.

The next challange in heat capacity measurements is likely to be

at temperatures above 3000 K where measurements will yield information

of practical and theoretical significance. It is important to resolve the

questions of whether the heat capacity of graphite reaches a constant

value at high temperatures, or increases sharply, as was reported by

Rasor and McClelland [7] and Sheindlin et aL [10].

6.2. Electrical Resistivity

A comparison of the present work and literature results on the

electrical resistivity of the two graphite grades is presented in

Figure 6 .

In addition to the present measurements, the only other known

measurements of the electrical resistivity of Poco graphite above

1500 K are those reported in the AGARD Report [11]. A comparison of the

present work results with the two different measurements indicates that

in one case the present work values are 8% lower (at 1500 K) and 1% higher

(at 2500 K) than the literature values; in the other case, an extrapolation over 200 K indicates that at 1500 K the present work value is

about 5% higher than the literature value.

23
2001

1000 1500 2000 2500 3000

TEMPERATURE, K

Figure 6. Electrical resistivity of Poco (AXM-5Q) and pyro lytic

graphite reported in the literature. The AGARD Work"

corresponds to measurements by. di-^e rent participants

reported in Reference [11].

24
Electrical resistivity of pyrolytic graphite was reported by

Pappis and Blum [121 up to 1700 K and by Petrov et al. [13] up to

2200 K. At 1500 K the present work result is 2 and 3% lower than the

values reported by Pappis and Blum, and Petrov et al., respectively;

at 1700 K it is TL lower than that of Pappis and Blum; at 2200 K it

is 5% higher than that of Petrov et al.

6.3. Hemispherical Total Emittance

No other measurements of the hemispherical total emittance of

Poco graphite have been located in the literature. The results for

other graphites such as Acheson graphite reported by Jain and Krishnan

[14] yield 0.81 at 1700 K and 0.83 at 2100 K which are within 370 of

the results of the present work.

Because of differences in the methods of fabrication for the specimens

and the anisotropic properties of pyrolytic graphite, considerable

differences in hemispherical total emittance measurements by different

investigators may be expected. As presented by Petrov et al. [15], the

values for emittance reported in the literature at temperatures above

1200 K range from 0.5 to 0.9. In addition to the large differences,

the trends (emittance versus temperature) are also considerably different, in some cases emittance is reported to increase with increasing

temperature and in others to decrease with temperature. The results

of the present work indicate a decrease of emittance with temperature

and their closest agreement is with those of Petrov et al . [15]. The

measurements by Petrov et al. show a decrease in emittance up to about

2000 K and a small increase above 2000 K. Extrapolation of the present

25
work results to 2000 K yields a value of 0.53 which is about 5% lower

than the value given by Petrov et al.

Acknowledgement

The authors express their gratitude to Dr. C. W. Beckett for his

encouragement of research In high-speed thermophysical measurements and

to Mr. M. S. Morse for his help with the electronic instrumentation.

26
7. References

1. A. Cezairliyan. - Measurement of the heat capacity of graphite

in the range 1500 to 3000 K by a pulse heating method, in

Proceedings of the Sixth Symposium on Thermophysical Properties,

P. E. Liley, ed . Am. Soc. Mech. Eng., New York, 1973, 279-285.

2. G. M. Foley. - High-speed optical pyrometer. Rev. Sci. Instr.,

1970, 41, 827-834.

3. A. Cezairliyan. - Design and operational characteristics of a highspeed (millisecond) system for the measurement of thermophysical

properties at high temperatures. J. Res. Nat. Bur. Stand. (U.S.),

1971, 75C (Eng. and Instrum.), 7-18.

4. A. Cezairliyan, M. S. Morse, H. A. Berman and C. W. Beckett. -

High speed (subsecond) measurement of heat capacity, electrical

resistivity, and thermal radiation properties of molybdenum in

the range 1900-2800 K. J. Res. Nat. Bur. Stand. (U.S.), 1970,

74A (Phys. and Chem.), 65-92.

5. International Committee for Weights and Measures. - The

International Practical Temperature Scale of 1968. Metrologia, 1969,

5, 35-44.

6. E. D. West and S. Ishihara. - A calorimetric determination of the

enthalpy of graphite from 1200 to 2600 K, in Advances in Thermo5. Gratcfc, e.d.

physical Properties at Extreme Temperatures and Pressures, Am.

Miw york, A

Soc. Mech. Eng., 1965, 146-151.

27
7. N. S. Rasor and J. D. McClelland. - Thermal properties of

graphites, molybdenum, and tantalum to their destruction

temperatures. J. Phys. Chem. Solids, 1960, 15, 17-26.

8. C. F. Lucks, H. W. Deem and W. D. Wood. - Thermal properties

of six glasses and two graphites. Am. Cer. Soc. Bull., 1960,

39, 313-319.

9. I. B. Fieldhouse, J. I. Land and H. H. Blau. WADC TR 59-744,

1960, 1-78 [AD 249 166].

10. A. E. Sheindlin, I. S. Belevich and I. G. Kozhevnikov. - Enthalpy

and specific heat of graphite in the temperature range 273-3650 K.

High Temperature, 1972, 10, 897-900.

11. E. Fitzer. - Thermo physical properties of solid materials -

Project section II - Cooperative measurements on heat transport

phenomena of solid materials at high temperatures. AGARD Report

606, 1973.

12. J. Pappis and S. L. Blum. - Properties of pyrolytic graphite. J.

Am. Cer. Soc, 1961, 44, 592-597.

13. V. A. Petrov, I.I. Petrova, V. Ya . Chekhovskoi and E. N.

Lyukshin. - Specific electrical resistivity of py rographite

.

High Temperature, 1971, 9, 271-274 .

28
S. C. Jain and K. S. Krishnan. - The distribution of

temperature along a thin rod electrically heated in vacuo.

Proc. Roy. Soc. (London), 1954, 225, 7-18.

V. A. Petrov, I. I. Petrova, V. Ya. Chekhovskoi and A. E.

Sheindlin. - Experimental determination of the emissivity,

electrical resistivity, and thermal conductivity of pyrolytic

carbon. High Temperatures -High Pressures, 1970, 2_, 155-160.

29
Chapter 2

SIMULTANEOUS MEASUREMENTS OF HEAT CAPACITY,

ELECTRICAL RESISTIVITY AND HEMISPHERICAL TOTAL

EMITTANCE BY A PULSE HEATING TECHNIQUE:

VANADIUM, 1500 TO 2100 K*

A. Cezairliyan, F. Righini** and J. L. McClure

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

Abstract

Simultaneous measurements of heat capacity, electrical

resistivity and hemispherical total emittance of vanadium in the

temperature range 1500 to 2100 K by a subsecond duration, pulse

heating technique are described. The results are expressed by the

relations

c = 56.34 - 3.839 x 10~ 2T + 1.563 x 10

_5

T

2

P

p = 8.794 + 6.282 x 10

_2

T -6.804 x 10

_6

T

2

- 1 - 1 -8

where c^ is in j-mol -K , p is in 10 Q»m, and T is in K. The

values for the hemispherical total emittance are: 0.313 at 1900 K

and 0.332 at 2000 K. Estimated inaccuracies of the measured propert

are: 3% for heat capacity, 0.5% for electrical resistivity and

5% for hemispherical total emittance.

This work was supported in part by the U. S. Air Force Office of

Scientific Research.

**Guest scientist from the Istituto di Metrologia "G. Colonnetti"

in Torino, under a fellowship from the Consiglio Nazionale delle

Ricerche of Italy.

30
1. Introduction ,

In this paper, application of a pulse heating technique to

the simultaneous measurements of heat capacity, electrical resistivity

and hemispherical total emittance of vanadium in the temperature

range 1500 to 2100 K is described.

The method is based on rapid resistive self-heating of the

specimen from room temperature to high temperatures (above 1500 K)

in less than one second by the passage of an electrical current

pulse through it; and on measuring, with millisecond resolution,

such experimental quantities as current through the specimen, potential

drop across the specimen, and specimen temperature. Details regarding

the construction and operation of the measurement system, the methods

of measuring experimental quantities, and other pertinent information,

such as the formulation of relations for properties, error analysis,

etc. are given in earlier publications [1, 2]^".

In the following sections of this paper a new approach - tabular

format - is adopted in presenting information on the specimen, measurements, system characteristics, results, and errors.

The reasons for adopting this format are: (1) to facilitate the

preparation of manuscripts, (2) to standardize the contents of the

papers on measurements using the present or similar systems in other

laboratories, (3) to facilitate information retrieval by the reader,

(4) to provide a means for efficient and accurate identification,

Figures in brackets indicate the literature references at the end

of this paper.

31
TABLE 1

Specimen information

No. Item Unit Explanation

ii Subs tance

:

Vr a 0 da t urn ^po iy cryb Lai line )

Z * Source Materials ttesearcn corporation

3 Purity 99 . 9 %

4 Impurities Listed in table la

5 Geomet ry Tube made from rod by electro-erosion

6 Dimensions

total length mm /O . ZD

•k-k effective length mm 25.53

outside diameter mm 6.3

wall thickness mm 0.5

blackbody hole mm 0.5 x 1

7 Weight

total weight oe 4.319

"kit effective weight g 1.438

8 Characteristics

^ 1" nmi p up i oVi t- density

-3

g-cm 6.1

resistivity at 293 K

10" 8Q-m 21.72

9 Special treatment Heat treated by pulse heating before

the experiments - 30 pulses to 1900 K

*The supplier is identified in this paper in order to adequately characterize the

specimen - Such an identification does not imply recommendation or endorsement

by the National Bureau of Standards. **Effective refers to the portion of the specimen between the voltage probes.

32
coding, characterization and data reduction by scientific and

J technical information centers, and (5) to ultimately lead to the

computerized preparation of papers.

2. Measurements

The details regarding the vanadium specimen used in the present

measurements are given in table 1. A summary of the measurement

technique and the operational characteristics of the system is given

in table 2. The polynomial functions (obtained by the least squares

method) that represent the experimental results are given in table 3.

The final values on properties at 100 degree temperature intervals

computed using the functions are given in table 4. The experimental

results are presented in the Appendix. Each number tabulated in

the Appendix represents results from over fifty original data points.

An estimate of errors in the measured and computed quantities is given

in table 5. All values reported in this paper are based on the

International Practical Temperature Scale of 1968 [3]. In all

computations, the geometrical quantities are based on their room

temperature (298 K) dimensions.

Table la

Element C Fe Nb N 0 P

ppm 120 20 60 10 15 15

Element Si Ta Ti W Zr

ppm 50 70 10 30 15

aThe total amount of all other detected elements is less than

50 ppm, each element being below 10 ppm limit.

33
TABLE 2

Measurement technique and system characteristics

No. I tern Unit Explanation and Data

1 General technique

2 ; Voltage measurement

3 Current measurement

i

4

j Temperature measurement

5 Specimen environment

6 Power source

Recording

Signal resolution

9 Time resolution

Data processing

Date of measurements

12 Number of experiments

13

J Temperature range

14 | Temperature subranges

Experiment duration

16 Current pulse length

17 Imparted power

18 Current

I 19 i Rate of current change

20 | Heating rate

21 Cooling rate

22 Radiative heat loss

1 (7o of input power)

ms

K

K

ms

msW

A

A-ms

1

K-ms

K-ms

-1

-1

Pulse heating (subsecond) [1, 2]

Across tungsten knife-edge probes

Across standard resistor (0.001 Q)

in series with the specimen

High-speed photoelectric pyrometer [4]

Vacuum 1.3 x 10" 3 N-m"

2

(- 10 torr)

Battery bank (14 series-connected

2V batteries, capacity 1100 Ah each)

Digital data acquisition system ~ 0.01% (at full scale)

0.4

Time -sharing computer

August 1973

4

1500 - 2100

I (1480 - 1710)

II (1690 - 1890)

III (1810 - 2050)

IV (2000 - 2130)

600 - 620

400 - 420

4000 - 5200

1300 - 1600

0.3 - 0.6

3.9 - 4.5

0.04 - 0.15

1% at 1500 K

47o at 2100 K

34
TABLE 3

Functional representation of results on va-O&ci Lum

Heat capacity (J-mol "*"K _)

-8, Resistivity (10 Q-m) Hemispherical total emittance

c = A + BT + CT

P

\ = 56.34

B = -3.839 x 10

C = 1.563 x 10" 5

1500 K < T < 2100 K

* = 1.1%

o = A + BT + CT

A = 8.794

B = 6.282 x 10" 2

C = -6.804 x 10" 6

1500 K < T < 2100 K

CT = 0.06%

e = A + BT

A = -5.413 x

10"'

B = 1.930 x 10

1880 K < T < 2050 K

a* = 0.05%

Standard deviation of an "individual point'

TABLE 4

Results on properties of N/3, na ol iurn

T

(K)

cp

(J -mol

p (10~*

e

1500 33 .92 87 72

1600 34 .93 91 89

1700 36 .25 95 92

1800 37 .88 99 83

1900 39 .82 103 59 0.313

2000 42 08 107 22 0.332

2100 44 .65 110 71

35
TABLE 5

Error analysis (at 2000 K)

Quantity Imprecision **

Inaccuracy

Temperature 0.5 K 4 K

Voltage 0 . 037. 0.17.

Current u . UJ7. U.J./.

Heat capacity 17. 37.

Electrical resistivity 0.17. 0.57.

Hemispherical total

emi ttance 0.17. 57.

Imprecision refers to the standard deviation of an individual

point as computed from the difference between measured value and

that from the smooth function obtained by the least squares method.

*Inaccuracy refers to the estimated total error (random and systematic).

36
3. Discussion

The heat capacity, electrical resistivity and hemispherical total

emittance of vanadium measured in this work are presented and compared

graphically with those reported in the literature in figures 1, 2 and

3, respectively.

The heat capacity results of this work are approximately 6-8%

lower than those of Jaeger and Veenstra [5] and Fieldhouse and Lang [6],

and are approximately 8% higher than those of Peletskii et al. [7]

over the respective overlapping regions. The results reported in the

literature were for temperatures below 1900 K. In this work, the

measurements are extended to 2100 K, which is approximately 90 K below

the melting point of vanadium.

The electrical resistivity results are in reasonably good agreement

(maximum differences about 270 ) with those reported by Horz et al. [8]

and Peletskii et al. [71. At 293 K, the electrical resistivity of this

-8

work is approximately 37o higher than the value (21.02 x 10 Q-m)

reported by Peletskii et al. [7]. In the range of the present measurements,

vanadium showed a negative departure from linearity in the temperature

dependence of electrical resistivity. A similar behavior was previously

noted for niobium [9] and tantalum [10], which belong to the same group

(V) on the periodic table.

Considerable differences in hemispherical total emittance results

of various investigators may be expected due to the differences in

specimen surface conditions. The difference between the present results

and the extrapolated values of Horz et al. [8] is approximately 6%.

37
45

T 40

£ 35

i±j

x

3%

JAEGER (1934)

FIELDHOUSE (I960

PELETSKII (1971)

PRESENT WORK

30 1 i

1200 1600

TEMPERATURE, K

2000

FIGURE 1. Heat capacity of vanadium as reported in the literature,

38
T

39
o

o

o

OJ

o

o

CO

o

o

CM

in

ro

O

ro

a

in

OJ

a

o

o* o

§

ct: yj

0L

0)

4J

CQ

1-4 0)

OJ

C

•H

0) U

u

oa

a)u

CO

cd a

•a

coc

cfl >

o

a)o

a

as •U

O

c0O

•H

J-l a;a,

COe

EC

OH

3DN\/±±IW3 "1V101 lV0IU3HdSllfl3H

40
As was the case with the earlier results on other refractory metals [2,

9, 10, 11] obtained with the present measurement system, heat capacity

of vanadium at high temperatures is considerably higher than the

Dulong and Petit value of 3R. Some of this departure is due to

c -c and the electronic terms. However, they do not account for

P v

the entire difference. Heat capacity above the Debye temperature

may be expressed by

c„ = A-^+CT+bc

-1 -1 -2

where the constant term is 3R (24.943 J.mol »K ), the term in T

is the first term in the expansion of the Debye function, the term

in T represents C p~c

v and electronic contributions, and the quantity

Ac represents excess in measured heat capacity at high temperatures,

which is not accounted for by the first three terms. The coefficients

5 -3

B (1.50 x 10 ) and C (4.86 x 10 ) were obtained from heat capacity

values at 270 K [12, 13] and at 1000 K. The value at 1000 K was

estimated based on the extrapolation of the present work results

and the low temperature results reported in the literature [12, 13].

Using the above equation and the heat capacity results of this

work, the quantity Ac was computed for temperatures above 1500 K.

The results for Ac in J.mol'^K

-1

are: 1.8 at 1500 K, 4.2 at 1800 K,

and 9.5 at 2100 K.

41
Although the mechanisms of vacancy generation become important

at high temperatures, it was not possible to attribute the high heat

capacity values entirely to vacancies. To demonstrate this, a crude

estimate of the contribution of vacancies to heat capacity was made

using the method described in a previous publication [2], The results

indicate that vacancy contribution would be small, approximately

0.03 J-mol'^K

-1

at 1500 K and 0.5 J-mol~»K~

1 at 2100 K, and would not

account for the high heat capacity values. If the entire difference

between measured and computed (using the first three terms in the

above equation) heat capacities is attributed to vacancies, values of

1.1 eV for vacancy formation energy and 3.87o for vacancy concentration

at the melting point are obtained. Both of these values, especially

the concentration, seem to be unrealistic for vanadium.

The new format adopted in this paper has demonstrated the

feasibility of concise yet complete and systematic documentation

of measurements performed with the present system. For reasons

enumerated in the Introduction, it is hoped that the approach of

a standardized quasi -tabular presentation will find wide acceptance

among the experimenters in the same and related fields.

Acknowledgement

The authors express their gratitude to C. W. Beckett for his

encouragement of research in high-speed thermophysical measurements

and to M. S. Morse for his help with the electronic instrumentation.

42
4. Appendix

TABLE A-l

Experimental results on heat capacity and electrical resistivity of vanadium

Temperature

(K) (J mol^K )

* AC

p

(%)

p (10"8

n-m)

* AP

(%)

1500 33.48 - 1.32 87.66 0.06

1550 34.50 + 0.33 89.81 0.01

1600 35.32 + 1.10 91.93 + 0.05

1650 35.88 > + 0.92 94.03 + 0.12

1700 35.81 - 1.23 95.83 - 0.09

1750 37.20 + 0.46 97.86 - 0.03

1800 38.26 + 0.99 99.87 + 0.05

1850 38.61 - 0.53 101.69 0.03

1900 39.71 - 0.30 103.56 0.02

1950 40.80 - 0.29 105.40 0.02

2000 41.96 - 0.30 107.20 0.01

2050 42.72 - 1.43 109.01 + 0.03

2100 45.34 + 1.51 110.70 0.00

The quantities ACp and Ap are percentage deviations of the individual

results from the smooth functions represented by the pertinent equations

in table 3.

43
TABLE A-2

Experimental results on hemispherical total emittance of vanadium

Temperature

(K)

e * Ae

a)

Temperature

(K)

e * Ae

(%)

1874.5 0.307 0. 12 2022.6 0.336 0.06

1878.4 0.308 0.03 2028.0 0.337 0.02

1882 .4 U . JU9 + 0.03 ftU . J

^ JOi a + 0.01

1886.4 0.310 + 0.06 2038.9 0.339 + 0.02

1890.5 0.311 + 0.06 2044.5 0.341 + 0.02

1894.7 0.312 + 0.03 2050.1 0.342 + 0.01

*The quantity Ae is percentage deviation of the individual results from

the smooth function represented by the pertinent equation in table 3.

44
5. References

Cezairliyan, A., Design and operational characteristics of

a high-speed (millisecond) system for the measurement of

thermophysical properties at high temperatures. J. Res. Nat.

Bur. Stand. (U. S.) 75C (Eng. and Instr.), 7 (1971).

Cezairliyan, A., Morse, M. S., Berman, H. A., and Beckett,

C. W., High-speed (subsecond) measurement of heat capacity,

electrical resistivity, and thermal radiation properties of

molybdenum in the range 1900 to 2800 K. J. Res. Nat. Bur.

Stand. (U. S.) 74A (Phys . and Chem.), 65 (1970).

International Practical Temperature Scale of 1968. Metrologia

5, 35 (1969).

Foley, G. M., High-speed optical pyrometer, Rev. Sci. Instr.

41, 827 (1970).

Jaeger, F. M., and Veenstra, W. A., The exact measurement of

the specific heats of solid substances at high temperatures.

The specific heats of vanadium, niobium, tantalum and

molybdenum. Rec . Trav. Chim. 53_, 677 (1934).

Fieldhouse, I. B., and Lang, J. I., Measurement of thermal

properties. Report WADD TR 60-904 (1961).

Peletskii, V. E., Druzhinin, V. P., and Sobel', Ya. G .

,

Thermophysical properties of vanadium at high temperatures.

High Temp. - High Press. 3, 153 (1971).

45
[81 Horz, G., Gebhardt, E., and Durrschnabel, W., Emissionvermogen und elektrischer widerstand von vanadium, vanadiumstickstoff- und vanadium-sauersto^- mischkristallen. Z.

Metallkunde 56^ 554 (1965).

[9] Cezairliyan, A., High-speed (subsecond) measurement of heat

capacity, electrical resistivity, and thermal radiation

properties of niobium in the range 1500 to 2700 K. J. Res.

Nat. Bur. Stand. (U . S.) 75A (Phys . and Chem.), 565 (1971).

[101 Cezairliyan, A., McClure, J. L., and Beckett, C. W., Highspeed (subsecond) measurement of heat capacity, electrical

resistivity, and thermal radiation properties of tantalum

in the range 1900 to 3200 K, J. Res. Nat. Bur. Stand. (U. S.)

75A (Phys. and Chem.), 1 (1971).

[Ill Cezairliyan, A., and McClure, J. L. , "High-speed (subsecond)

measurement of heat capacity, electrical resistivity, and

thermal radiation properties of tungsten in the range 2000

to 3600 K" , J. Res. Nat. Bur. Stand. (U. S.) 75A (Phys. and

Chem.), 283 (1971).

[121 Bieganski, Z., and Stalinski, B., Heat capacities and thermodynamic functions of vanadium and vanadium hydride within the

range 24 to 340 K. The hydrogen contribution to the heat

capacity of transition metal hydrides. Bull. Acad. Polon.

Sci. Ser. Sci. Chim. 9, 367 (1961).

[131 Anderson, C. T., The heat capacities of vanadium, vanadium

trioxide, vanadium tetroxide and vanadium pentoxide at low

temperatures. J. Am. Chem. Soc. 5_8, 564 (1936).

46
Chapter 3

SIMULTANEOUS MEASUREMENTS OF HEAT CAPACITY,

ELECTRICAL RESISTIVITY AND HEMISPHERICAL TOTAL

EMITTANCE BY A PULSE HEATING TECHNIQUE:

ZIRCONIUM, 1500 TO 2100 K*

A. Cezairllyan and F. Righini

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

Abstract

Simultaneous measurements of heat capacity, electrical

resistivity and hemispherical total emittance of zirconium in

the temperature range 1500 to 2100 K by a subsecond duration, pulse

heating technique are described. The results are expressed by

the relations:

C = 36.65 - 1.435 x 10

-2

T + 6.624 x 10" 6

T

2 P

o = 87.95 + 1.946 x 10" 2 T

e = 0.2031 + 6.362 x 10" 5

T

where C

p

is in J.mol" 1

- K~* , o is in 10" 8 n -m, and T is in K.

Estimated inaccuracies of the measured properties are: 3% for heat

capacity, 2% for electrical resistivity and 5% for hemispherical total

emi ttance

.

This work was supported in part by the U. S. Air Force Office

of Scientific Research.

Guest scientist from the Istituto di Metrologia "G. Colonnetti"

in Torino, under a fellowship from the Consiglio Nazionale delle

Ricerche of Italy.

47
I

L. Introduction

In this paper, application of a pulse heating technique to

the simultaneous measurements of heat capacity, electrical

resistivity and hemispherical total emittance of zirconium

in the temperature range 1500 to 2100 K is described.

The method is based on rapid resistive self-heating of

the specimen from room temperature to high temperatures (above

1500 K) in less than one second by the passage of an electrical

current pulse through it; and on measuring, with millisecond

resolution, such experimental quantities as current through the

specimen, potential drop across the specimen, and specimen temperature. Details regarding the construction and operation of the

measurement system, the methods of measuring experimental quantities,

and other pertinent information, such as the formulation of relations

for properties, error analysis, etc. are given in earlier

publications [ 1, 2]^.

In the following sections of this paper a tabular format is

adopted in presenting information on the specimen, measurements,

system characteristics, results and errors.

''"Figures in brackets indicate the literature references at the

end of this paper.

48
i TABLE 1

Specimen information

No. I tern Unit Explanation

1 Substance Zirconium ( po ly cry s ta 1 1 ine

)

2 * Source Materials Research Corporation

3 Purity 99 .98%

4 Impurities Listed in table la

5 Geometry Tube made from rod by electro-erosion

6 Dimensions (nominal)

total length mm 76 .2

-k-k effective length mm 25 .4 outside diameter mm 6 .3

wall thickness mm 0 .5 blackbody hole mm 0 .5 x 1 (rectangular)

7 Weight

total weight g 4 .312

effective weight g 1 .425

8 Characteris tics

atomic weight [ 4

1

91 .22

k-k-k density g.cm" 3

6 .53

resistivity at 293 K 10 _8Q-m 42 .8

The supplier is identified in this paper in order to adequately characterize the

specimen - Such an identification does not imply recommendation or endorsement

by the National Bureau of Standards.

k-k Effective refers to the portion of the specimen between the voltage probes.

k-k-kValue measured in the present work.

49
Measurements

The details regarding the zirconium specimens used in the

present measurements are given in table 1. A summary of the

measurement technique and the operational characteristics of the

system is given in table 2. The polynomial functions (obtained by

the least squares method) that represent the experimental results

are given in table 3. The values of properties at 100 degree

temperature intervals computed using the functions are given in

table 4. The experimental results are presented in the Appendix.

Each number tabulated in the Appendix represents results from over

fifty original data points. An estimate of errors in the measured

and computed quantities is given in table 5. All values reported

in this paper are based on the International Practical Temperature

Scale of 1968 [3] . In all computations, the geometrical quantities

are based on their room temperature (298 K) dimensions.

Table la

Impurities in the specimen

(according to the manufacturer's analysis)

Element c H

I 0 i N Al Fe Hf Ni Si Ti

ppm 6 3.3 125

r 1 2.1 3 30 40 1.5 1.5 1

V The total amount of all other detected elements is less than 6 ppm,

each element being below 1 ppm limit.

50
TABLE 2

Measurement technique and system characteristics

No. I tern Unit Explanation and Data

1 General technique Pulse heating (subsecond)

2 Voltage measurement Across tungsten knife-edge probes

3 Current measurement Across standard resistor (0.001 Cl) in series with the specimen

4

5

Temperature measurement

Specimen environment

High-speed photoelectric pyrometer[5]

Vacuum ~1. 3 x 10 J N-m (~10 _:> torr)

6 Power source Battery bank

2V batteries

(14 series -connected

, capacity 1100 A*h each)

7 Recording Digital data acquisition system

8 Signal resolution ~ 0. 01% (at full scale)

9 Time resolution ms 0.4

10 Data processing Time -sharing computer

11 Number of specimens 3

12 Number of experiments 12

13 Temperature range K 1500 - 2100

14 Temperature subranges K I II

III

IV

(1450 - (1680 - (1810 - (1840 -

1680)

1900)

2050)

2110)

15 Experiment duration ms 550 - 680

16 Current pulse length ms 350 - 480

17 Imparted power W 1700 - 3100

18 Current A 730 - 840

19 Rate of current change A

-1

• ms 0.08 - 0.13

20 Heating rate K

-1

•ms -1

• ms

2.9 - 4.8

21 Cooling rate K 0.08 - 0.3

22 Radiative heat loss

(% of input power)

2% at

10% at

1500 K

2100 K

If

I

51
TABLE 3

Functional representation of results on zirconium

Heat capacity (J-mol .^K ^)

-8

Resistivity (10 Q-m) Hemispherical total emittanrp

2 C = a + bT + cT

P

p = a + bT e = a + bT

a = 36.65 a = 87.95 a = 0.2031

b = -1.435 x 10" 2 b = 1.946 x 10" 2 b = 6.362 x 10" 5

c = 6.624 x 10" 6

1500 K < T < 2100 K 1500 K < T < 2100 K 1650 K < T < 2050 K

a* = 0.7% a* = 0.6% a* = 0.9%

Standard deviation as computed from the difference between the value of an experimental result (as tabulated in the Appendix) and that from the smooth

functions reported above.

TABLE 4

Results on properties of zirconium

T c

p

P e (K) (J-mol"

1

.

K

_1

) (10"8

Q. m)

1500 30.03 117.14 0.299*

1600 30.65 119.09 0.305*

1700 31.40 121.03 0.311

1800 32.28 122.98 0.318

1900 33.30 124.92 0.324

2000 34.45 126.87 0.330

2100 35.73 128.82 0.33 7*

•k Extrapolated values

52
TABLE 5

Error analysis (at 2000 K)

Quanti ty Imprecision

•k-k Inaccuracy

Temperature 0.5 K 4 K

Voltage 0.03% 0 . 1%

Current 0.03% 0 . 1%

Heat capacity 0 . 77 370

Electrical resistivity 0 . 67 27

Hemispherical total

emi ttance 0 . 97 57

Imprecision refers to the standard deviation of a quantity as computed from the difference between the value of the quantity

and that from the smooth function obtained by the least

squares method. The quantities in the case of temperature,

voltage, and current are the individual points measured in a single experiment, and in the case of heat capacity, electrical

resistivity, and hemispherical total emittance are the results

from all experiments as tabulated in the Appendix.

**Inaccuracy refers to the estimated total error (random and

systematic)

.

53
3. Discussion

The differences in the measured properties for the three specimens

were within the measurement resolution for the properties, and the final

smoothed results (represented by the equations in Table 3 and tabulations

in Table 4) were obtained from the combined data for the three specimens.

The heat capacity, electrical resistivity and hemispherical total

emittance of zirconium measured in this work are presented and compared

graphically with those reported in the literature in figures I, 2 and

3, respectively. The present results are for temperatures up to 2100 K,

which is approximately 30 K below the melting point of zirconium.

The heat capacity results of this work are approximately 1% lower

than those of Skinner [6] in the overlapping temperature region.

Extrapolation of the results of this work to lower temperatures (1200-

1400 K) yields values which are 3-670 lower than those reported by

Coughlin and King [7]. However, too much significance should not be

attached to the latter since: (a) the comparison is based on an

extrapolation of 100-300 K and (b) the constant heat capacity reported

by Coughlin and King [7] is not realistic.

The electrical resistivity results are in reasonably good, agreement

(maximum difference less than 1%) with those of Zhorov [8], and are

approximately 2-47Q lower than those of Peletskii et al. [9] in the

overlapping temperature regions.

54
Zirconium undergoes a solid-solid phase transformation around

1150 K. The measurements of the geometrical quantities of the specimen

after a number of experiments indicated permanent distortions (elongation)

due to repeated heating and cooling through the transformation point.

The reported electrical resistivity results are corrected for the

permanent geometrical changes . The magnitude of this correction was

-8

about 1%. At 293 K, the average electrical resistivity (42.8 x 10 Q-m)

of the three specimens used in this work is within 3.57» of the values

-8

reported in the literature by Adenstedt [10] (44.1 x 10 fi-m) and by Powell

-8 -8

and Tye [11] (42.2 x 10 Q-m and 44.3 x 10 Q*m). Some of the differences

in the electrical resistivity values may be due to differences in

the chemical composition of the specimens.

The hemispherical total emittance values reported in this work

are higher (10-25%) than those reported by Timrot and Peletskii [12],

Peletskii et al. [9] and Zhorov [8]. Considerable differences in

hemispherical total emittance results of various investigators may be

due to differences in specimen surface conditions. Changes in the specimen'

surface conditions were noticed during this work, with the initial

smooth polished surface changing to an uneven rough surface as the result

of repeated heating and cooling through the transformation point. This

may partially account for the high emittance values.

Acknow ledgement

The authors express their gratitude to C. W. Beckett for his

encouragement of research in high-speed thermophysical measurements and

to M. S. Morse for his help with the electronic instrumentation.

55

57
58
CM o m CO oo O CM cm o CM o CM co CO O O o CM O o o O o + + + 1 + + + +

!* f i < o CO

m o ON oo o CO CM VO CM o CO o o o o o o o o 1 + + 1 1 1 1 a

ON r-f O O

a

CDd

0)a

CD x;

-O

a. .-< cs

•iHOa

to

vo o O r-4 O i-H + +

VO

in »-< o+

hoa

"S

CDO

X!

TABLE A -3

Experimental results on hemispherical total emittance of zirconium

specimen-1

i— ' " specimen- 2

Temperature r/

* Temperature

v *w

e * Ae

(%)

1674.7 0.307

1

1 0.87 1650.5 0.301 - 2.37

1680.1 0.309 0.33 1655.5 0.304

1685.7 0.310 0.12 1660.7 0.307 - 0.58

1691.4 0.312 + 0.40 1666.0 0.310 + 0.28

1697.1 0.313 + 0.61 1671.4 0.312 + 0.81

1703.0 0.314 + 0.80 1676.9 0.315 + 1.65

1848.8 0.320 m 0.24 1980.7 0.326 - 0.96

1856.9 0.322 + 0.23 1991.0 0.327 - 0.86

1865.3 0.324 + 0.68 2001.6

1 0.328 - 0.75

1873.7 0.325 + 0.82 2012.3 0.329 - 0.65

1882.4 0,327 + 1.26 2023.3 0.329 - 0.87

1891.3 0.328

; + 1.39 2034.5 0.330 - 0.78

2003.3 0.330 0.18 . " i 2014.3 0.332 + 0.22

i

2025.6 0.333 + 0.30

!

1

I 2037.1 0.334 + 0.38

2048.9 0.335 + 0.45

2061.0 0.336 + 0.52

The quantity Ae is percentage deviation of the individual results from

the smooth function represented by the pertinent equation in table 3.

61
1 5. References

[1] Cezairliyan, A., Design and operational characteristics

of a high-speed (millisecond) system for the measurement

of thermophysical properties at high temperatures. J.

Res. Nat. Bur. Stand. (U. S.) 75C (Eng. and Instr.), 7

(1971).

[21 Cezairliyan, A., Morse, M. S., Berman, H. A., and Beckett,

C. W., High-speed (subsecond) measurement of heat capacity,

electrical resistivity, and thermal radiation properties

of molybdenum in the range 1900 to 2800 K. J. Res. Nat.

Bur. Stand. (U.S.) 74A (Phys. and Chem.), 65 (1970).

[31 International Practical Temperature Scale of 1968.

Metrologia 5, 35 (1969)

.

[41 IUPAC Commission on Atomic Weights, Atomic Weights of the

elements 1969. Pure Appl. Chem. 2J., 91 (1970).

[51 Foley, G. M., High-speed optical pyrometer, Rev. Sci. Instr.

41, 827 (1970).

[61 Skinner, G. B., Thermodynamic and structural properties of

zirconium. Ph.D. Thesis, Ohio State University, 1951.

[71 Coughlin, J. P., and King, E. G., High-temperature heat

contents of some zirconium-containing substances. J. Am.

Chem. Soc. 72, 2262 (1950).

62
[8] Zhorov, G. A., Emissivity of metals of the TS b subgroup

at high temperatures. High Temp. 8, 501 (1970).

[9] Peletskii, V. E . , Druzhinin, V. P., and Sobol', Ya . G.,

Emissivity, thermal conductivity, and electrical

conductivity of remelted zirconium at high temperatures.

High Temp. 8, 732 (1970)

.

[10] Adenstedt, H. K., Physical, thermal and electrical properties

of hafnium and high purity zirconium. Trans. A.S.M. 44 ,

949 (1952).

[11] Powell, R. W., and Tye, R. P., The thermal and electrical

conductivities of zirconium and of some zirconium alloys.

J. Less-Common Metals 3, 202 (1961).

[12] Timrot, D. L. , and Peletskii, V. E., The thermal conductivity

and integral blackness of zirconium. High Temp. 3_, 199 (1965).

63
Chapter 4

MEASUREMENT OF MELTING POINT, RADIANCE TEMPERATURE

(AT MELTING POINT), AND ELECTRICAL RESISTIVITY

(ABOVE 2100 K) OF ZIRCONIUM BY A PULSE

I HEATING METHOD*

A. Cezairliyan and F. Righini

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

Abst ract

A subsecond duration pulse heating method is used to measure the

melting point, radiance temperature (at 650 nm) at the melting point,

and electrical resistivity (above 2100 K) of zirconium. The results

yield a value of 2128 K for the melting point on the International

Practical Temperature Scale of 1968. The radiance temperature (at

650 nm) of zirconium at its melting point is 1940 K, and the corresponding

normal spectral emittance is 0.367. At 2100 K electrical resistivity

-8

is 128.7 x 10 Cl-m. Estimated inaccuracy is: 8 K in the melting point

and in the radiance temperature ,^3% in the normal spectral emittance and

in the electrical resistivity.

7"

This work was supported in part by the U. S. Air Force Office of

Scientific Research.

**Guest scientist from the Istituto di Metrologia "G . Colonnetti" in

Torino, under a fellowship from the Consiglio Nazionale delle Ricerche of Italy,

64
1 . Int roduc ti on

A millisecond resolution pulse heating technique was developed

earlier in connection with the measurement of selected thermophysical

properties of electrical conductors at high temperatures [1]. This

technique was also applied to the measurement of the melting point of

molybdenum [2], tungsten [3] and niobium [41, and the radiance temperature (at 650 nm) of niobium at its melting point [5].

In the present study, the same technique is used for the measurement of the melting point, radiance temperature at the melting point,

and electrical resistivity (above 2100 K) of zirconium.

The method is based on rapid resistive self-heating of the

specimen from room temperature to high temperatures (above 1500 K) in

less than one second by the passage of an electrical current pulse

through it; and on measuring, with millisecond resolution, such

experimental quantities as current through the specimen, potential drop

across the specimen, and specimen temperature. Temperature is measured

with a high-speed photoelectric pyrometer [6], which permits 1200

evaluations of specimen temperature per second. Details regarding the

construction and operation of the measurement system, the methods of

measuring experimental quantities, and other pertinent information, such

as the formulation of relations for properties, error analysis, etc.

are given in earlier publications [ 1, 7].

65
2. Measurements

Measurements were performed on zirconium specimens in the form

of tubes and strips, all of the same grade and obtained from the same

manufacturer. The specimens were 99.9$7o pure and manufacturer's typical

analysis indicated the presence of the following impurities in ppm by

weight: 0, 125; Hf, 40; Fe, 30; C, 6; H, 3.3; Al, 3; N, 2.1; Ni, Si,

1.5 each; and Ti, 1. The total amount of all other detected elements

was less than 6 ppm, each element being below 1 ppm limit.

Melting point and electrical resistivity measurements were performed

on three zirconium specimens in the form of tubes, designated as

specimen-I, II and III. The nominal dimensions of the tubes were:

length, 76.2 mm; outside diameter, 6.3 mm and thickness, 0.25 mm. A

small rectangular hole (0.5 x 1 mm) fabricated in the wall at the

middle of the specimen approximated blackbody conditions for temperature

measurements

.

The radiance temperature measurements at the melting point were

performed on thirteen zirconium specimens in the form of strips. The

nominal dimensions of the strips were: length, 50.8 mm; width, A . 7 mm

and thickness, 0.24 mm. The thin oxide coating present on the specimens

(strip) in the "as received" condition was removed using AbrdS iV2 . Four

different grades of Abrasive, were used yielding four different surface

roughnesses (ranging from 0.23 Mm to 0.95 \Jxa) for different specimens.

66
All the experiments, with one exception, were performed with the

-3 -2

specimen in a vacuum environment of approximately 1.3 x 10 N-m

(~ 10 torr), and in one case the specimen was in an argon environment

at atmospheric pressure. The heating rate for the tubular specimens

was approximately 3000 K-s ^ which corresponds to a specimen heating

period (from room temperature to melting point) of approximately 600

ms. The heating rate for the strips varied from 400 K-s * to 3200 K«s ,

and the corresponding heating periods changed from 1200 ms to 280 ms

.

The magnitude of the current pulses near the melting point was about

750 A in the case of tubular specimens and ranged from 40A to 300A

for the 9trips.

The high-speed pyrometer and the neutral density filters used

for its operation at different ranges were calibrated before and after

the entire set of experiments, using a tungsten filament standard lamp,

a ii which in turn was calibrated against the NBS Temperature Standard.

All temperatures reported in this paper, except where explicit^,

noted, are based on the International Practical Temperature Scale of

1968 [8].

3. Experimental results

3.1. Melting point

Temperature of the tubular specimens was measured near and during

the initial melting period, until the specimen collapsed. Typical

results for the variation of the specimen temperature as a function of

time (for specimen I) are shown in figure 1. The plateau in temperature

indicates the region of solid and liquid equilibrium. The complete results

67
c

<uE

•wu

<ua

CO

01u

9«

«a

E

CD U

y-io

Co

(0 >

4)

00

•ft

0a

60c

•rl

01£

41

M

a)C

0

c

0

•H

JJ0

c

3

x 'luniviiidwii

CM

68
Table 1

Experimental results of the melting point of tubular zirconium specimens

Specimen

number

Number of temperatures at plateau

Melting point

/rr\

( K)

Standard deviation

I 73 2127.3 0.4

II 20 2127.5 0.4

III 28 2127.8 0.6

69
for the three tubular airconium specimens are presented in table 1. The value of the melting point was obtained by averaging temperature

points on the plateau of a given specimen. The duration of the

plateau for specimens II and III was shorter than that of specimen I.

This may be attributed to an early collapse of these specimens. To

determine the trend of measured temperatures at the plateau, temperatures

for specimen I were fitted to a linear function in time using the least

squares method. The slope of the linear function was 4.7 K-s"

1

, which

corresponds to a maximum temperature difference of less than 0.3 K between

the begining and the end of the plateau. This procedure gave a standard

deviation of 0.4 K, the same as that obtained by averaging the temperatures.

Values of the same order of magnitude were found for specimens II and III.

The average melting point of the three specimens is 2127.5 K with an

from tto. rne^-n

average aksofatc. deviation of 0.3 K. It may be concluded that the

A

melting point of zirconium measured in this work is 2128 K.

3.2. Radiance temperature at the melting point

Radiance temperature measurements were performed on strips at 650 nm

which corresponds to the effective wavelength of the pyrometer's interference filter. The bandwidth of the filter was 10 nm. The circular

area viewed by the pyrometer was 0.2 mm in diameter.

Radiance temperature of zirconium at its melting point for the

thirteen experiments (corresponding to thirteen specimens) and other

pertinent results are reported in table 2. The variation of radiance

temperature as a function of time near and at the melting point is

shown in figure 2 for three typical experiments representing three

70
1945 1 1 1 1 1 r-1940.4 2 K

i

1940 • •

•

•

•

-

1935 •

•

•

•

•

• SPECIMEN -

i i .. -i

9

1

LU

cc

<

cc

1945

1940

C_3

<

<

CC

1935 -

1940.7

2 K]

0

Figure 2

••••

SPECIMEN - 3

1945

1

•

1 1 1 1 1

2 K

•

1

•

• /—1940.0

• • /

1940

•

•

•

•j.

• SPECIMEN - 7

1935

•

• L J_ _l_ _l_ _L. ,1. 40 80 120

TIME, ARBITRARY UNIT

Variation of radiance temperature (at 650 ran) of

zirconium as a function of time near and at its melting

point for three typical experiments (1 time unit =

0.833 ms).

71
X)o

•H aoo u 8 oi & 01 o

CL 4J

C

01 oo s u c at oi •H 0) 1-1 u 4J M-l

r-l Cd -H

CJ i-i xi £ ix

r4 x> c u o

co fl

73 4J C id

nj •H

4J >

cn de

1)

01 ^ O 3 B u „ co cd •H M W

cd o.

a;

B « 3 ^ nj «—<

0> 01 I Cu 4J CO O id • r-< r-l M

c/j O.

1j cd 01 Li j o> e o. 3 S

55 01

XJ

TJ

C P O

Cd -H 13 4J C cd

Cd -r-4 u >

en oi XI C CO •H • 4-> cd w

o> EE

0) to o cu cd c

c-i .£ M 00 3 3

CO o C cd

CU !- E 0)

•r-l .0 0 B

01

a

a c o o o

it

0> o

St o3 o

cr.

©

l-l .<t o d

1-4 u~l o o o

CIO o oo oo oo oo

u-i oo oo

<t * 0 0 cd

41 o 01 OJ

4-1 cti j=4J

CD 4J .c cd XI c a c s 3 cd E . o CO <4_l >•> •l-l CO H 00

,c (10 41 CU u-i td c 1 o c •H •H 3 *D CD

cu 3 C 4-1 <D ^ c "4-J c «/l cd *j td t4 •H ?

cd oc CU & S!

4-1 <s <u c 4-

x> 0) •Q 01 § o w o in

4) >

*J

—R c i 0 4J 11 QJ •H cd 3 O

4J

C 4J

C

r

u o <u cd cd

H 4J c 4J CD u i-i 0 cd 3 3

01 "O 4-> U-l 3 4J CL cd 2 u

cd CD

B

4) cu & 4) CD "O B 4J 4-1 "O p- G

f-i cd <u CD £ cd

4-J T3

u tJ

M 0)

a 0 c cd

D 4-» 4)

VI ,e il) 01 CO 9 3 cu 4J tu c cd r—i i—1

Ul CU CD 'H cd cd

l-i AJ

B 1-C

p

•n >

'4-1 > 4-1 W H 01

CO 01 •o -C o

4) l-l 4J

Li cd cd CD 3 4J 3 c c C

w

-u to cr o 4> •f-i cd

ra X) CO 4J 6 u cd •a i-i s s

01 01 4-1 «u CU o to o. l-i CO cu CO tt) <D s 3 cd D<, cd Cl M-l 9 (J 4) I

J3 0)

O 4J UJ 4J CO 1—1

cu

M

u 4-> 3 cd c c .3

41 41 41 cd

O 4) JC a. .c CD 01 M CD CO

4-1 e 4-1 o 4J o 4-> 5

41 c cd "M Cd 4J

U-4 4J 00 I

a. 1 •H CD 0 e o41 •H *o cy

g

41 & CO cd 01 'D CD > u 3 M J= cd O

•r-l 4J

m • 41

4-1 00 01 OJ 3 2

CJ

CO c 8 i

M-l > cd Cd

H P > •H 0 cd cu *0 CD cd •H 4-1 4-1 4-1 c •H

4-1 •o CD cd cd ^ -o

De •H

<4-( in

J

en in pi 4J >H nj

Ij

owinj in

ON

the

i-j ?

i-i o o

fo o

bel

OJ

a 4J

an o 0 i-i 4J

01 >N

T3 T3 in 1-1 C CU O od o 4-1

CO td cu

d •r4 o I-I M o

00

O CX) 1-4 o o n CL

1—4 CL 0 CO o cd c C 0 o 01

I-I •H ca" I-I J3 4J 3

CJ •H 4J T3 ro cd C c CM I-I *H o 01 o O CL

CO 4J 01

g

C o < 4J

4) cd B 14-1 cd •H I-I IJ 3 I

4J

01 CO cd aX u C XI

CU fo •H 41 4J

01 to cd J3 •o CU 3

4J 41 CO

CO CO cd tS 3 ne >

<u c CO j= 4J

01

a t>0 01 c

to o 3 4J •rl

OJ iH o cd o u 4-1 I-I I-i Cl

D- cd

01 4J 1-4 Ml ao

I-I 0 cd

C c c CJ •H •r-l 0 t4 4-1 4J

CO 41 CL cd l-l J= >N 4) OJ <!

cd

H

J3

4J CJ* e

T3 4-1 41 O

4->

O 3 a

CL CO BO 01

CJ X!eo

01 I-i Li M-l 3

4J 4J

cd cd U J3

01 4-1 a

§"8

4J Cd c cd

cd oi o 41 C 4J o

tj e

4-1 4)

cd cu

•t-4 5

XI 4)

l-i CJ cd c

X) cu C I-i cd 4) 4J M-l CO 14-1 t4

tO XI

4-1 4J J3 41 c O

•H 4J O O

CL 4J M-l e 3

4-1 S3

cd 4J

CO T-l CUC

cs 4J 4J i-l

4) •-I cd o

i—i

01 1—1 a E a

4) 00 G 01 01 c

JJ th 1-1 4J >> .—1

x> 4J at 1 cd E

XI i-i

4) 0) CO 4) c J3 4-1 JS

1-4 JJ

cd 3

4J CO 4-1 -Q O cu cd O o l-l t-4 01 ^ 01 o >N 3

t4 l-l 4-1 4J

4-1 41 cd

CO 4-> 00M

Li

a 4) X) g •H a

CO t>o

B 3 X cd 4) cr o u 4J

N ' l-l 0) a > 41 a a cd O o cd C

i-i c cd XI

xi cd

cu

u

CO3 4) J3

CO 4J

41

li E a o

41 t4 Oi C4-I

I-i • 4) XI > O

J3

41 4J U 41 3 0

cd ca

Wi 4)

41

U isoi cr

4J CO

cd

l-l CU 8.5

cd c

Li CU 41 B
specimens with different initial surface conditions. The magnitude of

the spike before the melting plateau for two of the specimens is related

to the degree of initial surface roughness of the specimens. However,

regardless of the initial surface and operational conditions, radiance

temperature at the melting plateau is approximately the same for all the

specimens

.

A single value for the radiance temperature at the plateau for each

specimen was obtained by averaging the temperatures at the plateau. The

number of temperatures used for averaging ranged from 12 to 102, depending

both on the heating rate and on the behavior of the specimen during melting.

The standard deviation of an individual temperature from the average was

in the range 0.2 to 0.3 K for all the experiments. Similar values (for

standard deviation) were obtained when fitting the temperature data

corresponding to the premelting period to a quadratic function in time.

This indicates that during melting no undesirable effects took place, such

as vibration of the specimen, development of hot spots in the specimen

and random changes in the specimen surface conditions.

To determine the trend of measured temperatures at the plateau,

temperatures for each experiment were fitted to a linear function in time

using the least squares method. The detailed results are reported in

table 2. The temperature difference between the beginning and the end of

La the plateau (corresponding to the slope in the plateau) is^the range

0.1-0.5 K. The standard deviation of an individual temperature from

the linear function was^the same as the standard deviation obtained

by direct averaging of the temperatures.

73
The average radiance temperature at the melting point for the

thirteen zirconium specimens was 1940.5 K with an average absolute

difference of 0.3 K and a maximum difference of 0.7 K. The results are

presented in figure 3. It may be concluded that the radiance temperature

(at 650 nm) of zirconium at its melting point is 1940 K.

The normal spectral emittance at the melting point was determined

using the results of the radiance temperature (obtained from the measurements on strip-shape specimens) and the melting point (obtained from the

measurements on tube-shape specimens). The results yield a value of

0.367 for the normal spectral emittance (at 650 nm) at the melting point

of zirconium.

Several additional experiments were conducted on zirconium strips in

the "as received" condition. The results of a typical experiment are

shown in figure 4. The temperature plateau during melting has a

considerable slope and the temperature values are 2 to 5 K higher than

the values obtained on specimens with clean surfaces. This may be

attributed to the presence of a thin oxide coating on the specimens; the

high temperature values are consistent with the general behavior of the

zirconium-oxygen system [9],

3.3 Electrical resistivity

Electrical resistivity of the tubular zirconium specimens was

computed using the relation p = RA/L where R is the resistance, A the

cross-section area and L the length of the specimen between the potential

probes. The dimensions were based on their room temperature values;

the cross-section area was determined from the measurement of weight and

74
75
X 3UniVU3dlAI31 33NVI0VU

76
density. Resistivity values above 2100 K are available only for specimens

II and III, since the melting point determination of specimen I was made

without the voltage probes.

Zirconium undergoes a solid-solid phase transformation around

1150 K [10]. As mentioned in an earlier publication [11], the measurements of the geometrical quantities of a zirconium specimen after a number

of experiments indicated permanent distortions (elongation) due to

repeated heating and cooling through the transformation point. The

reported electrical resistivity results were corrected for the permanent

geometrical changes. The results for the electrical resistivity of

specimen II above 2100 K are shown in figure 5. The average absolute

difference in the measured electrical resistivity of the two zirconium

specimens in the range 2100-2125 K was approximately 0.2%. The final

results for the electrical resistivity of zirconium were obtained by

averaging the results for the two specimens. This yielded the values

128.7 x 10"8 0-m at 2100 K and 128.9 x 10" 8

fi-m at 2120 K. As shown

in figure 5, the electrical resistivity continued to increase during

melting of the specimen.

4. Estimate of errors

Sources and estimates of errors in experiments similar to the ones

conducted in this study are given in detail in earlier publications [ 1,

2]. Specific items in the error analysis were recomputed whenever

the present conditions differed from those in the earlier publications.

77
o

COn 0 C a VB M

•H c

CJ •H

<U 4J a iH

co 0)E 6 CD D -C

4J c

CO at CSI I-i •H JL N

U-i

C

cfl

O iUJi a to nr 4J ne * •H

re 1 >

1st iJ

cfl LU (0 U

re

Vt i-i 4) LU CO 4J

Jk iP— o

-r-l U-i0 U c

a) 0

•H

0) 4JO

4-1

C oco CO

•r-l 4-1 CO

cfl cfl •HU /TM\

CO

H > H o u

00

78
A summary of the results on imprecision and inaccuracy of some of the

measured and computed quantities is given in table 3.

It may be seen from table 3 that the imprecision of blackbody

temperature measurements during heating of the specimen (before

reaching the melting point) was approximately the same as that during

the melting period. This indicates that in the experiment the initial

melting phase progressed normally and that there were no undesirable

effects during melting of the specimen, such as vibration of the specimen,

movement of the blackbody sighting hole in the specimen, and the

instantaneous development of hot spots or zones in the specimen. Also

the imprecision of the radiance temperature measurements was the same

as that of blackbody temperature measurements, which indicates that

the surface conditions of the specimen did not change in a random fashion

during the melting period.

5. Discussion

The values of the melting point of zirconium reported in the

literature are given in table 4. No large discrepancies are found: all

values are within the combined inaccuracies of the measurements. There

^"Imprecision refers to the standard deviation of an individual point as computed from the difference between measured value and that from the

smooth function obtained by the least squares method.

2Inaccuracy refers to the estimated total error (random and systematic)

.

79
Table 3

Imprecision and inaccuracy of measured and computed quantities

Quantity Imprecision Inaccuracy

Temperature: blackbody 0.5 K 5 K

(during heating)

Temperature: blackbody 4 0.5 K 5 K

(during melting)

Temperature: radiance 0.3 K 5 K

(during melting)

Voltage V . UJ u U . i/o Current 0.03% 0.1%

Melting point of zirconium 0.5 K 8 K

Radiance temperature of zirconium 0.3 K 8 K

at its melting point

Normal spectral emittance 0.3% 3% I Electrical resistivity 0.05% 3%

80
-0

cjcd

ll ^ O s—

in 00 00

CJ CM f—1

1—1 i

X)Co

T-)co •H

m

(J41 ^ CN o CO

—i o

J_| 1—1 a6i

jjo>

4_» (0 00 vO 00 v£> i—1

vO <r oo

CM i—t

CM CO CO CO CO CM

(11 !_| i—I

i—i

(—1

r—t

r—i F—4 pH

CM CN CM CM CN CM CN CM

H

CN <J ul

_ in i si CO lO in in w J (V Q~\ CJ\ QS

W*

41UC

CM co <t in v£> 00

01

41

r- 3 CO cd | 1 0) *-p- »J-i ttl COat Q \j 1 1 rY , l*< I— cd cd cd l-i 00 T3 o

•H c 4J

C 14-1

C

4J cd TJ cd CO IH c

(0 0) E 4J

0)

M 4J t4 cd o c

co

C •H •a 0) o a cd i—1 u cd ai CO

M PO 01 •H i-l cd

u .m 0)

0) l-l i-l CD cfl o

Tt o 3 O cn <C

00

v©I

01

4-1 u

01IOo

0>

cd

CO41oc

0) IM

0)

cdC

•w

00

1-1

I-l o

01 5

0)

4-1 uoa

0>

co

0)

t-i

4-1 cdu

0)I0)

81
are indications that the specimens used in some of the earlier measurements were less pure than those used in the present study. Some of the

high values may be attributed to relatively large hafnium (melting

point about 2500 K) content of the specimens.

Normal spectral emittance (at 0.645 nm) of zirconium at its melting

point is reported to be 0.318 [ 19 ]; this is approximately 13% lower

than the value obtained in this work. Since in both cases, the same

value for the melting point was considered, the difference in emittance

may be attributed to the difference in radiance temperature at the

melting point, which is 22 K. No satisfactory explanation for this

large discrepancy has been found.

In an earlier publication [11], measurements of the electrical

resistivity of zirconium were reported for temperatures up to 2100 K. At

2100 K the difference between the present value and that reported earlier

is approximately 0.17o . Electrical resistivity of zirconium up to 2000 K

were reported by Peletskii et al. [20] and by Zhorov [21]. Extrapolation

-8

of those results to 2100 K give the values 127.9 x 10 Q-m and

-8

132.0 x 10 Q-m, respectively. The results of this work differ from

the extrapolated values by 0.7% in the case of Peletskii et al. [20]

and by 2 . 6% in the case of Zhorov [21]. Electrical resistivity behaved

normally until approximately 5-10 K below the melting point (figure 5).

Above this, a departure from normalcy was observed which may be due

to: (a) premelting effects of impurities present in the specimen, and

(b) increase in vacancy concentration. Small temperature gradients

in the specimen also may partially account for this.

82
As it may be noted from table 2, the linear fitting of radiance

temperatures at the plateau shows a bias toward positive slopes. Two

possible explanations may be given for this gradual increase: (a)

a small change in the normal spectral emittance of zirconium during

melting, and (b) partial formation of zirconium oxide on the specimen

surface, due to the high chemical reactivity of zirconium. It may be

noted that, with the present system, it was not possible to follow the

entire melting process because the specimen collapsed and opened the main

electrical circuit prior to the completion of melting. Approximate

calculations in the case of zirconium strips indicate that approximately

one third of the specimen was melted during the experiment.

In conclusion, the results of this study have yielded new values

for the melting point and the electrical resistivity of zirconium above

2100 K, and have shown the constancy and reproducibility of the

radiance temperature of zirconium at its melting point. The scheme

of measuring radiance temperature at the melting point, so far

demonstrated for niobium [5] and zirconium, may be an easy, accurate

and practical way for performing secondary calibrations and for

conducting overall on-the-spot checks on complicated measurements

systems at high temperatures.

Acknowledgement

The authors express their gratitude to C. W. Beckett for his

encouragement of research in high-speed the rmo physical measurements

and to M . S. Morse for his help with the electronic instrumentation.

83
£# References

#> 1. A. Cezairliyan, M. S. Morse, H. A. Berman and C. W. Beckett. -

High-speed (subsecond) measurement of heat capacity, electrical

resistivity, and thermal radiation properties of molybdenum in

the range 1900-2800 K. J. Res. Nat. Bur. Stand. (U.S.), 1970,

74

A

(Phys. and Chem.), 65-92.

2. A. Cezairliyan, M. S. Morse and C. W. Beckett .- Measurement of

melting point and electrical resistivity (above 2840 K) of

molybdenum by a pulse heating method. Rev. Int. Hautes Temper,

et Refract., 1970, 7, 382-388.

3. A. Cezairliyan. - Measurement of melting point and electrical

resistivity (above 3600 K) of tungsten by a pulse heating method.

High Temp. Science, 1972, 4, 248-252.

4. A. Cezairliyan. - Measurement of melting point, normal spectral

emittahce (at melting point), and electrical resistivity (above

2650 K) of niobium by a pulse heating method. High Temp.- High

Press., 1972, 4, 453-458.

5. A. Cezairliyan. - Radiance temperature of niobium at its melting

point. J. Res. Nat. Bur. Stand. (U.S.), 1973, 7_7A (Phys. and

Chem.), 333-339.

6. G. M. Foley. - High-speed optical pyrometer. Rev. Sci. Instr.,

1970, 41, 827-834.

84
7. A. Cezairliyan. - Design and operational characteristics of a

high-speed (millisecond) system for the measurement of thermophysical properties at high temperatures. J. Res. Nat. Bur.

Stand. (U.S.), 1971, 75C (Eng. and Instrum.), 7-18.

8. International Committee for Weights and Measures. - The

International Practical Temperature Scale of 1968. Metrologia,

1969, 5, 35-44.

9. R. F. Domagala and D. J. McPherson. - System zirconium-oxygen.

Trans. AIME, 1954, 200, 238-246.

10. A. Cezairliyan and F. Righini . - Thermodynamic studies of the

0/ -> Q phase transformation in zirconium using a subsecond pulse

heating technique. J. Res. Nat. Bur. Stand. (U.S.), in pr<2£S

11. A. Cezairliyan and F. Righini. - Simultaneous measurements of

heat capacity, electrical resistivity and hemispherical total

emittance by a pulse heating technique: zirconium, 1500 to

2100 K. J. Res. Nat. Bur. Stand. (U.S.), 1974, 78A (Phys. and

Chem.) ; in fxm .

85
12. J. H. deBoer and J. D. Fast. - Uber die darstellung der reinen

metalle der titangruppe durch thermische zersetzung ihrer

jodide. III. Hafnium. Z. anorg. u. allg. Chem., 1930, 187,

193-208.

13. H. K. Adenstedt. - Physical, thermal and electrical properties

of hafnium and high purity zirconium. Trans. A.S.M., 1952,

44, 949-973.

14. R. A. Oriani and T. S. Jones. - An apparatus for the determination

of the solidus temperatures of high -melting alloys. Rev. Sci.

Instr., 1954, 25_, 248-250.

15. J. T. Williams. - Vanadium-zirconium alloy system. Trans.

AIME, 1955, 203, 345-350.

16. D. K. Deardorff and E. T. Hayes. - Melting point determination

of hafnium, zi rconium, and titanium. Trans. AIME, 1956, 206

^ 509-511.

17. R. V. Sara. - The system zirconium-carbon. J. Am. Cer. Soc,

1965, 48, 243-247.

18. R. J. Ackermann and E. G. Rauh . - Determination of liquidus

curves for the Th-W, Th-Ta, Zr-W, and Hf-W systems: the

anomalous behavior of metallic thorium. High Temp. Science,

1972, 4, 272-282.

86
19. D. W. BonnelljJ. A. Treverton, A. J. Valerga, and

J. L. Margrave. -The emissivities of liquid metals at their

ii fusion temperatures, in Temperature - tts measurement and

control in science and industry. H. H. Plumb^ Vol. 4,

part 1 (ISA, Pittsburgh, 1972), pp. 483-487.

20. V. E. Peletskii, V. P. Druzhinin and Ya. G. Sobol'. - Emissivity,

thermal conductivity, and electrical conductivity of remelted

zirconium at high temperatures. High Temp., 1970, 8, 732-736.

21. G. A. Zhorov. - Emissivity of metals of the IVb subgroup at

high temperatures. High Temp., 1970, 8, 501-504.

87
Chapter 5

Thermodynamic Studies of the

or -» 6 Phase Transformation in Zirconium Using

•k a Subsecond Pulse Heating Technique

•irk A. Cezairliyan and F. Righini

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

Abstract

Measurements of the temperature and energy of the oe -* 3 phase

transformation, and the electrical resistivity near and at the

transformation point of zirconium using a subsecond duration pulse

heating technique are described. The results yield 1147 K for the

transformation temperature and 3980 J-mol * for the transformation

energy. Electrical resistivity is found to decrease by 177o during the

transformation. Estimated inaccuracies of the measured properties are:

10 K for ^transformation temperature, 57Q for ^transformation energy, and

2% f or^electrical resistivity.

*

This work was supported in part by the U. S. Air Force Office of

Scientific Research.

Guest scientist from the Istituto di Metrologia "G . Colonnetti" in

Torino, under a fellowship from the Consiglio Nazionale delle Ricerche

of Italy.

88
1. Introduction

In 3.no.ti\t2<c publication [1]*, the applicability of a rapid

pulse heating technique to studies of solid-solid phase transformations

at high temperatures was demonstrated by measurements on iron at the

X

~* 6 transformation point.

The objective of this paper is to apply the same technique to

studies of the a -» p phase transformation in zirconium. Measurements of

the. the temperature and energy ofphase transformation, and electrical

resistivity near and at the transformation point are reported.

The method is based on rapid resistive self-heating of the specimen

from room temperature to high temperatures in less than one second by

the passage of an electrical current pulse through it; and on measuring,

such experimental quantities as current through the specimen, potential

drop across the specimen, and specimen temperature. Recordings of the

experimental quantities are made digitally every 0.4 ms with a fullscale signal resolution of approximately one part in 8000. Specimen

temperature is measured with a high-speed photoelectric pyrometer [2].

The details regarding the construction and operation of the measurement

system are given in earlier publications [3, 4],

Figures in brackets indicate the literature references at the end

of this paper.

89
2. Measurements

The measurements were made on three zirconium specimens of 99,98%

purity. The specimens were tubes fabricated from rods by removing the

center portion using an electro-erosion technique. The nominal dimensions

of the specimens were: length, 76.2 mm; outside diameter, 6.3 mm; and

wall thickness, 0.5 mm. The outer surfaces of the specimens were

polished to reduce heat loss due to thermal radiation. According to

the manufacturer's analysis, the specimens contained the following

impurities, in ppm by weight: 0, 125; Hf, 40; Fe, 30; C, 6; H, 3.3;

Al, 3; N, 2.1; Ni and Si, 1.5 each; and Ti, 1. The total amount of

all other detected elements was less than 6 ppm, each element being

below 1 ppm limit.

Duration of the current pulses ranged from 220 to 620 ms. Specimen

heating rates varied from 1800 Ks * to 4000 Ks All the experiments

were conducted with the specimens in a vacuum environment of approximately

1.3 x 10"3 N-nf2 (~ 10" 5

torr).

The a -» p transformation (from hexagonal close-packed form to bodycentered cubic) was manifested by a plateau in the temperature versus

time relation for the specimen during heating. The transformation

temperature for each specimen was obtained by averaging the temperatures

at the plateau.

90
The transformation energy was obtained from the time integral of

the power absorbed by the specimen during the transformation as

defined by the plateau. The instantaneous value of the absorbed power

was obtained by subtracting the power loss due to thermal radiation from

the imparted power (current through the specimen times the potential

drop across the specimen). The hemispherical total emittance needed

at 1147 K was obtained from the extrapolation of the measurements

above 1500 K reported in an earlier publication [5]. Since at the

transformation temperature power loss from the specimen due to thermal

radiation was approximately 0.7% of the imparted power, even considerable

uncertainties (10%) in the emittance do not contribute any significant

errors to the absorbed power.

3. Experimental results

Except where explicitly noted, all temperatures reported in this

paper are based on the International Practical Temperature Scale of

1968 [6] r In all computations, the geometrical quantities are based on

their dimensions at room temperature (298 K) . The experimental results

for the temperature and energy of the a -».f3 phase transformation are

presented in table 1.

The average value for the transformation temperature is 1146.6 K

with a maximum and average absolute difference from this value of ' 8 K

and 1.1 K, respectively. The average value for the transformation

energy is 3977 J-mol ^ with a maximum and average absolute difference

from this value of 0.4% and 0.3%, respectively. It may be concluded

that for ot -* (3 transformation in zirconium, transformation temperature

A

91
Co

•M

—

4-) r-1

rep

60 --I CO o 00

H

u o rs vO o cu S ON ON J-i CM c . co en CO o c

CO CM o E C V—' •M 3 to CU 4J •M u u 2 C H 3 E O 4-t M O tO o u u CM

•H cu co N & C E to CM cu M O 4-1 4J

CJ T> C c CU 60 t-i o o 60 U CO •i-l •M CO -o 4J <* CN 4-1 u c c CO S*S • • • CO 0)

<D CO •r-l ^ co co CO E >

4-1 > CO c CO 0) O o o CM CU •M CO

4-1 c 4J

CO cO e M e M 4-1 o O e W

<4-t o CD CU CM

CO t-l

U 60

C 4-t 3 CO 3

03 tO 4-1 onH cd

M

B CO • • • CU cu 4J w M ^ 00 c£> 4-1 o <t <f CO tO *S CM a r-l l—l l—l • i—i e co 6 r-l i-H I-l 4J CU Cu

co

C cu c

tO

H •H 4J cu

a)M o u H c 4-1 3 •M

4-1 c CO 4-1 cO o 4-1 cd M 1-1 X)

CU 4J o cu & CO i-l 6 E O 3

cu

M 4J 4-1

4-t CO o cd

cu CM •o

M c <4-l m CO cu cu o o 3 c CO §*

•H 4J CO 3 B

4-1 M. tO 1-1

M cu 2

CU

U CM <x> <r 4-1 3 4J

B .o CU tO u a CU CU i-H o S 4J cd CM Z cu 4-1 cd 3

co

H i—i "O

C 3 a 1-4 cO O > u i—i cu •H

4-1 CU X. TJ X 4J C • H cd •M C O CU 4J CU

<4-l 4J CO

C S

CO t-< oCO i-l CO M 1 o o r-l co o

*J co o o o CU cu CM CU i—1

60 o — 4J

M

O Cu 3 c — CO to 3 CO

co •I-l E 4J c

0) 4-1 •H cO

O co Pi to X )-i •H

cu o CU 4-J

M

PC

ua cd o

Cu E •H CM

Cu cu >

CO 4-> cu cu c TJ l-i *o CM CU 3

cu

O E 73 4J c 4J i-l l-i CO U CO M O tfl l-i e CU 3 CU CU TJ CU

1-4 .£> i—i Xi Cu

C Ou

O S t—1

CO CO E co to E

CU 3 > 3 4J CU W Z to CO 4-1 co CO a

92
is 1147 K and the transformation energy is 3980 J*mol

As discussed in an earlier publication [5], the measurements of

the geometrical quantities of a zirconium specimen after a number of

experiments indicated permanent distortions (elongation) due to

repeated heating and cooling through the transformation point. The

values reported in this paper correspond to the first experiment for

a specimen for which no correction was needed.

Typical experimental results are presented in figures 1, 2, and

3, all referring to specimen 3. Specimen

temperature near and at the transformation point is shown in figure ).

Figure 2 shows the variation of electrical

resistivity as a function of time, while the variation of resistivity

with temperature is shown in figure 3. The dashed lines in figure 3 are

the best least squares fittings of the resistivity versus temperature

data in the respective regions. It may be seen that the change in the

electrical resistivity (100(0, _ - p - ) during the transformation

before after

was about 1770 . Extrapolation of the resistivity values about the

transformation to 1500 K is in agreement, within 0.37o , with those

reported in an earlier publication [5].

The details for estimating errors in measured and computed quantities

using the present measurement system are given in an earlier publication

[4]. In this paper the specific items were recomputed whenever the

present conditions differed from those in the earlier publication.

93
>-cc<cc

O GO

»T-t r- CO

03

p

M » 1

rrt co

Q) 00

r*V* * on P

*H AJ

4J •HO O ap C •H s O CoO O i—

c •H 0 N 1 J _ 1 CO

CD

O c

03

a

C •H

CJ £ o 4) H Ou 9 CO 4J o O M •H 4J

0) 4J a CO CO e E

(-1 0) 01

4-> o M-4

M-4 01

<4-l co

U

O

C

0) c u o 4-1 1-1 3

4-1 01 o 4 .c

ft 4J U

4-1 > « -

01u3

60

CM

un

94
rr-J CO w ec

rrl onCO

nj 00 a o

A) II

II C

•r4 4-J

[

i •H

rfi-t I4_l w c

g p o *H o 1 i 4J

(J

-1 •

n3 o *—

CD

CO 4-1 B c •i-i o

>s o 0) 4J a

n > co o

4J »H u

M 4-1 t-l to

CO i

l-l <U

J-i o M-4 CM ai

<4-l co o C

cfl (1)

on t"r

L.V

•H 3 u (V CJ

(D X,

•r-l 4J U

4-1 > 03

0)

1-1

6C

CO CM

"•u9

.oi 'aiiaiisisu minDii]

95
- CD ^

u

a

<vc

0)u

COu

a>a

e

CO

u

60

O

a-ao

0)

cd ^ T3

TO C

> CO

CS!

m-Ug.Ol 'A1IAI1SIS3U W3iyi3313

96
The results for imprecision and inaccuracy are: 3 K and 10 K

for the transformation temperature, 17, and 5% for the transformation

energy, and 0.57, and 27, for the electrical resistivity.

In the case of temperature, the standard deviation of an

individual point from the average transformation temperature in a given

experiment is approximately 3 K. For the three experiments, the

average absolute difference of transformation temperatures from their

mean is 1.2 K. In the case of energy, the imprecision includes the

uncertainty in the computation of the time duration of the transformation

plateau. Different ways in selecting temperature points belonging to

heating or plateau regions lead to average energy differences of 0.67o .

4. Discussion

The first evidence of a possible solid-solid phase transformation

in zirconium was presented by Zwikker in 1926 [71 . Since his experiments

were performed on zirconium heated in air, the transformation occurred

over an extended temperature range. A sharp transformation was reported

by Vogel and Tonn [81 from dilatometric and metallographic measurements

and was confirmed by de Boer et al. [91, who noted that the temperature

2Imprecision refers to the standard deviation of an individual point as computed from the difference between measured value and either the

average or the smooth function obtained by the least squares method.

3

Inaccuracy refers to the estimated total error (random and systematic).

97
range was extended by small amounts of oxygen and nitrogen in zirconium.

The values for the a -* Q transformation temperature for zirconium

reported in the literature are given in table 2. Some of the old

results could not be corrected to IPTS-68, due to insufficient

information in the original papers. However, the contribution of the

possible differences in the temperature scales may not exceed a few

degrees at the transformation temperature.

The present value for the transformation temperature is higher

than most of the values given in the literature. This may partly be

due to the high heating rates used in this work. A similar effect,

though in the opposite direction, was observed by Duwez [10] in

experiments on rapid quenching of zirconium specimens (cooling rates

from 4 to 10,000 K«s The transformation temperature was found

to decrease with increasing cooling rate by as much as 15 K. This

behavior was confirmed by Hayes and Kaufman [15]. The result of the

energy of transformation of zirconium obtained in this work (3980 J«mol~*)

is 67, higher than the value (3740 J.mol" 1

) of Douglas and Victor [14],

37c higher than the value (3850 J.mol" 1

) of Coughlin and King [16], and

0.17„ higher than the most recent value (3975 J.mol" 1

) of Vollmer et al.

[13].

The general trend of the behavior of electrical resistivity near

and at the transformation point of zirconium is as follows (figures 2.

and 3). Resistivity reaches a maximum about 10 K below the transformation

point, then it decreases slightly and undergoes a large change (decrease)

at the transformation point, after which it decreases some more and

98
Table 2

s of the ot-Q transformation temperature of zirconium reported in the literatu

Investigator Reference Year Temperature

3

(K)

Vogel and Tonn oo

1 Q1 1 iyj l 1135 ± 5

de Boer et al

.

Qy LyjO 1 no _i_ i r\ LLjo ± 1U

Duwez IU 1 QC1 iy j l ll^J to llJo

Domagala and McPherson 1

1

1

1

lyD't 1 IOC

Kneip and Betterton 12 1956 1138 to 1146

Vollmer et al. 13 1967 1155

Present work 1147 ± 10

All temperatures in this table are those reported by the authors of the

original papers. No correction to IPTS-68 was possible, due to

insufficient information in the original papers.

99
reaches a minimum at about 5-10 K above the transformation point.

Above this minimum, resistivity increases with temperature almost

linearly

.

Because of the strong dependence of the electrical resistivity

on composition for zirconium at the transformation point, it is

difficult to compare resistivity values reported in the literature on

an absolute basis. However, a meaningful comparison may be made based

on the ratio of the maximum to the minimum resistivities for a given

specimen. The results of such a comparison are given in table 3.

High values for the ratio and small temperature range during which

transformation is completed are indications of the high purity of

the specimens.

Acknowledgement

The authors express their gratitude to C. W. Beckett for his

encouragement of research in high-speed thermophysical measurements

and to M. S. Morse for his help with the electronic instrumentation.

100
CU ] o\ <N o ON CO

O

u i-4 r-i t-4 CN 1—1 i-4 CN 3 • u o CO cO i-t u u 4J CU 0) CO cx

4J OS o CO •H 2 cx

r-4

CD • CO

co

C

4J I-l 1-1 0) 60 c 4-1 CX i-l

1-1 M-l i-4 O >

CO P

(X o

X> •H

r-4 CU 01 CO 4J 4J CD CO eg .e

I-l !" i-l

C 4-1 o 3 co o m CN CI CI 00 •H

cx 4J CD «r> <f <r rs

m 60C

0) cO l-i <t r-4 t-4 i—l i—i i-4 i—i i-l 1-4 U W

0) S w

CL,

g

uo co c S § a> i-i o 0) -r4 x. *J

i-4H

C 4J CO

4-) •H

B

CO S <4-l I-l o o

M-4 o co C

14-1 l-l i-t co o

£2 J= *J

CO

U

C

)-i 4-1 3 0)

4-1 •H CO 1-4

<4-l > CJ

01

O 1-4 0) 1-4 jC 4-1 •C

4J CO co 0) .H

4-1 U-43

00

M co o O r» oo r-^ ON <t r»> CO c 3 CU in CO vO 1-4 CN CM en Xi C

4J V4/-S 1-4 1-4

O 1-4 1-4 1-4 i-4 i-t

l-i co t»d XI B V CU o

X) at 3 4J 4J a s B 1-4 « X H co

epor due

•H 6 i-i GO co cu o 4-1 r-l rJ r-4 £)

1-1 N

IW

-o

vD>

1-4 <f <>

resu ossi o ON

l—l *r < < CX C

>> o u 4J

i-l X)

W > 0) 3

i-4 CO

4-1

Reference

cfl 00 1

resis ON e

are b

IPTS-6

CO r-H

O

CJ rO 4J

i-l CO

l-i 4-1 CO 4J 0)

CJ co 3

41

C T-4 r-4 i-4 CO co 4= CO

0) i-i o B

U-4

C

i-i

4-1 >

a) 4-1 • 3 0)C «-4 CO 1-4 CO 4-1 1-4 O

•s 00

i-4

CO tvd < X,

t-i co

C

M-4 4J 4-1 XI x> XJ o CU o O CO 41 C 4-1 c e 3 3 i-l 0) CO X3 CO CO r-l 4-1 01 > l-i U 0) 4-1 CO CJ 60 C 0) 0) CU 4-1 CO I—l e > <U C H o U CO I-l 1-4 0) I-i CO PO 1-4 C 4) 4) co r-4 VJ .C 1-4 3 0) 60 CU r-^ O o ? CU cr XJ O o I-l < CJ CO < 02 Pm CO

101
5. References

Cezairliyan, A. and McClure, J. L., A subsecond pulse heating

technique for the study of solid-solid phase transformations

at high temperatures: application to iron. Lri pr^ pai a-^iou.

Foley, G. M. , High-speed optical pyrometer. Rev. Sci. Instr.,

41, 827 (1970).

Cezairliyan, A., Design and operational characteristics of a

high-speed (millisecond) system for the measurement of

thermophysical properties at high temperatures. J. Res. Nat.

Bur. Stand. (U.S.), 75C (Eng. and Instr.), 7 (1971).

Cezairliyan, A., Morse, M. S., Berman, H. A., and Beckett, C. W.,

High-speed (subsecond) measurement of heat capacity, electrical

resistivity, and thermal radiation properties of molybdenum in

the range 1900 to 2800 K. J. Res. Nat. Bur. Stand. (U.S.), 74A

(Phys. and Chem.), 65 (1970).

Cezairliyan, A. and Righini, F., Simultaneous measurements of

heat capacity, electrical resistivity and hemispherical total

emittance by a pulse heating technique: zirconium, 1500 to 2100 K.

J. Res. Nat. Bur. Stand. (U.S.), 78A (Phys. and Chem.), Cn P<'4 S 5

,

International Practical Temperature Scale of 1968. Metrologia,

5, 35 (1969).

102
[7] Zwikker, C, Modi f icatieveranderingen bij zirkoon en hafnium.

Physica, 6,361 (1926).

[8] Vogel, R. and Tonn, W., Uber einen umwand lungs punk t des zirkons.

Z. anorg. allgem. Chem., 202, 292 (1931).

[9] de Boer, J. H . , Clausing, P. and Fast, J. D., The ct-Q transition

with mechanically treated and with untreated zirconium. Rec.

Trav. Chim.,55, 450 (1936).

[10] Duwez, P., Effect of rate of cooling on the alpha-beta

transformation in titanium and titanium-molybdenum alloys.

Trans. AIME.191, 765 (1951).

[11] Domagala, R. F. and McPherson, D. J., System zirconium-oxygen.

Trans. AIME.200, 238 (1954).

[12] Kneip, G. D. and Betterton, Jr., J. Floating zone

purification of zirconium. J. Electrochem. Soc, 103

,

684

(1956).

[13] Vollmer, 0., Braun, M. and Kohlhaas, R., Die Atomw'arme des

Zirkons zwischen 300 und 1700 K. Z. Naturforsch . , 22, 833

(1967).

[1'+} Douglas, T. B. and Victor A. C, Heat content of zirconium

and of five compositions of zirconium hydride from 0 to 900°C.

J. Res. Nat. Bur. Stand., 61, 13 (1958).

103
M [IS] Hayes, E. E. and Kaufmann, A. R., Observations on the alpha-beta

it transformation in zirconium in Zirconium and Zirconium Alloys,

p. 241 (American Society for Metals, Cleveland, Ohio 1953).

[ l<t>] Coughlin, J. P., and King, E. G., High-temperature heat contents

of some zirconium - containing substances. J. Am. Chem. Soc,

72, 2262 (1950).

[17] Squire, C. F. and Kaufmann, A. R., The magnetic susceptibility of

Ti and Z*- . J. Chem. Phys., 9, 673 (1941).

[18] Adenstedt, H. K., Physical, thermal and electrical properties

of hafnium and high purity zirconium. Trans. A.S.M.,44,

949 (1952).

[19] Rogers, B. A. and Atki ns, D. F., Zi rconium-columbium diagram.

Trans. AIME,203, 1034 (1955).

[20] Powell, R. W. and Tye, R. P., The thermal and electrical

conductivities of zirconium and of some zirconium alloys.

J. Less -Common Metals, 3, 202 (1961).

104
Chapter 6

RADIANCE TEMPERATURE (at 650 nm) OF MOLYBDENUM

AT ITS MELTING POINT

Ared Cezairliyan

National Bureau of Standards

Washington, D. C. 20234

Measurements of the radiance temperature (at 650 nm) of molybdenum

(99.95 percent pure) at its melting point were performed on 14

specimens in the form of strips. The nominal dimensions of the strips

were: length, 50.8 mm; width, 4 . 7 mm and thickness, 0.24 mm. Before

the experiments, specimen surface was treated using abrasive. three

different grades of c2br<3Sii/£ were used yielding three different

surface roughnesses (ranging from approximately 0.2 to 0.5 Mm) for

different specimens.

All the experiments were performed with the specimen in an argon

environment at atmospheric pressure. The heating rates for different

specimens were in the range 1200 K«s * to 3500 K*s , corresponding to

specimen heating periods (from room temperature to the melting point)

in the range 0.4 - 1 s.

105
Radiance temperature of molybdenum at its melting point for the

14 specimens and other pertinent results are reported in Table 1.

The variation of radiance temperature as a function of time near and

at the melting point is shown in Figure 1 for three typical experiments

representing three specimens with different initial surface conditions.

The magnitude of the spike before the melting plateau for the specimens

is related to the degree of initial surface roughness of the specimens.

However, regardless of the initial surface and operational conditions,

radiance temperature at the melting plateau is approximately the same

for all the specimens. Temperature of the spike in all the experiments

ranged from 4 to 16 K above the plateau temperature.

A single value for the radiance temperature at the plateau for

each specimen was obtained by averaging the measured values of the temperatures

at the plateau. The number of measurements used for averaging ranged from

25 to 99, depending both on the heating rate and on the behavior of the

specimen during melting. The standard deviation of an individual measurement

from the average was in the range 0.3 to 0.4 K for all the experiments.

Similar values (for standard deviation) were obtained when fitting the

temperature data corresponding to the premelting period to a quadratic

function in time. This indicates that during melting no undesirable

effects took place, such as vibration of the specimen, development

of hot spots in the specimen and random changes in the specimen

surface conditions.

106
CO CD 4J B

•i-4 ti

4-> cd r-l

and CO

4-1 o C

0) vO

ea im 4J c >j

cd <u

1—'

me dx

a) •H a)

i_i 4J

i—i

1

<4-l cd

cd o o M •H

<D c tx a o >> B •r4 4-1 Q) 4J

4-1 nc e

e

OJ 3 u

a M-4 XI c 4J

cd cd •H (-1 T) CO o

cd cd 4-4 CO u

4J B

4-4 §

C ro o •H co O oo c T) (X o .O O

•H >•» 60

4-1 T-l (3 II cd o i-l 1-4 e 4-1 4J

!-i i-4 cd 14-1 0) c > O S 3

3

60

•H

>l '3yniVU3dlAI31 33NVI0VU

107
C

0) 13

SOOe

U-lOEo

in

4J

to

o>

>j3u

n)u

OJCL6

0)

4-1

0)oc

n)

01 •f-J T3 X to to H U-lo

4-1 cs

0)

>j3

raois

oi .c

i-j

ij fo

to

i-i c

oiB

r-iu

o>clX

0)o

tfl

•rl T3

C

rl

O

fO *t-t CO co CO CM CO CO CO CO CO <t CO

TJ 4-1 c n) o O

O o o O

O o o o o o o o

4-> >

CO oj TJ

OJ

(11M

O 3 C 4-1 vO co uo CM r-- CO <f LO CM <f r-. Os

tO to •H U Jyi

O ctn o o o O o o CJi

O o o o

•o OJ co cm CO CO CO CO CO CO CO CM CO CO CO CO

tO Cle tN CM CN CM CM CM CM CM CM CM c-i CM CM CM

01 4J

O

*t-l CL60

Ij E 0)

01 0)

u

a. 4-1

C

0) CO CN CM «* CM <t CO LO

60 3 l-i !*! o O o o o o C 10 0) O O o o o O O

O

•rl 0) M-4 1 4J 4-1 U-l i—

tO *rl oj 1-4 T3

;£ CU

4-1 4-1 r-

to 3 1 tO 01

Ol 0) o> CM r>

X CO

CL 4-1 • o o o o o o

r-l ,-4 ^ °P i CO Cl

OJ

01

0) M-l 1>J O 3

4-1

1-4 10 ON CM OS 00 U0 00 00 LO o> 00

<U >-4 co co * CM \D

m r~ <* cr- CM

m

-9 01 E CL 3 e Z o) 4J * M O

fO 'rl T3 4-1 co CN CO CO CO <r CO CO CO <t

C! n)

4-1 >

CO 01 •o ~o b• HM

0)Cl60

u c Ol

•rl 4-1

4-1 tOM o O o o o o o o o O o o o O 0) r-4 o o o o o o o o o o o o o o e DO 1 uo <t CO CO m LO <f LO LO o- CM U3 LO

oi

C oi co CO CO CO CM CM CM CM CM CM CM r-l CM CM

M •rl .

toOJ X

OJ tn u at

to

C

U 60 3 3

COO

C

01 CO S P

01

B

a.

a

CO

C

QJ -C CU 4J r;

QJ 4-1 e 4-1 c c (0 o CO 4J Jq

QJ •H to M bO

4J 60 CO QJ U-I fO CJ c ZJ J-I *d c •H to T3 a) u c (-1 4J QJ c c QJ cO 4-1 CO H •H > J_i n3 to QJ CL QJ u QJ QJ Cl rC

X) QJ Lj 0 5 4-t 0 c QJ u

*H QJ 4-1 4J

B c x. cO to o o 4J Lj QJ n) •H

*J c

pe

nc

aj

U-I

(J o QJ to t_i 4J c U CD QJ tO 4J T3 4J pC

U-I 4-J to tO 4J

rO QJ

M

u

OJ QJ _D cO QJ TJ g 4J CL Cl

•r-l tfl OJ P QJ qj u 1—

CJ * i QJ

CX. o c 4-J QJ

(0 QJ a OJ 4J M QJ rrl i—

to _G 0) QJ rj QJ CO tO

j-i j-i e U-l £ >

<u 4-1 > 4-1 (SI H <4-t •H

fO OJ X) o 0 > 0)

J-J

M CO cO QJ *o T) QJ 4J 3 U QJ c C 03 M

tO cr to QJ •r-l CO fd *CJ c*0 JJ CO E QJ 4J

r-J CO •H c E cO

<U QJ 4-t

U

U tO

H

CL QJ

D QJ QJ QJ 3 cO CL cO a U-| r* Cl s 4-J QJ & QJ to o 4J g

4_J tO i—

QJ 4-1 QJ

u 4-1 fO to j_j 1) QJ QJ o QJ Cl QJ CL u GJ QJ u B u o 4J

QJ c QJ U-I <0

U-t 4-J GO (0 QJ cO o c H 4J >

QJ «rH QJ QJ *0

a)X to cO U-IM *o 0) cO > 4J 3 J-l 0 - tO CJ

•r-1

G »-i • T3) £

1-1 tiO QJ

g T>

O QJ

D P QJ

C £ C *H > to tO J-i CO > • H >H s QJ 4-> CO QJ X) QJ QJ

4-1 4J •rl

U JJ c U-I JJ

u 4-1 QJ

C QJ (0 to U-i cd

a) •rH

a to *J »H

Q 4-t U-I

H cl

•H T3

a

C 0)

-rl Cl

cO oi 01 4-1 01 X 0)

rl

O rC rC to 4-1 4J 3 0

00 Ol o cr 4-1 U-I c a) 4-1 0 01 0 3 6 3

4-1 CL CO 4J Cd 4-1 1 01 • Ol c

r-l 3 01 Cd 4J 4-1 -rl i—

o O X. CD C CO O o 1-4 4J r-l .H r-4 CL

"4-1 01 01

O CL XI CO B 01 CL 60

01 o 0) c

01 rl 4J 60 .C *rl 4J U U-4 a 4-1 4-1 o 3 rS -rl r-l O 4-1 4-1 J3 4J 4-1 0) 4J CO r-4 CO B

CO >, l-i TJ 0) -O LO OJ 4J g; s to oi c • 01 a c 4J -C o o 4J B •a •rl 01 r-l 4-1 Cl tO 01 c cd X. 3

CO ~ B 4-1 cd 4J 4J 01 4J

01u •H rO 01 to

U r-l a)

O 3 u

u •- 0 to 3 O 01 O 00 3 y—s I—

01

u

O CO CL o (0O 01 rC 3 a •r4 > •rl rQ 4-1 4J

t/l o CO > 4J CO c •r4 cd S«i 60 U o - 0) Ol rl C 01 •H CO Vj c >-i T) O •h a

4J 3 •rl 3 td o 60 E

•i-4 4J to 3 -4 cd 3

T3 CO cO

C cd cr rl 4-1

C CM Ij CO 01 ^ fo 01 O • Ol E

1—1 > 01

O

O CL U-4

C 01 tO o e O OJ O l-i c

0) Ol T-4 cd

C CO o < 4-1 a 4-1 4J B •rl -rl

to o O -rl -o

U-I tO •rJ

C

C

X •a co 4J ai 3 0 o> u Si 4J tO 0) U-I (J tfl to •rl 3 CL 3 0) > 4-1 o) a X.

•a 01 atB to 01 4J

O -H ai •a £> •rl 0)

U-I 4-1

u -a V4 IJ

to CO -o 0) c 3 O

-O 01 3 u o oi ai 4-1 U-l V W —

CO c 3 w cd

t/l t/l tO o 01 to

X

U 01 3 0) > a u U 01 Oi 3 c ai • CO 01 01 CL i—

2 -= 4-1 4-1 U-I > to E to C 60 01 c to U-I 4-1 OJ > O 3 4J -rJ •rl 0) CO 4-1 •H O CO O 01 •a rl O 01 4J yj t-i a. 4-1 3 u-l 00

CO c 01 4-1 o to 4J H 60 60 11 -c CO • u o cd a c to 4J >J -o rl 01 C u •r4 -r-l <u 01 o 01 >

•r4 4-1 4-1u Q-E XI to 01 CL tO —4 a E 4-1 I p

Q

01 01 01 01 Ol J* e OS •o

U-I

u

g Z to

01
To determine the trend of measured temperatures at the plateau,

temperatures for each experiment were fitted to a linear function in

time using the least squares method. The detailed results are reported

in Table 1. The temperature difference between the beginning and the

end of the plateau (corresponding to the slope in the plateau) is in

the range 0 - 0.5 K. The standard deviation of an individual temperature from the linear function was approximately the same as the

standard deviation obtained by direct averaging of the temperatures.

The average radiance temperature at the melting point for the

14 molybdenum specimens was 2530.4 K with a standard deviation of 0.6 K

and a maximum absolute difference of 1.2 K. The results are presented

in Figure 2. It may be noted that the maximum absolute difference

of the results for the specimens with condition A surfaces (least

rough) is only 0.7 K. The two experiments (corresponding to specimen-2

and specimen-10) with relatively large negative deviations (about

-1.1 K and -1.2 K) have caused a downward shift of the average by

about 0.2 K. In order to reduce the contribution of these two

experiments, the average temperature is rounded-off to the higher value.

This is also compatible with the average (2530.6 K) of the results for

the specimens with condition A surfaces. It may be concluded that

the radiance temperature of molybdenum at its melting point is 2531 K,

with an estimated inaccuracy of 10 K.

109
110
The radiance temperature (2531 K) and the melting point (2894 K)

measured with the present system [1] yield a value of 0.334 for the

normal spectral emittance (at 650 nm) of molybdenum at its melting

point

.

Several additional experiments were conducted on molybdenum in

"as received" condition. The results of these experiments were

generally 3-5 K higher than the value 2531 K. The higher values might

be attributed to contamination on the specimen surface. Because of

the high vapor pressure of molybdenum at its melting point, it was

not possible to conduct meaningful experiments with the specimen in

a vacuum environment.

Bonnell et al. [2] have reported a value of 2510 K for the

radiance temperature (at 645 nm) of molybdenum (99.9 percent pure)

at its melting point. No satisfactory explanation for the large

discrepancy (21 K) between the result of Bonnell et al. and that of

the present work has been found. In the past [3, 41, differences of

the same magnitude and direction were also noted in the results obtainpH

bv the two laboratories for other refractorv metals. The

differences were 20 K for niobium (at 2425 K) and 22 K for zirconium

(at 1940 K).

Ill
References

c. W.

1. Cezairliyan, A.^Morse, M. S., and Beckett. Measurement

of melting point and electrical resistivity (above 2840 K) of

molybdenum by a pulse heating method. Rev. Int. Hautes Temper.

et Refract., 7, 382,(l97o).

2. Bonnell, D. W., Treverton, J. A., Valerga, A. J. and Margrave

J. L.j "The emissivities of liquid metals at their fusion

temperatures", in Temperature - its measurement and control in

science and industry, H. H. Plumb. ed.,Vol. 4, part 1 (ISA,

Pittsburgh, 1972), p. 483.

3. Cezairliyan, A., Radiance temperature of niobium at its melting

point. J. Res. Nat. Bur. Stand. (U.S.), 77A (Phys . and

4. Cezairliyan, A., and Righini, F., Measurement of melting point,

radiance temperature (at melting point), and electrical resistivity

(above 2100 K) of zirconium by a pulse heating method. In

preparation

.

112
^napter /

Matrix Isolation Studies on the Reaction of

Iron Vapor with Oxygen

S. Abramowitz and N. Acquista

National Bureau of Standards

Institute for Materials Research

Washington, D. C. 20234

Introduction

The reactions of metallic vapor beams with oxygen species such as N2O, 0, O2, and O3, are often exothermic enough to populate electronically

excited levels of the diatomic oxides formed. Recently several groups

(1,2) have shown that reactions of Ba(g) with N 2 0 and O3 give high yields

of electronically excited BaO (on the order of 10% of the barium vapor

consumed results in photons emitted in the A-X system of BaO) . In order

to fully understand such processes and to evaluate them for possible use

as chemical laser systems a knowledge of the rates of all the reactions

involved and the nature of any chemical intermediates is necessary.

The methods of matrix isolation spectroscopy are particularly useful

for identifying possible intermediates in oxidation processes. The

infrared spectra of matrix isolated Ba0 2 formed by the reaction of Ba(g)

with O2 has been observed (3). Simple oxides of metals such as Pb(4),

Sn(5), Ge(6), Ni(7), Pt(8), Pd(8), Cu(9), Cr(9), Li(lO.ll), Na(12),K(13)

and Rb(13) have been identified using this method. In addition to these

species reaction of alkali metals (14,15,16) and some alkaline-earth metals

with 03/Ar (17) have given infrared spectra of matrix isolated MO3 species.

In some cases where the AH of reaction is sufficient to yield the monoxide

(when the metal vapor is reacted with 0 2 ) the monoxide, dioxide and higher

oxides are observed. Mole ratios of the observed oxides can often be con- trolled by the 0 2 /Ar (or other matrix gas) used. Such was the case for the

reaction of U( g) (18) and Th(g) (19) with 0 2 or N 2 0 where varying ratios of

U0, U02 and U0 3 (and ThO, Th0 2 ) are observed as a function of the 0 2 or N2 0

concentration. The U02 , UO3 and Th0 2 formed in these reactions have the same structures as those obtained by generating the metallic oxides using standard

Knudsen effusion techniques. The reaction of Fe(g) with 0 2 and N2 0 is reported

in this study. The reaction of Fe(g) with 0 2 to produce FeO is endothermic by

about 20 kcal/mole and is not expected to proceed. Rather a Fe0 2 species is

expected. The reaction of Fe + N2 0 to give FeO + N2 is exothermic by 60

kcal/mole and is expected to proceed.

Experimental

The experimental apparatus used in these studies has been described (18).

An Air Products closed cycle helium refrigerator was used to obtain liquid

hydrogen temperatures. Temperatures of the deposition holder were measured

using a hydrogen bulb thermometer and a gold-iron vs. chromel thermocouple.

113
A heater at the deposition plate allowed temperatures to be varied to

obtain good matrices and to carry out controlled diffusion studies. The

iron was vaporized from tungsten and molybdenum Knudsen cells. In some

of the experiments boron or carbon liners were used to minimize reactions

of the iron with the tungsten and molybdenum. Temperatures of the Knudsen

cell were measured using W 25% Re vs W3% Re or Pt vs. Pt/Rh thermocouples,

or in some cases an optical pyrometer. An electron beam furnace is used

to generate the iron vapor in the one to ten micron pressure range. Argon

and nitrogen were used as the matrix gases. Isotopically enriched oxygen

samples obtained from the Miles-Yeda company were used in some of the

studies

.

Infrared spectra were observed with a Perkin-Elmer model 99G mono- chromator equipped with either a 40 or 1502./mm diffraction grating for

the 500 and 1000 cm

-1 region. Interference filters were used to block

out higher order radiation. A Perkin-Elmer model 301 was used to obtain

infrared spectra in those parts of the 500 cm

-1 region where water vapor

lines are strong. Calibration of both infrared instruments is accomplished

with water and ammonia lines. It is estimated that the frequencies are good to ±0.5 cm

-1 in both regions studied with the 99G . The PE 301 spectra

observed in the 500 cm

-1 are probably accurate to +0.8 cm" 1

.

Results

The infrared spectrum of the product of the reaction of Fe(g) with

0 2 /Ar (1/100) is shown in Figure 1. The extent of reaction and/or the

absorptivity coefficient of the species formed is small since many hours

of reaction are required in order to obtain the spectrum shown. Spectrum

a is that of Fe(g) +

16 0 2 /Ar (1/100). The main peak in the spectrum is at

945.9 cm

-1

. Other peaks at 954.7, 969.5, 918.8 and 915.3 era" 1 are due to

polymeric features (or those possibly involving one iron atom and more than one 0 2 unit).- These features are increased in intensity relative to the

945.9 cm

-1 which diminishes in intensity when controlled diffusion of

the matrix at temperatures of about 30K is allowed to proceed. These features are also more prominent when lower dilutions of 0 2 /Ar are used. The

945.9 cm

-1 is extremely narrow with a Avj/p (on an absorbance scale) of

about 1 cm 1. In addition to this feature at 945.9 cm 1 another band

attributable to a low molecular weight species appears at 517.1 cm

-1

. This

feature also loses intensity at about the same rate as the 945.9 cm

-1

upon

controlled diffusion. Other weak features in the 300 cm

-1 region are not

reproducibly present and do not behave in a similar manner upon controlled

diffusion. The 517.1 cm

-1 feature is much weaker than its 945.9 cm-1 counterpart. A rough measurement of peak intensities indicate about a seven to one

ratio. The 517.1 cm" 1 feature appears to be also narrow, however due to its

weakness it is difficult to measure its half width.

An isotopically enriched sample of 0 2 was used in the spectrum b. The

oxygen contained 30.5% 180 2 , 19.5% 16 02 , 48.7% 16 0

180 and insignificant

amounts of 1

7

0 2 , 17 0

180, and 16 0

17 0. The single peak at 945.9 cm

-1 is

replaced with three peaks in the peak intensity ratio of about 2:5:3 at

114
945.9, 930.8, and 911.4 cm

-1

. (These spectra are direct reproductions

of those obtained on the PE 99G } which is a single beam instrument.

Therefore, the Io is not flat, but rather tends to increase in going to

higher frequency due to the blackbody characteristics of the Globar

source, transmission of the interference filter, and the diffraction

grating efficiency.) This ratio is in good agreement with that of the

isotopically enriched oxygen sample used. In the 500 cm

-1 region a feature is found at 508.1 cm

-

*

. The weakness of this feature precludes

the observation of the 517.1 cm

-1 feature in the same spectrum. Similarly it wasn't possible to observe the feature which will be seen to

be assignable to Fe 18 0 2 in this spectrum.

In order to observe the features due to Fe 18 02 it was necessary to use an isotopically enriched * 8 0 2 sample con taining 86.0% 1

8

0 2

, 12.2%

16 0

18 0, 0.4% 16 0 2 , and similarly insignificant amounts of 17 0* 80, 17 0

160

and an 17 0

16 0 and an 170 2 concentration about two orders of magnitude

smaller. The spectrum in Figure lc is that of the product of the reaction

of Fe(g) with this oxygen sample diluted in 50 parts argon. The 911.4 cm

-1

feature assigned to Fe* 8 0 2 is prominent in this spectrum. The 930.8 cm

-1

feature, assignable to Fe* 6 0

180 is also clearly seen. The intensity of

this feature relative to that of Fe 18 02 is approximately 7:1 in agreement

with the isotopic abundances of 1

8

02 and 16 0* 8 0 in the isotopically enriched

oxygen sample used. A peak at 494.0 cm

-1 was also found. As was the case

in the experiments with the sample containing 48.7% 16 0

18 0 and lesser amounts

of the other isotopic varieties it was not possible to see any features due

to 160

180 in this region. The low intensity of all the features in the

500 cm

- * is responsible for this. It might be added for completeness that

these low intensities only allowed controlled diffusion experiments to be

performed with the 16 0 2 sample. (This is the only sample containing essentially 100% of one isotopic variety of oxygen.)

In a separate set of experiments the reaction of Fe(g) with N 2 0/Ar has

been studied. FeO is the principal product of this reaction and was found

in the argon matrix at about 880 cm

-

* in good agreement with the gas phase

value derived from its electronic spectrum. Another peak located at some- what higher frequency is also observed. It is believed this peak is assignable to a Fe-nitrogen complex, possibly FeN 2

. However a proof of this and

elucidation of the bonding obviously requires isotopic studies; utilizing

N2 and 14N

15 N.

Discussion

A M02 species can either have a side-on or end-on structure.

M-0=0 M

0=0

end-on . , side-on

The side-on structure shown is a monodentate model while an isosceles

triangle structure is

115
0 0

also possible. Both limiting models of the side-on structure have

structure. The end-on structure will either have C or C symmetry

depending upon whether the molecule is linear or ben^ . Enl-on structures

have been found for several metal nitrogen complexes. The spectrum

expected for the end-on and both limiting cases of the side-on models

in the 0-0 stretching region are shown below for a 1:2:1 mixture of

M

16 0 2 , M

16 0180 and M* 8 0 2

.

M

lb 0ia0 end-on

side-on

A three line spectrum with an intensity ratio of 1:2:1 is expected for

a side-on model. The central component shows the spectral equivalence

of the mixed isotopic species for this model. The end-on model gives a four line spectrum with a closely spaced doublet with absorption intensities in the ratio of 1:1:1:1. The inequivalence but equal probability of

M

18 0180 and M

18016 0 results in a small separation and equal intensities

of the central doublet.

The MO stretching region would show either a triplet or quartet for

side-on and end-on models of MO2 respectively. These modes are expected

to be as shown below for an isotopic abundance of 1^02 : 2* 6 0* 8 0: 1 18 0 9 .

M

16 02 M

1 8 0, M

16 0 2 M16 018 0 M180

16 0 M1802

M^O 1 °0

side-on end-on

The side-on model would exhibit the same type pattern as shown for oxygen

stretching region. The end-on model (be it C or C symmetry) is expected

to have two closely spaced doublets with no absorption in between. The

spacing of the doublets is expected to be small since only a small

frequency difference is to be expected in the MO stretching between the

pairs of molecules M

16 0

160 and M* 6 0

18 0, and M180

18 0 and M

l8016 0.

The observed spectrum in the oxygen stretching region has been shown

in Figure 1. The three lines observed are in the proper intensity ratios

for a side-on M0 2 molecule. The reduction in the observed frequency from

the 1060-1120 cm

-1 region expected for 0 2 seems to indicate some charge

116
transfer from 0=0 to the MO bond. The narrowness of the Fe 16 0

180 feature

which appears to have a Avi/ 2 of about 1 cm

-1 would make the presence of

another unresolved component to the doublet (as would be required for end- on bonding) improbable.

The M-0 stretching modes in the 500 cm

-1 region have already been

discussed. The weakness of these modes made diffusion experiments difficult for all but the 16 02 case. It was also not possible to observe all

the modes of the three isotopic species Fe 16 0 2 , Fe 16 0

18 0, and Fe 1802 in one experiment. Three separate experiments were necessary to obtain the

modes of the three isotopic species. Despite these difficulties, however

it should be noted that a synthesis of the three observed spectra gives a three line spectrum with features at 517.1, 508.1 and 494.0 cm

-1

. This

pattern is expected for a side-on model of Fe02 • It should also be noted

that the relative intensities of the 517.1, 508.1 and 494.0 cm

-1 to their

counterparts at 945.9, 930.8 and 911.4 cm

-1 are approximately the same for

each pair. This coupled with the controlled diffusion experiment, possible

with only the Fe 16 0o sample, showing similar ratios of disappearance of the

945.9 and 517.1 cm

-

* features lends some confidence to the assignment of the

0-0 stretching mode and an Fe-0 stretching mode of a side-on Fe0 2 molecule.

A detailed assignment of the observed vibrations of Fe02 to normal modes

is not possible since only two of the three vibrations have been observed.

Prolonged periods of deposition of Fe(g) + 0 2 /Ar have not yielded any other

features assignable to Fe02 . It is expected that the missing fundamental

which is a Fe-0 stretching mode is at a lower frequency than the observed

517.1 cm

-1 for Fe 16 02« The observation of only two vibrational modes is

not unexpected. Of the previous molecular complexes of this type observed,

three modes have been observed for only alkali dioxides such as Li0 2. Indeed

for most of the molecules studied such as Pd0 9 , Ni0 9 etc., only two modes

have been observed for the M^C^ species. Two modes have also been

observed for Ba^02 and Ba^fy^ and only a BaO stretching mode for Ba 180*ko. The ratio of the observed frequencies for

the 0-0 stretching mode of Fe 180 2 and Fe 160 2 911.4/945.9 = 0.9635 is considerably greater than 0.9428 expected for a pure 0-0 stretching mode. This

indicates that this vibration is mixing with an FeO stretching mode. The

product rule for v 2 of a C^v XY 2 end-on model is

i i

v2

2my + m

i x

2 my + m

f 2 1 my mx

2 m m

1 y-r x J

0.9089

1 a i fi The observed ratio for (v^ v 2 ) Fe O2/ (v^ V2) Fe O2 is

vj v 2 ~~i i

vj v 2

(911.4) (494.0)

(945.9) (517.1)

= 0.9205

117
This is larger by about 1.3% than the ratio expected for harmonic vibrations. An alternative assignment of the 494.0 and 517.1 cm

-1 features

as due to V3 the asymetric stretching mode of a C model is not very

satisfying. Using these two frequencies an O-Fe-0 angle of 87.3° is

computed. This angle is larger than one would expect for such a molecule.

A summary of the results obtained is given in Table 1.

There have been several solid and liquid phase studies of the molecular complexes of oxygen and hemoglobin type molecules. These studies were designed to elucidate the bonding between oxygen and iron in hemoglobin.

A preliminary report on an X-ray diffraction study of a model porphryn

molecule seems to indicate end-on bonding with a bent Fe-0-0 bond (21).

Some infrared (22) and resonance Raman spectroscopic studies (23) would

seem to support this view. Both the infrared and Raman studies only inves

tigated 16 02 and 18C>2 samples. As was seen in the 0-0 stretching region

previously, both end-on and side-on bonding WOuld give similar spectra.

The spectra of the mixed isotope, 1& 0

180 bonded to Fe would clearly distinguish between the two proposed models in these condensed phases.

Conclusion

Spectra of the molecular complex formed by the reaction Fe(g)

with oxygen have been studied by the methods of infrared matrix isolation

spectroscopy. Spectra were observed using both normal and isotopically

enriched oxygen samples. While a complete spectrum was not obtainable

due to the weakness of the observed bands the weight of evidence is

indicative of a side-on isoceles triangle (C„ ) model for FeOo.

zv

Table 1

Observed Fundamental Modes for Fe02(cm-1

)

Assignment Fe 16 p? Fe 16 Q? Fe 16 0

180

911.4 930.8

494.0 508.1

0-0 Stretch 945.9

Fe-0 Stretch 517.1

118

References

1. C. R. Jones and H. P. Broida, J. Chem. Phys . 59, 6677 (1973).

2. D. J. Eckstrom, S. A. Edelstein, S. W. Benson, J. Chem. Phys.

60, 2930 (1974).

3. S. Abramowitz and N. Acquista, J. Res. NBS 75A , 23 (1971).

4. J. S. Ogden and M. J. Ricks, J. Chem. Phys. 56, 1658 (1972).

5. J. S. Ogden and M. J. Ricks, J. Chem. Phys. 5_2, 352 (1970).

6. J. S. Ogden and M. J. Ricks, J. Chem. Phys. 53, 896 (1970).

7. H . Huber and G. A. Ozin, Can. J. Chem. 50, 3746 (1972).

8. H. Huber, W. Klotzenbucher , G. A. Ozin, A. Vander Voet, Can.

J. Chem. 51, 2722 (1973) .

9. J. H. Darling, M. B. Garton-Sprenger , J. S. Ogden, Faraday Symposium,

In proof.

10. L. Andrews, J. Chem. Phys. 50, 4288 (1969).

11. L. Andrews and R . R. Smardewski, J. Chem. Phys. 5_8, 2258 (1973).

12. L. Andrews, J. Phys. Chem. 73, 3922 (1969).

13. L. Andrews, J. Chem. Phys. 54, 4935 (1971).

14. M. E. Jacox and D. E. Milligan, J. Mol. Spectroscopy 42, 148 (1972).

15. R. C. Spiker and L. Andrews, J. Chem. Phys. 59, 1851 (1973).

16. L. Andrews and R. C. Spiker, J. Chem. Phys. 59, 1863 (1973).

17. D. M. Thomas and L. Andrews, J. Mol. Spectroscopy 5j0, 220 (1974).

18. S. Abramowitz and N. Acquista, J. Res. NBS 78A, 421 (1974).

19. N. Acquista, S. Abramowitz, M. Linevsky , to be published.

20. Certain commercial instruments are identified in this paper to

specify completely the experimental procedure. In no case does such

identification imply a recommendation or endorsement by the National

Bureau of Standards.

120
21. J. P. Collman, R. P. Gagne , C. A. Reed, W. T. Robinson, G. A.

Rodley, Proc. Nat. Acad. Sci. 71, 1326 (197A).

22. C. H. Barlow, J. C. Maxwell, W. J. Wallace, W. S. Caughey, Biochem.

and Biophys. Res. Comm. 5_5, 91 (1973).

23. J. S. Loehr, T. B. Freedman , T. W. Loehr , Biochem. and Biophys.

Res. Comm. 56, 510 (1974).

121

e
Chapter 8

Studies of the Reactions of Ba(g) with O3

W. Braun, M. Kurylo, S. Abramowitz

The kinetics of the reaction of Ba(g) with ozone is being studied

using modulation techniques. By exciting ozone vibrationa 1 ly with a mechanically chopped monochromatic carbon dioxide laser, one can measure

several parameters. In addition to being able to measure the ratio of

the rates, k, and k„

Ba(g) + 0^ -» BaO + 0 9 + hv

Ba(g) + 0

3

-* BaO + 0

2 + hv

one can measure (by using a suitable multichannel analyzer) the rates

of growth and decay of luminescence (produced by the reaction) in the

millisecond time regime. In this way, one can in principle measure the. rates of production and loss of the various excited species that may

be present in the flame.

The projected experiments will measure these variables as a function

of argon pressure, in order to try to elucidate the proposed mechanisms.

The luminescence will also be passed through a fast monochromator in

order to investigate its wavelength dependence as a function of argon

pressure and time.

Very preliminary data using the total luminescence obtainable from

the reaction indicate a rate enhancement when vibrationally excited ozone

is used . In these experiments pressures of barium in the ten micron range

are used. The barium is driven by Ar through a resistively heated

1/4" O.D. stainless steel tube into a small reaction chamber. The ozone which is generated, using a commercial ozonator, is vibrationally pumped

with the P. line of a CC>2 laser. Chopping speeds are used such that

a full on-orf wave of 10 milliseconds is investigated. Argon pressures

of about 5 torr were utilized in the initial experiments.

122
Chapter 9

DISSOCIATION ENERGIES OF THE SCANDIUM GROUP AND

RARE-EARTH GASEOUS MONOXIDES

Ralph F. Krause, Jr.

Abstract

The dissociation energies of the scandium group and

rare-earth gaseous monoxides are evaluated by reviewing

the literature available on Knudsen effusion rates and

mass-spectrometric data. The rate of effusion data for

vaporizing the solid sesquioxides to form gaseous monoxides

and monatomic oxygen are corrected for the presence of other

vapor species. These include metal atoms, dioxides, diatomic

oxygen, and oxides of the container and except for the metal

atoms were not considered in the original sources. The

results from various sources are compared by using the same auxiliary data which are needed to derive the dissociation

energy of each monoxide. Selected values of thermodynamic

properties are provided for all of the vapor species and

solid sesquioxides under consideration. Corrections of the

rate of effusion data for the presence of neodymium dioxide

are found ambiguous. Using the dioxide data from one source

leads to a molar ratio of dioxide to monoxide near unity.

From another source the dioxide data, though inconsistent with

the rate of effusion data, indicates this molar ratio to be negligible. This ambiguity suggests that the extent of forming this

dioxide and perhaps others should be examined further. When

a tantalum container is used, corrections of the rate of effusion

data for the presence of tantalum oxides are found substantial

in all the cases of the sesquioxides effused. When a tungsten

container is used, corresponding corrections appear appreciable

only in the case of europium sesquioxide whose effusion also

appears to require an appreciable correction for diatomic oxygen.

Corrections for the presence of metal atoms seem negligible

in most cases, but they are appreciable in the effusion of the

sesquioxides of europium, thulium, and ytterbium. Finally,

differences between dissociation energies of several pairs of

monoxides are compiled from published mass-spectrometric

studies of isomolecular oxygen exchange reactions.

123
I. Introduction

The scandium group and rare-earth metals L appear as possible

candidates for chemical lasers in the visible spectrum. Consider

the bimolecular gaseous reaction,

in which XO may be N2O or 0-,. A test for a metal atom to be a candidate is that the monoxide is formed in an excited state which

has an excess energy equivalent to an electronic transition in the

visible spectrum, namely more than 40 kcal mol~^. These metal monoxides

meet this criterion because their dissociation energies are greater

than the sum of the above minimum transition energy and the dissociation energy of either XO.

Values of the dissociation energies D° , corresponding to the

all gaseous reaction,

are provided in table 1. The last column gives values obtained from

the present work; details are given in subsequent sections. Other

columns give values reported earlier in other compilations. Those

of Suchard (1974) and Rosen (19 70), are both primarily collections

of spectroscopic data. Although Schumm et_ al_. (1973) made selections

from among published values which they adjusted to be consistent

with their values of the heats of formation of related compounds, the

documentation of their efforts has yet to be published. Brewer and

Rosenblatt (1969) estimated Gibbs free energy functions for the

gaseous monoxides and recalculated dissociation energies from the

published values of selected equilibria measurements. Ames et al.

(1967) performed an extensive series of measurements. They used the

Knudsen method to study the vaporization of sesquioxides and mass- spectrometry to study several isomolecular exchange reactions.

Determining accurate dissociation energies from weight-loss and

mass-spectrometric data is fraught by several difficulties. An

erroneous assessment of the vapor composition could made an otherwise

accurate set of weight-loss data become misleading. It appears that

earlier investigators failed to consider adequately the possible

effects that the presence of gaseous dioxides might extend. Other errors in weight-loss data will result from vapor unsaturation and

also from reactions between the sample and its container. Reliable

results from ion intensity data depend upon identifying the ion which

was produced by electron impact and properly selecting its molecular

progenitor. While temperature dependent errors limit the accuracy of

results obtained by the 2nd Law method, errors in the Gibbs free energy

functions will cause a systematic dispersion of results obtained by

L + XO -> LO + X (1)

LO -+ L + 0 (2)

124
r+i

CJ ASo

(J o oQ

4-1 3

CD A! rH

O rH

O oo VO rH o ON

O o m o CM

COU VO on ON vD 0 <r co VO r--»

m

mm CO o vD

0)O rH rH rH rH rH rH rH r-l rH rH rH rH rH rH rH rH

ri rs

m• T3 «-n CM CO CO CO CO CO CO CO CO

>-i <r 3 r- +1 +1 +1 +1 +1 +1 +1 +1 +1 X ON 1 00 1 1 1 1 1 1 CJ rH CO o CM m 3 v-^ • • • • • • • CO O o o CO 00 CM CM CO CM vO

vO on ON r- <r co

m vO

rH rH rH rH rH i-H rH rH rH rH

U• s~\

4J|CO •a 4H on m vo CM CM r~- cm sr co CO o CO rH oo a 1-1 • B N—* CN CO o O CM r-«. 1 ON CM rH rH oo co 00 CO 1 VO VO ON ON 00 vO CO CO 1— <r m <* co vO rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH w "cc]| m in

CM • CM • CM CO CO CO CO CO CO CO co CO CO CO CO e o +1 +1 +1 +1 +1 +1 +1 +| +1 +1 +1 +1 +1 +1 +1

0) r-. I CO on <f <r co o r~- m rH 00

O r- r» CO co r-~ 5 H

Pi ^ o o o CO rH CM CM CO CO co o CM rH ON 00 vO

vO ON ON 00 r- co r- in

m in CO 00 vO

rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH

*J on

O o o O

mm

Qj|vO

mmm 00 00 CO rH VO 00 rH rH rH rH rH 00

ON

rl rH +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1

CO | 1 •* rH ON r~- CO ON rH Jm 00 VD rH 00 m VO 00 VO CO CM VO VD <r CM ON m

rH rH rH rH rH rH rH rH rH rH rH rH rH rH

PQ cd|

mmmmmmmmmm

m

mmm

m

m

4J VO +i +i +i +i +1 +1 +1 +i +1 +1 +1 +i +1 +1 +i +i

CU ON

i-H rH 00 CM CM

m o r- o r-» CO co r^. CO ^£ • m rH CO CO rH CM © CM CO CO co o CM rH ON oo vo 9 j_i i VO r- ON ON 00 vO o- CO m m m co 00 vo

i-H rH rH rH rH rH rH rH rH rH rH rH rH rH rH

V rH

m

CM

i—l

m

m 3

co CM CM

mm co CO

O 00 +1 +1 +1 +1 +1 +i +1 +1 +i T3 VD

>-. ON ON

m 1 1 1 1 1 1 3 rH • • O 00 ON m rH -vl- rH m CM vO vO oo 00 vD VO CM

rH rH rH rH rH rH rH rH rH

0) "3aso o o o o o o a o 3 <u u t3 8 W >h ,j O Ph S3 Ph o o o o o o 3 -3 Xi O M W O H Q X W o o

00

St

II

ct) o

VDo

co

CM

or A

CD3

T3

a) 4Ju%oo

a;u

0)&

ajou3o

CO

CU

<4-l o

CO9

rH>

a)

a) fj

M-lo3O CU •H o

4J

u

Cfl 3 e o

CO o

<4H CU ,3

4H 4J O

>N

CO rO

4J

CO •3

CD CU J= 4JO

CU CU rH

CUco

co

CU3

rH

C3>6ou

l*H •3

CU3odo

CU

rl

CUS

CD iH3

82 •H

00

CO

CU3

rH^

CU

CU

rl

CU&

sio

•H&3

CU00

5?oBo

4J

n3

CUS

co3O

CU

CO3

00

•3

«HXo3oB

ON

ail

eg3O

aico3 3 3Oyo

CD

CU 5

rl60

-a

cuo3

«H3

4-1 3

co3&O

iH•is

rH3>

*33

4Ja

•H3

CUu3

co

m

rH• CO

ON

CNI

4J

COaH

cti >

125
the 3rd Law method. Although It is beyond the scope of this paper

to examine the extent of all these errors, an attempt has been made

to become critical of some.

II. Weight-Loss Vaporization of Sesquioxides

Several investigators have studied the vaporization of the sesquioxides by weight-loss methods, including Knudsen-ef fusion in tungsten,

tantalum, or rhenium cells, Langrauir-tors ion in molybdenum cages, and

entrainment in a container of the sample itself. In many cases investigators had assumed that the vaporization process occurred practically

as

Even though reaction 3 may not be a practical process for evaluating

the weight-loss data of all the sesquioxides, it will be taken in this

paper as a convenient reaction whose equilibrium will be evaluated.

Vapor pressure measurements as a function of temperature are meaningful if the chemical system Is univariant. When the sample container

is excluded, one may realize from the Gibbs Phase Rule that a two com- ponent system will be univariant if three phases, for example two solids

and the gas phase, are present. Although White et al. (1962) perceived

by x-ray powder analysis only a single solid phase during the complete

process of vaporizing each of several sesquioxides, the composition of

this phase remained constant for a particular sesquioxide and varied

among them from 2.96 to 2.99 atomic oxygen per 2 L. White et al.

also observed constant effusion rates between the limits of 20 and

80% of sample vaporized. Consequently, it appears that these sesquioxides vaporize as azeotropes, making a two component system univariant.

If the solid-phase were a mixture of L2O3 and LO, the mol fraction of

the latter would appear as high as 0.077; and if the solid phase were an ideal solution, this mol fraction would be the error in the pressure of

L0(g). It can be shown that for measurements at 2500 K a correction

for this error would lower the calculated dissociation energy by 0.6

kcal mol~l.

In accord with reaction 3, weight-loss data alone would uniquely

define the vapor composition if the vapor contained only two gas

species. In general, "the vapor may be considered to contain many

species -for which an investigator should account. When a sesquioxide

is, for example, in a tungsten container, vaporization may be expressed

as

L

2 0

3 (s) -> 2 L0(g) + 0(g). (3)

L

2 03

(s) + n WOi) "> a 0(g) + b 0

2 (g) + c L(g) + d L0(g) +

e L0

2 (g) + T. k± W

x

0 (g) + ... (4)

If reaction A is assumed to vaporize congruently, a mass balance

provides

c + d + e + = 2 (5)

126
a + 2b-fd + 2e + £ y k + . . . - 3 (6)

and

£ x

jL k1 = n (7)

The vapor composition of more than two gas species is not defined by

weight-loss data unless other data are available to relate all the

variables. Table 2 gives thermodynamic values for several equilibria

which involve gas species implicated by reaction 4.

One of the gas species which remains undefined is the metal atom.

Table 3 shows that the mass-spectrometric ion-intensities from sesquioxide vaporization indicate that the L /L0+ ratio has two cycles of

increasing values for the series of rare earths including lanthanum.

These values might be on the high side because the high ionization

potentials which were used might have fragmented the L0+ . Ackerraann

et al . (1964) point out that some caution must be exercised in evaluating a meaningful L+/LO+ ratio, which they believe cannot be obtained

at a single arbitrarily selected electron energy. Using ionization

efficiency curves, they observed a saturation plateau for Y+

at approxi

mately 10-12 eV and for Y0+ at approximately 20 eV; from these they

evaluated the Y

+ /Y0+ saturation ratio to be 0.015, which is about 1/4

that observed by Ames e_t al. Extrapolating these curves to zero intensity they found appearance potentials of 5.5 and 6.0 eV for Y0+

and Y+

, respectively. If they had observed an appearance potential for

Y near 13 eV, one would have suspected its presence due solely to

fragmentation of Y0+

, which their ionization efficiency curve showed

to be appreciable above 20 eV. Conversion of a ratio of ion-intensitie

to a ratio of pressures in the last column of table 3 depends on the

proportionality of the following relation

P

jL « I 1

+

T/a

i (8)

in which is a cross-section for detection of the species i in a particular instrument. +

Using rate of effusion data, Ames et al.

(1967) deduced for Y , YO , La+ . and LaO+ with respect to that

of Ag+

. The results for the L+/L0 ratio of cross-sections averaged

1.6 with a difference of 0.2. Although the values in the last column

of table 3 may be useful for comparison, a preferrable method, which

is similar to one used by White et al . (1962), provides a relationship

between the pressure of a metal atom and the published data for the

atomization of its sesquioxide.

L

2 0

3

(s) + 2 L(g) + 3 0(g) (9)

and this method will be described below.

The weight-loss method which was predominantly used for the sesqui

oxide vaporization measurements in the literature was the Knudsen

effusion method. At temperature _T the vapor pressure for a vapor

species of molecular weight is obtained from

127
Table 2* Some Equilibria Involved with the Vaporization of Sesquioxides.

Reaction 6 AHq A[-(G°-Hn)/Tl/cal moj~V^ Ref« Vpal TTinl

^"

i\ La 1 UlUl 2000 K 2200 K 2400 K 2600 K

2 0 + 0

2 -117.98 -29.91 -30.10 -30.26 OA /.I -30. 41 a

Nd + Nd0

2 * 2 NdO - 10.5 4.01 3.96 3.65 3.07 b

NdC>2 * NdO + 0

c 101 26.93 27.01 27 .06 Z/.ll

Ta(s) + 0 + TaO - 6.88 7.24 6.95 6.69 6.44 d

Ta(s) +20+ Ta0

2 -163.93 -27.10 -27.41 -27.67 -27.90 d

W(s) + 0 -y WO 42.74 9.41 9.11 8.84 8.57 a W(s) + 2 0 -> WO

L -99.10 -20.02 -20.41 -20.76 -21.08 a W(s) + 3 0 -* W0

3 -245.92 -57.65 -58.04 -58.38 -58.69 a

2 W(s) + 60 + (WO.). -630.70 -146.71 -147.03 -147.31 -147.56 a

3 W(s) +80+ W O

g -878.30 -212.72 -213.15 -213.51 -213.84 a

3 W(s) +90+ (W0

3

) 3 -1011.56 -247.87 -248.30 -248.65 -248.97 a

4 W(s) + 12 0 + (WO a

). -1374.59 -344.85 -345.27 -345.61 -345.92 a

aStull and Prophet (1971).

Pupp and Gingerich (1971).

Calculated by the 3rd Law from the Kp data of Staley and Norman (1969)

dSchick (1966).

Gaseous species except where noted.

Table 3. Ratio of Mass-Spectrometric Ion Intensities from Vaporization of the Sesquioxides.

T

Solid Panish (1961), Shchukarev & Semenov (19617

20 eV 10 eV 45 eV

Ames et. al. (196 Tj~

25 eV

Average PT /P a L LO

SC2°3 l/8

b 0.2 0.16 0.1

Y2°3 1/16 0.06 0.04

La2°3 0.16 <0.01 0.08 0.05

Ce2°3 0.20 0.2 0.12

Pr

2 0

3 <0.1 0.36 0.2 0.1

Nd

2 0

3 <0.1 0.25 <0.01 0.1 0.06

Sm

2 03 0.5 to 1.0 1.3 1.0 0.5 0.9 0.6

EU2°3 8±2, 9±1 7 5 10 9 6 Gd

2 0

3 <0.1 1.2 0.3 0.5 0.3

Tb 2°3 <0.1 0.9 0.2 0.4 0.3

Dy

2o3 0.4 1.7 0.5 0.5 0.8 0.5

H°2°3 1.0 2.2 1.3 0.5 1.2 0.8

Er

20

3 1.5 ± 0.5 1.4 1.0 0.5 1.1 0.7

Tm

20

3 15 ± 5 10 10 12 8 Yb

203 (>30) >50 50 30

Lu

2 03 . <0.1 1.7 1.1 0.5 0.8 0.5

The ratio of cross-sections (L+

/L0+

) was assumed as 1.6; see text.

^Semenov (1965). 128
P = w

i

V2 RT/M /(tBW

b

f) (10)

in which is the mass of species i that effuses in time _t through

an orifice with a Clausing factor and an area IS. The value of

the constant R is (8. 314 34)10 7 erg K-lmol-1, and 1 atra is (1.01325)106

dyn cm~2. Paule and Margrave (1967) show that the fraction of

saturation _f of the vapor in a Knudsen cell with a Clausing factor

W_ and an area A may be estimated by

f = [1 + (BW,/A)(a

_1 + W"

1 -2)1

_1

(11)

D a in which _a is the vaporization coefficient of the condensed sample.

Values of Clausing factors are tabulated in an appendix of reference

35 as functions of the length and radius of a cylinder. The mass w^

of species i^ is related to the total mass w of sesquioxide of molecular

weight M by

w

± - w k M

1 /M (12)

in which k^ is the coefficient of a vapor species in reaction 4.

When eq. 10 is used to calculate a hypothetical Knudsen corres- ponding to the w and M of a sesquioxide,

P

i = ki

P

k VVM (13)

Using eq. 13, the k^ of species i may be expressed as a function of

a known Kp for a reaction in which the species i is also involved; for

example in the case of a metal atom L in reaction 9

c = K

p

^ /(a P k

^ ) (14)

The K of a reaction at a given temperature is calculated from the

corresponding AHg and A [-(G°-Hq) /T] as

K = exp{A[-(G°-H°)/T]/R - AH«/(RT)} (15)

p u u In like manner the procedure of the preceding example may be applied

to other equilibria, such as those in table 2, which contribute to

the definition of vapor species in reaction 4. After values of a and

<i are evaluated by simultaneous solution of eqs. 5 and 6, the Kp of

reaction 3 may be calculated simply as

K

p

(3) '

P

L0

2

P

0

(16)

129
in which the _Pjl are determined by eq. 13. When the Langtnuir method

is employed, eq. 13 could also be used since it involves using the

Y^i term of eq. 10 similar to the Knudsen method. If reliable Ffc data as a function of temperature are available, the d(£n P]c )/d(l/T)

could be applied to define an unknown variable in eqs. 5 and 6.

In principle the entrainment method offers yet another means to

evaluate an unknown variable in eqs. 5 and 6 when it is combined with

the Knudsen method. In practice, however, experimental imprecision of

the two methods often outweighs any meaningful contribution. The

entrainment method, which is truly a vapor density measurement, would

result in defining the pressure of vapor species i_ as

P

t = (w /V)RT/M (17)

When eq. 17 is used to calculate a hypothetical entrainment Pg

corresponding to the w and M of a sesquioxide,

P

t = kt P

e (18)

which is analogous to eq. 13.

III. Auxiliary Data

The published data necessary to evaluate the Kp of reaction 9 are assembled in tables 4 and 5. Holley et al. (1968) nad reviewed

extensively the published thermodynamic data for the sesquioxides.

Table 4 includes some revised values which have been measured recently.

The values of (H°-Hq) and -(G 0 -Hq)/T in table 4 are extrapolations

which were calculated using expressions of the form

(H°-H° ) = A + BT + CT

2 + D/T (19)

which Holley et a_l. had determined from relative enthalpy data.

Holley e_t al^. had selected the coefficients J) so that the high temperature data joined smoothly with the low temperature heat capacity

data. Since the sources in table 5 gave values of the Gibbs free

energy functions with respect to 298.15 K, they were appropriately

adjusted to zero Kelvin.

Since reaction 9 is the sum of reaction 3 and twice reaction 2,

the dissociation energy of a monoxide is related as

D°(L0) = [AH°(9) - AH°(3)]/2 (20)

130
00 ON NO

CO NO NO NO

oo co in co

rr

coo

no no on

NO NO no

co oo co m

NO nO NO

ON OO CM 00 On

r-4 NO NO OV 00

on oo oo oo r>.

J •* HO

i** co <t N 00 O r(

in in oo

NO NO NO nO no m

NO nO nO NO NO NO m

oo oo oo

oo en en no

no cn no

O m m

co co . co

oo oo oo oo m

ON no r*i

-a

>> O 0) 4-1 X. J2 in CM r- CM in 00 ON 00 00 CM in <t m oo 01 T) o o o o O O o o o i—

1

o r-l o -f

re

01 U co

-II +i +1 +l 41 +1 +1 +1 +1 +1 +1 -i i -l-l +1 +'i CO ca CO ON

<t r-^ CI in <f ON

' ON NO CO m NO <f On t/i fi NO ?—

i

d 0) •o ON m 00 On CM CM m vf <t in m On CO 1—

1

CO oo <n c

in CM CM CO en ON CO vt m in co st 01 1-1 <!" <r <t <t CO <j- o- vt <J JSu >N

al

EC 3= SB )£ je o

CO CO CO CO CO CO CO O O O o O O o

CM CM CM CM CM CM CM

Ol u o 6 3 •o o P-J z CO W u H

co <r") CM CM CM

SI

31

o

3

-g m

CO 01 i—

I

01 CO

3= C

Oa j-> 01 £.oo H

0) .o3

1 3i
IW

t—

CM CM m <f CM 00 00 CM CO 00 in in 00 VD O c^ o m On O o in 00 CM CM E o OS 00 as o CM vD <f CM (—1 CO <^ oo CO as

t—

o

00 o co CM CM i—

O m m. CM CM r—

O o CO

ca CM <( in in m m m in in m in in m in in

a r-^ CM 00 00 r-l O <t 00 00 <t oo CM o oo CM

in r-l CO CM o 00 as CO r-- O O

o CM O sD in 00 o <f m o as co CM as as CM o o

o \D 00 as CM O o Os CM CO O as m as CO

CM <t m in m in <t m m in m in <t <t

O CM 3

oo si

i-( r-4 -CM

as -d oo co in as (—i CM 00 CO o as 00 CTN m 00 CM 00 00 00 00 00 00 o

in in -d as <r 00 <r <t <J- <t vO

t—

r—i—

i—

i—i—

CM <t

in m in m CM in m CO

i—O o o CO o O o O o O i—

o iH r—

-I I +1 +1 +1 +1 •) 1 H 1 +i -I I •11 1

+1 II +1 •1 1 +1 as

CM m CM m

CO in o o O CO d- as o as <t as 00 in CO m

CM o CO t—

in 00 as m CM as i—

in in sD O as

0> O o o 00 <t as c^ r- in CO i-l m

t-i as

3 c^

SI

131
The 2nd or 3rd Law Method may be used to obtain the of reaction 3

from measured values of the corresponding^. I f _Kp data are available

as a function of temperature, the 2nd Law would give

AH° - -ft[d(in Kp)/d(l/m - A.(Hj-H°) (21)

in which values of (HTM-H°) for atomic oxygen were obtained from Stull

and Prophet (1970) ana values of (H£-H°) for all these monoxides were obtained from Ames et. a_l. as 16.82, 18.59, 20.37, and 22.15 cal mol" LK

at 2000, 2200, 2400, and 2600 K, respectively. At a given temperature

the 3rd Law gives

AHj = T |a[-(G°-H°)/T]- R in K } (22)

in which values of -(G°-Hq)/T for all these monoxides were also

obtained from Ames e_t. a_l. and are given in table 6. Differences in

the results of the two methods indicate either errors in K , in its

derivative with temperature, or in the auxiliary thermodynamic functions.

The -(G°-Hq)/T values in table 6 are those used in the present work,

but they appear somewhat uncertain. Table 7 shows -(G°-H°)/T values

which were estimated either by Ames e_t. al . (1967) or by Brewer and

Rosenblatt (1969). Using the values of the latter would lead to values

of dissociation energies which are approximately 6 kcal mol" smaller

than those derived from table 6. Both sources appear to have selected,

respectively, similar ground state vibrational frequencies for all the

rare-earth monoxides, and these estimates are approximately the same as those which DeKock and Weltner (1971) observed recently in the infrared

between 808 and 832 cm" by matrix isolation.

The major cause of the discrepancy is that the above two sources

chose different electronic multiplicities for the ground and lowlying states. These multiplicities affect mainly the entropy of a monoxide. While both sources reported using a divalent-ion model for

the electronic partition functions, Brewer and Rosenblatt used higher

multiplicity values; for example, with ScO Ames e_t.a_l. considered only

the ground state and assumed it to have a multiplicity of 2, whereas

Brewer et . al . used 4 along with that of 6 for an assumed low-lying

energy level which they took as 197 cm"*, the value for the divalent

ion. The values of Ames et . a 1 . are nevertheless preferred. Approximate

wavefunctions for ScO were calculated by Carlson e_t. al . (1965) who

concluded that 2^ is the ground state of the molecule. Kasai and

Weltner (1965) presented experimental evidence which they believed was conclusive that ScO, YO, and LaO all have ground states. Finally

Green (1971) presented evidence that the unobserved low-lying electronic

states of ScO, YO, and LaO can be interpreted using a model, but he

concluded that these states make no appreciable contribution to the

electronic partition functions.

133
Table 6. Values of the Monoxides

. Gibbs Free Energy Functions for the Gaseous

Oxide Electronic -(G*-H°)/t/ cal Tnol _1

K-1

Multiplicity 2000 K 2200 K 2400 K 2600 K

ScO 2 61.19 61.99 . 62. 72 A 1 10

YO 2 63.55 64. 35 65 .09 A ^ 77

LaO 2 64.97 65 . 78 66. 51 £7o / • onzu CeO 3 65.71 66.52 67.25 0/i7J

PrO 4 66.37 67. 18 67.92 Aft AH

NdO 5 66.86 67.67 68.41

SmO 7 67.66 68.46 69.20 AQ ft A

EuO 8 67.96 68. 76 69.50 / U • lu GdO 9 68.29 69.09 69.83 70 M

TbO 8 68.09 68.90 69.63 7fi 11

DyO 7 67.89 68. 70 69 .4 3 HoO 6 67.63 68.43 69.17 AQ ft^

ErO 5 67.31 68.11 68.85 AQ ^ 1

TmO 4 66.90 67.70 68.44 AQ 1 9

YbO 3 66.40 A 7 on 0 / . 74 Aft A 9

LuO 2 65.61 66.42 67.15 67.83

Reference . Ame s e t . a 1 . (1967).

Table 7. Differences in Dissociation Energies from Different Values of the Gibbs Free Energy Functions for the Gaseous Monoxides.

Oxide T/K -<G°-H°)/y cal mol K AD°(L0)

a

0 Ames et. al. (1967) Brewer et. al. (1969) kcal mol 1

ScO 2600 63.39 66.46 8.0 YO 2600 65.77 68.53 7.2 LaO 2400 66.51 68.79 .. 5.5

CeO 2000 65.71 68.90 6.4 PrO 2000 66. 37 53.

0

b

NdO 2400 68.41 54.

4

b

SmO 2400 69.20 71.5 5.5 EuO 2200 68.76 70.7 4.3

GdO 2600 70.51 72.55 5.3

TbO 2000 68.09 69.2 2.2 DyO 2600 70.11 72.4 6.0 HoO 2600 69.85 72.2 6.1 ErO 2600 69.53 72.0 6.4 TmO 2400 68.44 71.0 6.1 YbO 2400 67.94 70.6 6.4 LuO 2600 67.83 53.

6

b

'Calculated as Ames' value of [-(G°-H°)/T] less Brewer's value.

o Apparently an error in the source's text.

134
IV. Errors in Vapor Composition

A possibly serious systematic error in the calculations using

weight-loss data might exist if the formation of metal dioxides and more complex oxides are neglected. As shown above in table 2, Staley

and Norman (1969) and Pupp and Gingerich (1971) have studied equilibria

involving NdC^. Since their data will be shown to be disparate, the

extent of Nd02 formation is difficult to evaluate. The last column of

table 8 shows values of Dq for NdO which were calculated by varying

the AHq as shown in column 1. Corrections were applied for the formation

of diatomic oxygen, tungsten oxides, and the Nd atom, using the

sesquioxide atomization data. A value of AHq for reaction c_ that is as low as that shown in the last line of column 2 is inconsistent

with the rate of effusion data because there is produced P^d/^NdO < 0. In the next to the last line the mo 1 fraction of Nd02 is assumed zero.

If the data of Pupp and Gingerich were believed, one would judge from

the results in line 1 that Nd203 vaporizes practically as

Nd

203 (s) > NdO(g) + Nd0

2 (g) (23)

Also, the negligible amount of atomic oxygen shown in line 1 would

correspond to the fact that no tungsten oxides were detected mass- spectrometrically by Goldstein e^ a_l. (1961) . The presence of other

metal dioxides are apparent. De Kock and Weltner have observed

infrared spectra which they have assigned to CeCb, P r(^2» an<^ TbC^.

The extent of formation of these and other dioxides would help define

the vapor composition of weight-loss studies and provide more accurately calculated dissociation energies.

The use of mass-spectrometry to study equilibria involving

LO2 might entail some difficulties especially when too high an ionization potential is used. Using ionization efficiency curves

for CeO+and Ce02+

, Ackermann and Rauh (1*571), ref. 3, found appearance

potentials of 5.2 and 10.3 eV, respectively, based on the known 5.5 eV

ionization potential for Ce + . They found the onset of fragmentation

of Ce02 to CeO+at about 11 eV and of CeO to Ce+ at about+

13.5 eV.

After an interval of time they observed the amoun£ of CeO had

increased by a factor of 7 and the amount of Ce02 had decreased by

a factor of 2. A decrease in the pressure of atomic oxygen would

account for the shift of Ce02 to CeO. It seems entirely possible

that the use of mass-spectrometry could miss LO2 entirely unless

a sufficient pressure of oxygen were present.

Errors which result from sample reaction with its container appear

most pronounced when sesquioxides are vaporized in tantalum Knudsen

cells. Using the rate of effusion data of Kulvarskaia and Maslovskaia

(1960), eqs. 5 and 6 were solved simultaneously with and without

corrections for the tantalum oxides. The results are shown in table 9.

Corrections for diatomic oxygen and the sample-metal atoms, using the

atomization data for the sesquioxides, were applied; but the sample135
Table 8. Effect of the Uncertainty of Forming Neodymium

Dioxide Gas on Calculations Using Sesquioxide Rate of Effusion Data

c

Assumed Calculated Averaged Results ( 30 runs

2255-2434 K)

AH° (b) AH°(c)

P /P Mole Ratio per Nd,, 0^ (vaporized) D°(Nd0)

f

kcal niol ^ kcal mo 1

^" Nd NdO W (vaporized) 0(g) NdO(g) NdO (e) kcal mol ^

-io

d 148. 3 0.016 /„* ,„-5

(2)10 0.007 0.9 7 1.01 158.2 -20 141.7 0.002 (9)10-5 0.026 1.02 0.98 16l!7

-30 135.0 (3)10-^ c\ no/. 1.09 0.91 165.0

-40 128.2 (5)10"° 0.003 0.27 1.28 0.72 168.2 -50 120.9 (1.4)10" 5 0.012 0.56 1.60 0.40 170.9

(6)10-5 0.03 0.87 2.00 0 173.0

101e <0

aGoldstein et al. (1961).

C Nd0

2 (g) > NdO(g) + 0(g)

S Staley and Norman (1969)

bNd(g) + Nd0

2 (g) - 2 NdO(g)

dPupp and Gingerich (1971)

f Third Law values

Table 9. Effects of Correcting for Gaseous Tantalum Oxides on Calculations Using Sesquioxide Rate of Effusion Data

c

L

2 0

3 (s) Without Correction With Correction

PL

/P

L0

Mole Ratio

0(g)/L

2 0

3 (vaporized)

D°(LO) b VP L0 Mole Ratio per L

2 03 (vaporized) D°(L0) b

kcal mol

^ Ta(vaporized) 0(g) kcal mol

^

La2°3 io-9 0.61 208 io"6 0.58 0.0033 197

Pr2°3 io6 0.85 190 io-A 0.68 0.009 180

Nd 2°3 IO"

5 0.87 179 io"2 0.72 0.014 169 Sm^ io"

4

0.8'0 154 0.28 0.90 0.009 143 Eu2°3 io'

4 0.41 140 2.0 1.23 0.0032 125

Gd 177 2°3 IO"

6 0.91 187 io" 3 0.72 0.011

Dy

2 03 io"

4 0.94 164 0.11 0.94 0.021 155

Ho

2 0

3 io"

A 0.97 166 0.13 1.03 0.023 156

Er 2°3 io" 3 0.99 166 0.16 1.12 0.027 157

Yb

20

3 io" 3 0.76 138 3.1 1.44 0.010 123 Lu

2 03 io"6 0.90 19 3 ioA 0.76 0.012 183

^ulvarskaia and Maslovskaia (I960)

Third Law values.

136
metal dioxides were assumed absent. The general effect of correcting

for the tantalum oxides is to reduce the value of the calculated

dissociation energy by approximately 10 kcal mol~l. The correction

of course depends upon the pressure of atomic oxygen; so if the

formation of a sample-metal dioxide were appreciable, alternative

results would be obtained. Goldstein e_t a_l. (I960) detected no tantalum oxides mass-spectrometrically when they s tud led sesquioxide

effusion in a tantalum cell, but they observed that the total weightloss of the cell and sample exceeded the sample mass.

The effects that other assumptions have upon the calculations of

dissociation energies are shown in table 10. Here are analysed the

sesquioxide rate of the effusion data of Goldstein e_t al_. (1961) and

of Ames et al, (1967), both of whom had used a tungsten cell. The

variation in the calculated dissociation energy for LaO is

representative of those for the monoxides of Sc, Y, Nd, Sm, Gd, Dy,

Ho, Er, and Lu. Calculations using the effusion data for YD2O3

yielded negative P(L)/P(L0). In assumptions 1 through 4, the samplemetal atoms were corrected by the atomization data for the sesquioxides.

The first assumption, which is the one employed by Ames et al.,

considers that only the a, £, and d of reaction 4 are important.

The second assumption includes _b, and the third assumption includes

the for the various tungsten oxides. Assumptions 3 and 5 differ

in that the latter uses values in the last column of table 3 instead

of the atomization data. The P(L)/P(L0) calculated by assumption 3 for all the sesquioxides follows the same two cvclic pattern as table 3 except that assumption 3 gives them one or more orders of

magnitude smaller. Even though Ames ejt al_. detected no tungsten oxides

mass-spectrometrically, they did observe nearby 0.1 mole of

tungsten-loss per mole of L2O3. The results in table 10 indicate

that the corrections for the tungsten oxides have appreciable effects

mainly for the case of E^O^. This correction is confirmed to some extent by the results of Petzel and Greis (1971) who used iriduimlined Knudsen cells to study the vaporixation of EU2O3 in the presence

of W.

An approximation of the effect of vapor unsaturation in the Knudsen

cell is shown by assumption 4 in table 10. Although vapor unsaturation

produces a shift in the vapor equilibria of complex vaporization, the

approximation is based upon an estimate of by eq. 11. The cell

dimensions reported by Goldstein e_t a_l. (1961) and used by Ames e_t al. were such that A/B , V^, and were evaluated as 16, 0.3, and 0.5,

respectively. Goldstein et al. (1961) believed that a > 0.5; so it

appears that they and Ames e_t al. reported mass-effusion rates which

included a value of _f as 0.91. More recently Messier (1967) observed

Knudsen effusion rates for Gd203 through each of two orifices of

different size. As will be described later in Section VI under Messier,

the vaporization coefficient 0^ for r^O-^ was deduced to be 0.074.

When this value of _a is used to revise the work of Goldstein et al.,

_f becomes 0.68 instead of 0.91 to produce the results of assumption 4.

137
3

OiCD

prf tJ

CDm

cd

0)

TJ

CDN

•rlM

O

OCO>

cn O

cn

U

CDa

o

•r-4 4-1 CO Pi

o t—

1

CTV CN $

o vO r-l m 3

CN CN ON

'—

s

o on o i—

1

l—l r-l 00 00 vO

1-4 o O O O r-l O o o O r-l r-l r-l r-l CN O

cn

ON cn

on

CNav on

vO

CNON m

cn cn

vo

i—i cn

on oo CT\ C7\ 00 00

CNcn

cn

CN cn 3

cn cn

i

CN cn 00 vO cn m 00 ON o r-l i—i cn O o O 1 1 CN cn I I o o o • O o o o o o o o o

o o o o i—i cn

r-l 1-1 1-1 r-l in o o CN r-l cn vO On ^\ y—\ O o o o o cn

vO vO 00 <t

v

/ V

/ o o o o O vO o o O O 00

u 3

a> 3 3 3

rfi io CO a CO 3 CO rO 3 CO \—

4J 4-1 0) CD 14-1 CU .o CD CD <4-l CU CD CD VH Pd O CO 0 60 TJ U-l —

B 00 TJ U-l *£ E 00 TJ «4-4 3 o •H CD o 1-4 CD s~\ o i-l <D

cO r-l 4J & X O J 4J X o rJ r-l 4-1 X O r4 of r-la

< o O o

p-> 0000 < O o o

P-. < O o CJ V—< X CN 1—1 CJ c I—I i—l CJ c CN i—l CJ 3 • co CO a) 1 CO CD CL CM CO CD a cfl •H CD a. •

4-1 3 <f 4-1 4-J CO 4-1 1 4J 4J 4J O U e 4-1 cd 4-> CJ o r-l cn o co > CJ CD O CO > CJ m CD 0 CO > O

fl> 1-4 r-l CM 3 4J 00 CD X 4-1 00 CD <f 52 4J 00 CD

<4-l 4J 3 CM CO c •a a ON CO 3 tj a CM cO 3 TJ Cu

14-4 a M-l <4-l •H 3 CD to f—l IM T-l 3 CD C/3 14-1 i-l 3 CD C/5 w um to O Q H i

s 1CO O Q H is 1CO co O Q H is 1to

CO o c 3 00 00 > CO co c 00 00 > co %

3 00 > to o co 1+-4 e

o 3 c CD 3 o s c O if 3 CD co r—

t

< 4-J ti TP TP Oi 2

•H

4-1 TP TP £4 tl TP TP Oi 53

9) X CN cO 3 3 00 00 CO 3 3 00 r-4 3 3 00 00

r-l CD B

r-l r-l s 3 ON 1

1—1 r-l 3 1-4 i—i r-4 3 3

rO 4-1 a O 1-1 •r-l CJ o 1-4 i-i

I—

.

o CJ i-l •H

CO o 3 3 co co o s 3 co co o 3 3 CO co H. CU cn Pn H H 33 cn M t—

I

Z3 » cn Pn M 1—4 E3 C3

CD ol o O CO CN CN

rl CM cn m s r-l CN cn m A r-4 CN cn m CO

138
V. Equilibria Data by Mass Spectrometry

Differences between the dissociation energies of several pairs

of monoxides, LO and MO, have been determined from equilibria studies

of isomolecular oxygen exchange reactions in the gas phase

L + MO + LO + M (24)

Several investigators have used mass-spectrometry to measure ionintensities as a function of temperature for different condensed

mixtures of two or more metals and oxides, or of oxides only. They

calculated the of reaction 24 by assuming that the corresponding

ratio of cross-sections were unity, which seems satisfactory according

to the measurements of the cross-sections for Y+

, Y0+

, La+

, and LaO+

discussed in Section II above. Results by the 2nd and 3rd Law methods

are assembled in table 11. The extent of fragmentation of LO to L was neglected; however, Smoes e_t al_. (1965) and Ackermann and Rauh (ref. 2) were so concerned about the ill-effects of fragmentation that they

used lower ionization potentials. Values of the dissociation energies

in the last column of table 11 were calculated from the selected

values in the next to the last column. The results for LaO has

particular significance because it depends upon that for SiO which

was derived from an independent review by Stull and Prophet (1971).

Another method which has been used to evaluate dissociaiton

energies by mass-spectrometry involves measuring the LO VL ratio

of ion- in tens ities for the vapor species which are in thermodynamic

equilibrium with both L(£) and L2 0 3 (s) . A difficulty with this

method is the uncertain activities of the condensed phases, i.e.

their mutual solubilities. Using eq. 8 and independent data for

the pressure of L(g) , the Kp of reaction 25

1/3 L(g) + 1/3 L

2 0

3 (s) -> LO(g) (25)

may be calculated from

%

=P

L

2/3

(I LO+/I

L

+)(oi>,.0

+

> < 26)

in which the L+/LO+

ratio of cross-sections was shown in Section II

above to be approximately 1.6.

A third application of mass-spectrometry involves measuring as

a function of temperature the L0+ ion-intensity which is proportional

to the pressure of LO vapor in equilibrium with L20^(s). When the

pressure of atomic oxygen is assumed proportional to the pressure of

the monoxide over the temperature interval of measurement, the

enthalpy change of reaction 3 may be approximated from

AH° = -3R[d(ln P

L0 )/d(l/T)] (27)

139
asCo

•H

4-1 Ua

0) cd

a)60

cd rCuXw

l-l cd i-^3

CJ

cu2eo

CO Hmo

CO

00cu +

Cu

r—1 s

cd < X T

4-1 fl Kg

X) +

a>CF

J

(Uu

(U Q

>>

r=H

r-Jcdo

r4

)u 4J

0)B0

!-i 4Ju

CDa. w?03

to

60

Cu

w

AH

*. 1 00 00 LP, t—

CsJ oo 00 CNJ rrt 00 J

W1 ( 1 Cm Cm 0s* U> 00 t—-4 rr\ UU inUo

vO r\ 0s* 00 r*^ <t lO iO

M

cn

T3C

cd o r—

r-l r-l i—f—

f—

f—

J

v£>

O

O i—i i—lO r-* <^ ON On oo ON T)C

X3

O

cm o

cr\ oo

CN CM

JO CJ 0)

C~> vO nO ON ON ON

nO cn O OI I o o u cj CJ o O o o on m <t CNJ CN 00 cn i—i i—i nO tO

•—

i CN i—i CN .—I CN

CN r-~ cn r-i

O oo

m in nO CN r-l 1 i 1

i.

O nO CM i—i

O CN in <£> cn vO o <t

t—

CN CN i—l CM CM i—i 1 i CM r-l

v CN

CN CN lO

r-l r-l CN

cn

m

<-* CN o

CO

m

O

cn cn

m in

m

CN CN cm

m

CM inCM

m

m

CM CM o o o o o <r 00 o o 00 O o o O o

00 CN

r o 00 00

m nD 00

m o ON in 00

CU

m CN

O CM CNJ r-l o i—iO o O in cnO r-l 6£ CM CN CM CN CNJ CN CM CM CM CM CM CM CM CN CM CNJ C 1 1 1 1 1 1 1 1 1 1 1 i i 1 1

ct) o O o O o cn 00 in ON ON o O o O o H Cd r-l 00 ON CO 00 ON CM <t CNJ CN r-~. cn

OO 00 00 00 00 vO r»- 00 CO

CN

CN

CM

00

i—i r-l

33

O cjO

CO CO LO

d) CO ci) rlrllJ

>< ?H >H

cn

CO CO

l-J hJ

0) OJ

CO T3 rO

rJ !Z

H

rJ P l-l Cu CU CU E

CO3

CO -O

rO rQ

in

CNHO 3

EC rJ

CO

O T) OJ

CM

Q)60

COU>

cd

dJ rC

+J

COcoO

a)

r-l

a)COBo

l-l 4-1

TJ

0) U

CO3

^"N ON i—i o

l-l 1—

o X-N ~N NO N_/ ON cd CM r-l in ON i—i o

cn v£> vD 1—

J=

CN ON ON NO

N ' 3 CD 1 r-l I—I ON

,5

4-1 l-l

O

N—

v«/ 1—1 cd QJ CD On i

rG

O DCNJ c O

•31 cd Pr s

SI

C l-l SI c o

SI

ii

ns

cd

an

M-l

(0 co to

CO 0) CO cx co <S) 1—1 o a i—l 3

CO

B I o o 3 I-U 3 cn a < St

cd

140
VI. Recalculated Results

Using the weight-loss and ion-intensity data which are available

in the literature, the K of reactions 3 and 25 are evaluated; and the

corresponding dissociatTEn energies are calculated from the auxiliary

data which are given in Section III. Second Law and average Third

Law values of the dissociation energies for the monoxides are reported

in table 12. Selections of Dq values listed in tables 11 and 12, are compiled in the last column of table 1. Comments on the results

from each source follow below in the order that they appeared in the

literature.

Chupka e_t aJL. (1956) had used mass-spectrometry in 4 experiments

to measure the LaO+/La+ ion-intensity ratio, which is proportional to

the LaO/La pressure ratio in equilibrium with La(&) and La20^(s)

.

Instead of using their estimate of 0.5, the value of 1.6 deduced

by Ames e_t a_l. was used in eq. 26 for the La+/LaO+ ratio of crosssections. The resulting Dq value is exceptionally close to that in

table 11 for the isomolecular reaction involving Si.

Kulvarskaia and Maslovskaia (I960) had studied the vaporization

of several sesquioxides by Knudsen effusion. The 3rd Law Dq in table 12 are those from table 9 which were corrected for tantalum oxides.

Second Law values of Dq were obtained by using eqs. 20 and 21.

Goldstein e_t al . (1961) had used both Knudsen-ef fusion and mass- spectrometry to study the vaporization of La203 and Nd203. The Knudsen

value of the dissociation energy for NdO was selected as the average

of the extremes which are reported in table 8 and is strikingly close

to the mass-spectrometric value which resulted, using eq. 27. The

Knudsen value of Dq for LaO is the result of assumption 3 described

above for table 10. Similar to the NdO results the higher value of

Dq for LaO by mass-effusion than by mass-spectrometry corresponds

to a possible presence of the dioxide which was not corrected.

Ackermann et_ al . (1964) had studied the vaporization of Y2O3

by Knudsen effusion. The corrections which correspond to assumptions

1, 2, and 3 in table 10 had negligible effect on calculating the

dissociation energy for YO.

Semenov (1965) had used mass-spectrometry to measure the Sc0+

ion-intensity which corresponds to the vaporization of SC2O3. The 2nd

Law value of Dq for ScO in table 12 was calculated, using eq. 27. The

3rd Law value of D° was calculated from the K_ of reaction 3, using

Semenov' s values or the pressures of ScO and 0 which he had calculated

from his measurements of the effusion rate for SC2O3 and which he had

corrected with his estimate of 8 for the ScO/Sc pressure ratio.

Alcock and Peleg (1967) had measured rates of effusion for Gd203

and Y2O3 by torsion-effusion and L an gmuir- torsion experiments. They

had assumed that vaporization occurs as reaction 3 and had plotted

log(P/atm) versus 1/T. Their "total pressure" was interpreted as the sum of the LO and 0 partial pressures so that the Kp of reaction 3 was evaluated by reading their small graph.

141
Table 12. Dissociation Energies Recalculated from Published Weight-Loss and Mass Spectrometric uata

Sample T/K

Range Source DQ(LO)/kcal mol"

Znd Law 3rd 2400-2570

2551-2567

2555-2693.

Mass. Spect. (10 dV) Effusion Rate (3 runs Knudsen (5 runs) .} Semenov (1965) Ames et. al. (1967)

172

160.4 159.4

160.9

YO 2509-2720

2250-2390

2492-2697 2220-2620

Knudsen (11 runs) Langmuir-torsion, Knudsen

Knudsen (14 runs) Mass-Spect. (11 eV)

Ackermann et. al_. (1964) Alcock et. al_. (1967) Ames e_t. al. (1967) Ackermann et. al. (1973)

185

173 181 171

167.2

162 170.5

LaO

La + La 20

3 La

203 + Ta

La 2Oj

La

2 0

3 + Re

1650-

1980- 2234-

2015-

1490- 2150-

2258-

1778-

1900 2220

2441

2280

2190

2560

2427 2308

Mass Spect. (40 eV) Knudsen

Knudsen (22 runs) Mass Spect. (25 eV) Mass Spect. Transpiration

Knudsen (5 runs) Mass-Spect. (11 eV)

Chupka et. al. (1956) Kulvarskaia et. al. (1960) Goldstein et. al. (1961) Bushkovich et. al. (1967) Benezech et. al. (1969) Ackermann et. al. (1971)^

259 200

187

181 194

191.1

197 192.7

199 192.1

2060-2400 Kulvarskaia et . al. (1960) 214 180

NdO

Nd

20

3 + Ta 2080-2670

2255-2434 2095-2520

2210-2560

Knudsen

Knudsen (30 runs) Mass Spect. (25 eV) Transpiration }

Kulvarskaia et. al. (1960) Goldstein et. al. (1961) Benezech et. al. (1969)

205

166 168

169

166

178

Sm

2 03 Sm

2 0

3

W

2120-2350 2333-2499 2410-2670Knudsen Knudsen (9 runs) Transpiration

Kulvarskaia et. al_. (1960) Ames. e_t. al. (1967) Benezech et. al. (1969)

179 138.9

130

143 138.1

133

Eu

2 0

3 Eu

203

TaW 2050-2300

1984-2188

2192

Knudsen

Knudsen (9 runs) Knudsen

Kulvarskaia et. al. (1960) Ames et. al. (1967) Petzel et. al , (1971)

139

94 125 131.6

131 a

GdO

Gd

2 03 + Ta

+ W

2080-2380 2160-2390

2408-2546 2350-2590

2380-2670

Knudsen

Langmui r- torsion Knudsen (9 runs) Knudsen (18 runs) Transpiration

Kulvarskaia e_t. al. (1960) Alcock et._al. (1967) Ames et. al. (1967) Messier (1967) Benezech et. al. (1969)

222

114

183 171.4

169

177

157 169.2

165.8

172

DyO Dy 0

Dy

2 03

+ Ta + W 2260-2460

2432-2637 KnudsenKnudsen (16 runs) Kulvarskaia

Ames et. al

et. al. (1960) (1967)16158155 148.1

HoO Ho

20

3 Ho

2 0

3

+ Ta + W

2230-2490

2487-2711 KnudsenKnudsen (13 runs) Kulvarskaia

Ames et. al

et. aj.. (1960)

, (1967)

131 48

156 153.1

Er

20- + Ta

Er

2 03 + W 2270-2490

2492-2687 Knudsen Knudsen (16 runs) Kulvarskaia

Ames et. al

et. al. (i960)

(1967)

154 170

157 151.4

2450-2641 Knudsen (11 runs) Ames et. al. (1967) 163 134.8

Yb 0

3 Yb

2 0

3

+ Ta + W 2060-2400

2371-2626 Knudsen Knudsen (12 runs) Kulvarskaia

Ames et. al et._al. (1960) (1967)

144 127123

93

LU 2 U

3 Lu.2-3 + Ta + U 2120-2400

2615-2700 KnudsenKnudsen (9 runs) Kulvarakaia

Ames et. al

et. al. (1960) (1967)84128183 157.2

As reported by source Reference 2.

142
Ames et al_ . (1967) had measured the rates of effusion for several

sesquioxldes . Except for YbO the values of D~ in table 12 are the

results of assumption 3 described for table 10. In the case of YbO,

assumption 5 described for table 10 was used.

Bushkovich et al . (1967) had tested their mass-spectrometer by

subliming La203. They had measured the LaO+ ion-intensity as a function of temperature and deduced a AH^ to be 4 35 kcal mol~l,

presumedly for reaction 3.

Messier (1967) had measured rates of effusion for Gd20.j in a tungsten cell with 0.47 cm radius for which the Clausing factor was estimated to be 0.53. This cell was fitted with either of two lids

with orifices which had radii of 0.450 and 0.855 mm and Clausing

factors of 0.356 and 0.507, respectively. Using the average rate

of effusion through each orifice, simultaneous solution of eqs. 10

and 11 gives the vaporization coefficient cx as 0.074 and the vapor

saturation _f for each cell as 0.96 and 0.82, respectively. The D°

for GgO in table 12 was calculated by using assumption 3 described

above for table 10.

Benezech and Foex (1969) had used the entrainment method and a rotating solar furnace to study the vaporization of sesquioxides which

served as their own containers. Thev had assumed that vaporization

occurs as reaction 3 and had calculated pressures of the monoxides of

La, Nd, Sm, Dy, Tb , Gd, Er t ard Ho, which they gave on a small graph.

At this time no attempt was made to read the graph; however, the authors

did report 2nd and 3rd Law values of the AHq of reaction 3, involving

La, Nd, Sm, and Gd, although they gave no sources for the values of

the Gibbs free energy functions they had used.

Petzel and Greis (1971) had used the Knudsen effusion method

to study the influence of tungsten cn the vaporization behavior of

Eu2 0

3 at 2192 K. They had placed be th W and Eu2 0

3 in an iriduim-lined

cell to control solid-solid contact, had analysed the effusate for

a Eu/W molar ratio of 3.7 to 3.8, and had calculated partial pressures

of various tungsten oxides and the cissociation energy of EuO which

is given in table 12.

Recently Ackermann and Pauh (refs. 2, 3, and 4) have used both

Knudsen effusion and mass-spectrometry to study the vaporization of some sesquioxides both alone and in the presence of their metals. They

had also studied several isomolecular oxygen exchange reactions. The

values of D° for LaO in table 12 were calculated from their rate of

effusion and ion-intensity data which corresponds to the La203 vaporized

in a Re cell. Only corrections for the metal atom and diatomic

oxygen were made. A review of ref. 3 was not completed in time for

inclusion here. In ref. 4 Ackermann and Rauh had used only mass- spectrometry to study the vaporization of Y2O3. Their YO ionintensity data was used to calculate from eq. 27 the 2nd Law value

of D° for YO in table 12.

14 3
VII. References

R. J. Ackermann, E. G. Rauh, and R. J. Thorn, J. Chem. Phys.,

40, 883 (1964).

R. J. Ackermann and E. G. Rauh, J. Chem. Thermodynamics, 3_ 445 (1971).

R. J. Ackermann and E. G. Rauh, J. Chem. Thermodynamics, 3_, 609 (1971).

R. J. Ackermann and E. G. Rauh, J. Chem. Thermodynamics, _5, 331 (1973).

C. B. Alcock and M. Peleg, Trans. Brit. Ceramic Soc, 66, 217 (1967).

L. L. Ames, P. N. Walsh, and D. White, J. Phys. Chem. _7_L 2 ? 07 (1967).

F. B. Baker and C. E. Holley Jr., J. Chem. Eng. Data, 13, 405 (1968).

F. B. Baker, G. C. Fitzgibbon, D. Pavone, and C. E. Holley Jr.,

J. Chem. Thermodynamics, 4, 62 L (1972).

G. Benezech and M. Foex, C. R. Acad. Sci., Paris, C268, 2315 (1969).

L. Brewer and G. M. Rosenblatt in "Advances in High Temperature

Chemistry," Vol. 2, Leroy Eyring, Editor, Academic Press, New

York, 1969, pp. 1-83.

S. N. Bushkovich, A. A. Ganichev, G. N. Petrov, and Yu. S.

Rutgaizer, Industrial Lab. (USSR), 33_, 441 (1967); Zavod. Lab.,

33, 376 (1967).

K. D. Carlson, E. Ludena, and C. Moser, J. Chem. Phys. 43,

2408 (1965).

W. A. Chupka, M. G. Inghram, and R. F. Porter, Jr., J. Chem. Phys.

24, 792 (1956).

P. Coppens, S. Smoes, and J. Drowart, Trans. Faraday Soc,

63, 2140 (1967).

144
15. R. L. DeKock and W. Weltner, Jr., J. Phys . Chem., 75, 514 (1971).

16. R. C. Feber and C. C. Herrick, Atomic Energy Commission Report

LA-3184, Los Alamos, N. M. (1965).

17. R. C. Feber and C. C. Herrick, J. Chem. Eng. Data, 12, 85 (1967).

18. G . C. Fitzgibbon, E. J. Huber, Jr., and C. E. Holley, Jr., J.

Chem. Thermodynamics, 4, 349 ( 1972)

.

19. G. C. Fitzgibbon, E. J. Huber, Jr., and C. E. Holley, Jr., Rev.

Chim. Min., 10, 29 (1973).

20. A. G. Gaydon, "Dissociation Energies and Spectra of Diatomic

Molecules," Chapman and Hall Ltd., London (1968).

21. B. C. Gerstein, F. J. Jelinek, J. R. Mullaly, W. D. Shickell,

and F. H. Spedding, J. Chem. Phys., 4_7_, 5194 (1967).

22. H. W. Goldstein, P. N. Walsh, and D. White, J. Phys. Chem.,

64, 1087 (1960).

23. H. W. Goldstein, P. N. Walsh, md D. White, J. Phys. Chem., 65

1400 (1961).

24. D. W. Green, J. Phys. Chem., _7>, 3103 (1971).

25. C. E. Holley, Jr., E. J. Huber, Jr., and F. B. Baker in

"Progress in the Science and Technology of the Rare Earths,"

Vol. 3, Leroy Eyring, Editor, Pergamon Press, Oxford, 1968,

p. 343-433.

26. E. J. Huber, Jr., and C. E. HoLley, Jr., J. Amer. Chem. Soc,

77, 1444 (1955).

27. E. J. Huber, Jr., G. C. Fitzgibbon, and C. E. Holley, Jr.,

J. Chem. Thermodynamics, 3, 643 (1971).

28. R. Hultgren, P. D. Desai, D. T. Hawkins, M. Gleiser, K. K. Kelley,

and D. D. Wagman, "Selected VaLues of the Thermodynamic Properties

of the Elements," American Society for Metals, Metals Park,

Ohio (1973).

145
M. G. Inghram, W. A. Chupka, and J. Berkowitz, Mem. Soc. Roy.

Sci. Liege, 18, 513 (1957).

B. H. Justice, E. F. Westrum, Jr., E. Chang, and R. Radebaugh,

J. Phys. Chem., 73, 333 (1969).

P. H. Kasai and W, Weltner, Jr., J. Chem. Phys., 43, 2553 (1965).

B. S. Kulvarskaia and R. S. Maslovskaia, Radio Eng. and Elect.

(USSR), 5, 89 (1960); Radio tekh. i Elektron., 5, 1254 (1960).

D. R. Messier, J. Amer. Ceramic Soc, 50_, 665 (1967).

M. B. Panish, J. Chem. Phys. 34, 1079 (1961); J. Chem. Phys.,

34, 2197 (1961)

.

R. C. Paule and J. L. Margrave in "The Characterization of High

Temperature Vapors," J. L. Margrave, Editor, John Wiley & Sons,

Inc., New York, 1967, pp. 130-151.

T. Petzel and 0. Greis, Rev. Int. Hautes Temp. Refract., 8_, 269 (1971).

C. Pupp and K. A. Gingerich, J. Chem. Phys. 54, 3380 (1971).

B. Rosen, "Spectroscopic Data Relative to Diatomic Molecules,"

Pergamon Press, Oxford, 1970.

H. L. Schick, "Thermodynamics of Certain Refractory Compounds,"

Vols. 1 and 2, Academic Press, New York, 1966.

R. H. Schumm, D. D. Wagman, S. Bailey, W. H. Evans, and V. B.

Parker, National Bureau of Standards Technical Note 270-7,

U. S. Government Printing Office, Washington, D. C. 1973.

G. A. Semenov, Russian J. Inorg. Chem., 10, 1300 (1965).

S. A. Shchukarev and G. A. Semenov, Dokl. Akad . Nauk USSR,

141 , 652 (1961).

S. Smoes, J. Drowart, and G. Verhaegen, J. Chem. Phys., 43 , 732 (1965).

146
44. H. G. Staley and J. H. Norman, Int. J. Mass. Spect. and Ion

Phys., 2, 35 (1969).

45. D . R. Stull and H. Prophet, "JANAF Thermochemica 1 Tables",

2nd Edition, NSRDS-NBS 37, U. S. Government Printing Office,

Washington, D. C., 1971.

46. S. N. Suchard, "Spectroscopic Constants for Selected Heteronuclear

Diatomic Molecules," Vols. I, II, and III, The Aerospace

Corp., El Segundo, Calif., 1974.

47. D . D. Wagman, W. H. Evans, V. B. Parker, I. Halow, S. M. Bailey,

R. H. Schumm, and K. L. Churney, "Selected Values of Chemical

Thermodynamic Properties", National Bureau of Standards Technical

Note 270-5, U. S. Government Printing Office, Washington, D. C,

1971.

48. P. N. Walsh, D. F. Dever, and I). White, J. Phys . Chem., 65, 1410

(1961) .

49. E. F. Westrum, Jr. and F. Gr^n^old in "Thermodynamics of Nuclear

Materials", International Atomic Energy Agency, Vienna, 1962,

p. 20.

50. D. White, P. N. Walsh, L. L. Anes, and H. W. Goldstein in

"Thermodynamics of Nuclear Materials," International Atomic

Energy Agency, Vienna, 1962, pp . 417-443.

Acknowledg ement

Thanks go to R. H. Schumm and other members of the Chemical

Thermodynamic Data Center at the National Bureau of Standards for use of their indexed files of published papers which they have been

collecting for several years. A search of the literature was made

considerably easier.

147
Chapter 10

Bibliography on Spectroscopy of

Fluorides and Oxides

Belonging to Lantbanide Series

This bibliography lists papers cn the spectroscopy of lanthanide

fluorides and oxides in gas, liquid, or solid phases. It also includes

some papers dealint with the chemiluininescence or quenching of these

compounds in excited states.

The list is divided into fiftenc sections:

I . Cerium

a. Cerium fluorides

b. Cerium oxides

c. Cerium oxide fluorides

II. Dyspros ium

a. Dysprosium fluorides

b. Dysprosium oxides

c. Dysprosium oxide fluorides

III. Erbium

a. Erbium fluorides

b. Erbium oxides

c. Erbium oxide fluorides

IV. Europium

a. Europium fluorides

b . Europium oxides

c. Europium oxide fluoride;

V. Gadolinium

a. Gadolinium fluorides

b. Gadolinium oxides

c. Gadolinium oxide fluorides

VI. Holmium

a. Holmium fluorides

b. Holmium oxides

c. Holmium oxide fluorides

14>
VI I • Lanthanum

a* Lanthanum fluorides

b. Lanthanum oxides

c. Lanthanum oxide fluorides

Till, Lutetlum

a* Lutetiun fluorides

b, Lutetlum oxides

IX. Neodymlum

a* Neodymlum fluorides

b. Neodyaiua oxides

c, Neodymlum oxide fluorides

X. Promethium

a, Promethium fluorides

b. Promethium oxides

XI, Praseodymium

a. Praseodymium fluorides

b. Praseodymium oxides

c. Praseodymium oxide fluorides

XII, Samarium

a. Samarium fluorides

b. Sanarium oxides

c. Samarium oxide fluorides

XIII, Terbium

a. Terbium fluorides

b. Terbium oxides

c. Terbium oxide fluorides

XIV. Thulium

a. Thulium fluorides

b. Thulium oxides

149
XT. Ytterbium

a* Ytterbium fluorides

b. Ytterbium oxides

The list 1b based on the files of the Chemical Kinetics Information

Center and an examination of Chemical Abstracts* (1967-1974)

Suggestions, additions and corrections are welcome.

The Chemical Kinetics Information Center, Institute

• for Materials Research, National Bureau of Standards,

Washington, D.C. 20234, is ^art of the National Standard

Reference Data System. The Center prepares bibliographies

for general distribution and also in answer to specific

requests.

The Center does not, normally, distribute copies of

published papers or reports, although it will assist in the

location of obscure or hard-to-obtain material. Papers

should be obtained locally or from the author or publisher.

Gorernment R&D reports that are available to the public

may be purchased from the National Technical Information

Service, Springfield, Virginia 22151.

The Center indexes and stores copies of published papers

and reports of research on chemical kinetics, photochemistry

and collision dynamics. Contributions to its collection are welcome.

150
I, Cerium

(a). Cerium fluorides

Batsanov, S. S # , Derbeneva, S. S., and Batsanova, L. R. t Electronic Spectra

of Rare Earth Metal Fluorides, Qxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 10., 332 (1969) (Russ); Chea. Abstr. 70:101332k (1969)

Baunan, R. P., and Porto, S. P. S., Lattice Vibrations and Structure of

Rare-Earth Fluorides, Phys. Rev. 161, 8*2 (1967); Chea, Abstr.

67: 112549a (1967)

Claudel, J., Hadni, A., and Striraer, P., Low-Frequency Vibration of

Lanthanide Fluoride Lattices, C. R. Acad. Sci«, Ser. B 274. 943

(1972) (Fr); Chea. Abstr, 77:40868k (1972)

Hadni, A., Striaer, P., and Vermillard, F,, Far Infrared Absorption

Observation of the Low Frequency Lines of Praseodymium Fluoride

and Other Rare-Earth Fluorides, C. R. Acad, Sci., Ser. 3 gg,

1113 (1969) (Fr); Chem. Abstr. 72:49216a (1970)

Ovsyannikova, I. A., and Nasonova, L. I,, Ljjj X-Ray Absorption Spectra

of Praseodymium and Cerium and Effective Coordination Charges,

Zh. Strukt. Khinu XL, 548 (1970) (Russ); Chem. Abstr. 73:82137u (1970)

Wertheim, G, K# , Cohen, R. L. , and Rosencwalg, A., Multiplet Splitting

and Two-Electron Excitation in the Trivalent Rare Earths, Electron

Spectrosc, Proc. Int. Conf. 1971, p. 813 (1972), Shirley, D, A,, Ed.,

Chem. Abstr. 77:158530x (1972)

(b). Cerium oxides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R«, Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh, Prikl.

Spektrosk. 1Q, 332 (1959) (Ru3s); Chem. Abstr. 70: 101332k (1969)

Bloor, D., and Dean, J. R. t Spectroscopy of Rare-Earth Oxide Systems.

I, Far-Infrared Spectra of the Rare-Earth Sesquibxides, Cerium

Dioxide, and Nonstoichiometric Praseodymium and Terbiua Oxides,

J. Phys. C 5, 1237 (1972); Chea. Abstr. 77:64303j (1972)

Bonnelle, C., and Karnatak, R. C., Distribution of f-States in RareEarth Metals and Oxides, J. Phys. (Paris), Colloq. 230 (1971) (Fr);

Chem. Abstr. 77:26817m (1972)

Bonnelle, C, and Karnatak, R. C., Distribution of f States in

Rare-Earth Metals and Oxides, Colloq. Int. Cent. Nat. Rech.

Sci. 1971, No. 196, 230 (Fr); Chea. Abstr. 77:81451n (1972)

Davidson, F. D., and Wyckoff, R. V. C, L and M X-Ray Spectra in the

Region 2-a5 A, Advan. X-Ray Anal. 9, 344 (1966); Chea. Abstr.

66:99767c (1967)

15 L
Demekhin, V. P., Platkov, A* I., and Lyubivaya, M. V*, Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chen. Abstr. 68:737355 (1968)

Fischer, D. W., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray M

a

and Mp Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 38., 4830 (1967); Chem. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with Bl^ symmetry. III. The Spectra of Rare

Earth Carbonates and their Thermal Decomposition Products, Spectrochim. Acta, Part A 22, 1909 (1967); Chen. Abstr. 67:68968k (1967)

Haensel, R., Rabe, P., and Sonntag, B., Optical Absorption of Cerium,

Cerium Oxide, Praseodymium, Praseodymium Oxide, Neodymium,

Neodymium Oxide, and Samarium in the Extreme Ultraviolet,

Solid State Commun. 8, 1845 (1970); Chem. Abstr. 74:58999b (1971)

Lowndes, R. P., Parrish, J. F., and Perry, C* H., Optical Phonons and

Symmetry of Tysonlte Lanthanide Fluorides, Phys. Ret. 182 . 913

(1969); Chem. Abstr. 71:75340y (1969)

McCrary, J. H., Slngman, L. V., Ziegler, L. H., Looney, L. D.,

Edmonds, C. M., and Harris, C. E., L Fluorescent X-Ray RelativeIntensity Measurements, Phys. Re?. A £, 1587 (1972); Chem. Abstr*

76:133772U .(1972)

Ovsyannikova, I. A., and Kasonora, L. I., Ljjj X-Ray Absorption Spectra

of Praseodymium and Cerium and Effective Coordination Charges,

Zh. Strukt. Khim. H, 548 (1970) (Russ); Chem. Abstr. 73:82137u (1970)

Petru, F. , and Muck, A., Chemistry of Rare Earth elements. XXXVII*

Infrared Absorption Spectra of CeO^ Pr6

0u, Nd2 03

and Sro^,

Z. Chem. 7_, 27 (1967) (Ger); Chem. Abstr. 67:27441q (1967)

Petru, F. , and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lan thanides Eu. . .Lu,

Z. Chem. 2, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. Y. , Zykov, V. S.,

Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Ka^

Lines During Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Yeshchestva £, 172 (1969) (ftiss);

Chem. Abstr. 74:117626c (1971)

15Z
Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, £• Y., Zykov, V. S,,

Egorov, A* I., and Grushko, A* I., Chemical Shifts of the

Kctj X-Ray Lines During Oxidation of Rare Earth Metals. Role of

f-electrons, Zh. Eksp. Teor. Fiz. 56, 536 (1969) (toss);

Chen. Abstr. 71:7985z (1969)

Tainshtein, E. E., Blokhin, S. M. t and Bertenev, Y, M., X-Ray Spectrum

Study of Some Cerium and Praseodymium Compounds, Izv. Sib* Otd.

Akad. Nauk SSSR Ser. Khim. Nauk, 59 (166) (Russ); Chem. Abstr.

66:41906f (1967)

Veltner, W. # Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J, Phys. Chem. 25, 514

(1971); Chem. Abstr. 74:105048c (1971)

(c). Cerium oxide fluorides

Batsanov, S. S., Derbeneva, S. S«, and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

II. Dysprosium

(a). Dysprosium fluorides

Batsanov, S. S., Perbeneva, S. S. # and Batsanora, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1959) (Suss); Chem. Abstr. 70:101332k (1969)

Chase, S. W., Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 4£, 2512 (1969);

Chem. Abstr. 71: 34384J (1969)

Chen, Y. S. ( DePaolis, M. V., Jr., and Kahng, S., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IKES £g, 184 (1970);

Chem. Abstr. 72: 1158162 (1970)

Vertheia, G. K., Cohen, R. L., Rosencvaig, A., and Guggenheim, H# J. t Multiplet Splitting and Two-Electron Excitation in the Trivalent

Rare Earths, Electron. Snectrosc, Proc. Int. Conf. 1971, p. 813

Chem. Abstr. 77:158530x (1972)

Verthein, G. K., Rosencwaig, S., Cohen, R. L., and Guggenheim, H. J.,

Exchange Splitting in the 4f Photo electron Spectra of the Rare

Earths, Phys. Rev. Lett. 22, 505 (1971); Chem. Abstr.75: 103444a

(1971)

153
(b). Dysprosium oxides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Bare Earth Metal Fluorides, Oxyluorides and Oxides, Zh. Prikl.

Spektrosk. JLH. 332 (1969) (Russ); Chea. Abstr. 70:101332k (1969)

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems. I*

Far-infrared Spectra of the Rare-Sarth Sesquioxides, Cerium Dioxide,

and Nonstolchiometric Praseodymium and Terbium Oxides, J. Pays. C

1237 (1972); Chea. Abstr. 77:54303j (1972)

Bonnelle, C, aid Karnatak, R. C., Distribution of f States in Rare Earth

Metals and Oxides, Colloq. Int. Cert. Nat. Rech. Sci. Ho 196, 230

(1971); Chem. Abstr. ?7:31451n (1972)

Bonnelle, C, and Karnatak, R. C, Distribution of f-States in Rare-Sarth

Metals and Oxides, J. Phys. (Paris), Colloq., p. 230 (1971);

Chem. Abstr. 77:26817m (1972)

Chen, Y. S., DePaolls, M. V., Jr., and Kahng, D., Characteristics of

•

; ><sd Electroluminescence irom Zinc Smlfid® Filias

Containing Rare Earth Fluoride, ?roc. IEEE 59, 184 (1970);

Chea. Abstr. 72:11581tfz (1970)

Davids on s F. D. # and Vyckoff, R* V. G., L and M X-Ray Spectra in the

i ='P5 A 0 k» I-fey M&l g0 344 (A4444: 1 i,u y &M%?Q 66J997S7C (1967)

Demekhin, ?. F., Platkov, A. I., Lyubivaya, M. V., Multiplet

Structure of the L-5eries Lines of Rare-Earth Elements,

Zh. Bcsp. Teor. Fiz. £2, 49 (1972) (Russ); Chem. Abstr.

76s 1060 15t (1972)

Dental, A. G., Fluorescent High Alumina Ceramic Substrates,

Amer. Ceran. Soc, Bull. 51, 681 (1972); Chem. Abstr.

77:143291w (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 125, 1062

(1967); Chem. Abstr. 68:73735g (1968)

Fischer^ D. W., and Baun, W. L., Self-Absorption Effects in the

Soft X-Ray Ma and M0 Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 22, 4830 (1967); Chea. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross., S. D. , Factors Affecting the Infrared

Spectra of Some Planar Anions with It^ Symmetry. II. The Spectra

of Rare Earth Carbonates and Their Thermal Decomposition Products,

Spectrochin. Acta, Part A 23, 1909 (1967); Chera. Abstr. 67:68968k

(1967)

1 54
Petru, F. , and Muck A«, Chemistry of Rare Earth Elements. XL* Infrared

Absorption Spectra of Oxides of the Lanthanides Eu...Lu, Z. Chem. £,

159 (1967); Chem. Abstr. 67:27442r (1967)

Ratlnen, H., X-Ray Excited Optical Fluorescence of Nine Rare Earth Ions

in Yttrium Oxide, Gadolinium Oxide, and Lanthanum Oxide, Acta

Polytechn. Scand., Chem, Incl. Met. Ser. No* 107 (1971);

Chem. Abstr. 76: 106021s (1972)

Sumbaev. 0. I., SmlrnoT, Yu. P., PetroTich, £• v«» Zykov, V. S.,

Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Ka^

Lines During Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Veshchestva £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovlch, E. Zykov, S. t Egorov, A. I., Grushko, A. I., Chemical Shifts of the K

al

X-Ray Lines During Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. FU. 56., 536 (1969) (iiiss);

Chem. Abstr. 71:7985z (1969)

Weltner, V., Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. 7J>. 514 (1971);

Chen. Abstr. 74:105048c (1971)

\lhite, V. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 21, 167 (1967); Chem. Abstr. 67:69158h (1967)

(c). Dysprosium oxide fluorides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

III. Erbium

(a). Erbium fluorides

Batsanov, S. S., Derbeneva, S. S. , and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Cnem. Abstr. 70: 101332k (1969)

Chase, E. W., Hepplewhite, R. T., Krupka, D. C, and Kahng, D. , Electroluminescence of Zinc Sulfide Lunocea Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 40. 2512 (1969);

Chem. Abstr. 71:34384j (1969)

155
Chen, T. S., DePaolis, M. V., Jr., and Kahng, D., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. I£££ £8, 184 (1970);

Chen, Abstr. 72:115816z (1970)

Hadni, A., Morlot, G. , and Striaer, P., Far- Infrared Electronic

Transitions in Solids, J, Quantum Electron. 3, 111 (1967);

Chen. Abstr. 67:86235y (1967)

Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chea. j>, 425 (1973); Chem. Abstr. 78:130353u (1973)

Taylor, M. D., Cheung, T. T., and Hussein, M. A., Variations of the

Infrared Spectra with the Nature and Structure of the Rare Earth

Metal Halides, J. Inorg. Micl. Chem. £4, 3073 (1972);

Chem. Abstr. 77:132692b (1972)

Yakhidov, Sh. A., Kaipov, B. t and Tavshunskii, G. A., Luminescence of

CaF^jflFg Crystals in a Cobalt-60 Y-Ray Field, Opt. Spektrosk. £8,

949 (1970) (Russ); Chem. Abstr. 73:32314z (1970)

Verthela, G. X,, Cohen, R. L., Rosencvaig, A., and Guggenheim, H. J.,

Multiplet Splitting and Two-electron Excitation in the Trivalent

Hare Earths, Electron Spectrosc., Proc. Int. Conf. 1971, p. 813

Chem. Abstr. 77 i 153530 x (1972)

(b). Erbium oxides

Batsanov, S. S. f, Derbeneva, S. S., and Batsanova, L. R. # Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Hu33); Choa. Abstr. 7C:101332k (1959)

Bloor, D., and Dean, J. R., Spectroscopy of Rare-iiarth Oxide Systems. I.

Far-infrared Spectra of the Rare-ferth Sesquioxides, Cerium Dioxide,

and Nonstoichiometric Praseodymium and Tarbium Oxides, J. Phys. C 5,

1237 (1972); Chem. Abstr. 77:54303j (1972)

Davidson, F. D., and Wyckoff, R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 9_, 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V. F. , Platkov, A. I., and lyubivaya, M. V.,

Multiplet Structure of the L-Series Lines of Rare-Earth Elements,

Zh. Eksp. Teor. Fiz. 62, 49 (1972); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden Zone for

Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 125, 1062 (1967) (ftiss);

Chem. Abstr. 68:73735g (1968)

156
Fischer, D. W., and Baun, V. L. , Self-Absorption Effects in the Soft

X-Ray Mac and M3 Emission Spectra of the Dare Earth Elements,

J. Appl. Phys. 2S# 4830 (1967); Chem. Abstr. 681 17303c (1968)

Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with symmetry. III. The Spectra of Hare

Earth Carbonates and Their Thermal Decomposition Products,

Spec tro chi m. Acta, Part A 23., 1909 (1967 5; Chem. Abstr. 67i6896Bk

(1967)

Gruber, J. B., Two Photon Spectroscopy. Rare Earth and Actinide Ions in

Single Crystals, Proc. Rare Earth Res. Conf., 9th 1971, 2, p. 455

Chem. Abstr. 77:11898q (1972)

Grass, L. L., Electronic Spectra of Solid Solutions of Erbium and

Ytterbium Oxides, Diss. Abstr. Int. B 5902 (1971);

Chem. Abstr. 76:8365n (1972)

Guazzoni, G. £., and Shapiro, S. J., Spectral Emlttance of Neodymium,

Samarium, Erbium, and Ytterbium Oxides at High Temperatures,

Nat. Tech. Inform. SerT., AD 708547 (1970) ; Chem. Abstr.

74:36594p (1971)

Hoskins, R. H., and Soffer, B. K., Energy Transfer and CW Laser Action

in HD2+:Er

2 02 f IEEE (Inst. Elec* Electron. Eng.), J. Quantum

Electron. £, 253 (1966); Chem. Abstr. 66:60594u (1967)

Joergensen, C. K., and Berthou, H., Measurements of Photo electron

Spectra and Charging Effects in Fluorides, Iodates, and Oxides*

J. Fluorine Chem. £, 425 (1973); Chem. Abstr. 78: 130353a (1973)

McMahon, V. R., Hemispherical Spectral Emlttance of Selected Rare

Earth Oxides, U.S. At. Energy Comm., IS-T-182 (1967);

Chem. Abstr. 69:6796k (1968)

Matsubara, T., Mixed Rare Earth Phosphors, Japan Kokai 73 26, 685

(C1.13(9)-C112, 7 Apr 73, Appl. 71 61,170, 11 Aug 71;

Chem. Abstr. 79:25573h (1973)

Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu. . .Lu,

Z. Chem. 7, 159 (1967) (Ger) ; Chem. Abstr. 67:27442r (1967)

Satybaev, N. M., and Ganichenko, L. G., Photo luminescence of Some Rare

Earth Oxides, Dokl. Nauch.-Tekh. Konf. Itogam Nauch.-Issled Rab.

1966-1967 gg. Mosk. Energ. Inst. Sekts. Elektron. Tekh. Podsekts.

Poluprov. Proborov. p 150 (1967) (Russ); Chem. Abstr. 69:72576q (1968)

157
SunbaeY, 0, I. t SmirnoY, Yu. P., PetroYlch, E. V., tykov, V. S.,

Egorov, A, I., and Grushko, A. I., Chemical Shifts of X-Ray ia^ •

Lines During Oxidation of Rare Earth Metals, Rentgen. Spektry

ELektron. Strukt. Veshchestva £, 172 (1969); Chem. Abstr.

74? 117626c (1971)

SumbaeY, 0. I., SmirnoY, Yu, P., PetroYlch, E. V., tykoY, V. S.,

EgoroY, A. I., and Grushko, A, I., Chemical Shifts of the Ka. x-Ray

Lines During Oxidation of Rare Earth Metals. Role of f-Electrons,

Zh. Ekspo Teor. Fiz. 56., 536 (1969) (Russ); Chenu Abstr,

71s7985z (1969)

Weltner, W. Jr., and De Kock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. £5, 514 (1971);

Ghee. Abstr. 74:105048c (1971)

White, W. B. t Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. £1, 167 (1967); Chen. Abstr. 67:69158h (1907)

(e). Erbium oxide fluorides

Batsanov, S 9 S., Derbenera, S. S., and BatsanoYa, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. Ifl, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

I?. Europium

(a). Europium fluorides

BatsanoY, S. S., Derbeneva, S. S., and Batsanov a, L. R., Electronic Spectra

©f Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh, Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Caspers, H. H., Rast, H. E., and Fry, J. L. , Optical Absorption and

Fluorescence Spectra of Europium Trifluoride, J. Chem. Phys 42.

4505 (1967); Chen. Abstr. 68:55153m (1968)

Chase, E, W., Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices C ontaining Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 4£, 2512 (1969);

Chem. Abstr. 71:343840 (1969)

DeKock, C, W., Wesley, R. D., and Radtke, D. D., Infrared Spectra and

Geometries of Rare Earth Dihalides. Saoarium(II) Fluoride, Samarium(ll)

Chloride, Europium(II) Fluoride, Europium(II) Chloride, Ytterbium(Il)

Fluoride, and Ytterbiua(II) Chloride, High Temp. Sci. £, 41 (1972);

Chem. Abstr. 76:119423e (1972)

158
Preiser, M. J., Hbltzberg, F., Methfessel, S. I., and Pettit, G. D.,

Shafer, M. W., and Suits, J* C, Magnetic Red Shift in Europium * Chalcogenides, Helv. Phys. Acta £1, 832 (1968); Chem. Abstr.

70:329973 (1969)

Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. 2, 425 (1973); Chem, Abstr. 78:130353u (1973)

Petrovich, E. V., Smirnov, Tu. P., Zyko?, V, S., Grushko, A. 1.,

Suabaev, 0. I., Band I* M., and Trzhaskovskii, M. B., Chemical

Shifts of the taj

2 K0 1>3 and 1#2 4

X-Ray Lines in Heavy Elements

due to s-, p~, d-p or f-Valency Electrons, Zh. Eksp. Teor. Fiz. 61. 1756 (1971) (Russ); Chem. Abstr. 76:65903k (1972)

Taylor, M. D. , Cheung, T. T., and Hussein, M. A,, Variations of the

Infrared Spectra with the Hature and Structure of the Rare Earth

Metal Halides, J. Inorg. Nucl. Chem. 3073 (1972); Chem. Abstr.

77:132692b (1972)

Verthelm, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim U. J.,

Multiple t Splitting and Tvo-iiectron Excitation in the Trivalent

Rare Earths, Electron Spect rose. , Proc. Int. Conf • 1971, p. 813,

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:168530x (1972)

(b). Europi ua oxides

BatsanoT, S. S., Derbeneva, S. S,, and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Qxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1959) (Hass); Chem. Abstr. 70:101332k (1969)

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Ceriun

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides

J. Phys. C 5, 1237 (1972); Chem. Abstr. 77: 54303j (1972)

'

Bonnelle, C., and Karnatak, R. C, Distribution of f States in

Rare-Earth Metals and Oxides, Colloq. Int. Cent, IfeU. Feoh.

Sci. 1971, No. 196, 230 (Fr) ; Chem. Abstr. 77:8145In (1972)

Bonnelle, C, and Karnatak, R. C, Distribution of f-States in

Rare-Earth Metals and Oxides, J. Phys. (Paris), Colloq. p. 230

(1971) (Fr) ; Chen. Abstr. 77:26817m (1972)

Busch, G., Guentherodt, G., and Wachter, P., Optical Transitions and

the Energy Level Scheme of the Europium Chalcogenides, J. Phys.

(Pari3), Colloq. 1971, No. 1 Part 2, CI, 923; Chem. Abstr.

75:27774r (1971)

Demekhin, V. F. , Platkov, A. I., and tyublvaya, M. V., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 6£, 49 (1972) (Rass); Chem. Abstr. 76:1050lot (1972)

?39
I

Dental, A, &., Fluorescent High Alumina Ceramic Substrates, Amer. Ceraa.

Soc, Bull. 51, 681 (1972); Chea. Abstr. 77tl43291w (1972)

DerbeneTa, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (196'.') (Russ); Chem. Abstr, 58:73735g (1968)

Dlramock, J* 0., Hanus, J., and Felnleib, J,, Multlplet Structure In the

Reflectance Spectra of Suropiura Chale ogen ides, J. Appl. Phys. 4,1,

1088 (1970); Chen. Abstr. 73:3Q105y (1970)

Fischer, D. W., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 22, 4830 (1967); Chen. Abstr. 68:17303c (1968)

Preiser, M. J., Holtzberc, Methfessel, S. I., Pettit, G. D.,

Shafer, M. W# , and Suits, J. C., Magnetic Red Shift in Europium

Chalcogenides, Helv. Phys. Acta £1, 832 (1963); Cheo. Abstr.

70:32997s (1969)

Golding, B., Bamatz, M., Buehler, E, , and Salamon, M. B. , Critical

Acoustic Relaxation in Europium(II) Oxide, Phys. Rev. Lett. £0,

968 (1973); Chera. Abstr. 80:74399* (1974)

Goldsmith, J. A., and Ros3, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with symmetry. III. The Spectra of Hare

Earth Carbonates and Their Therm.il Decoimositior. Products, Spectrochia. Acta, Part A £2, 1909 (1967); Chen. Abstr. 67:68963k (1967)

Guentherodt, G., Vachter, P., and Imboden, D. M. v Energy Level Scheme

and the Effect of Magnetic Order on the Optical Transitions in

Europium Chalcogenides, Phys. Kondens. Mater, 12, 292 (1971);

Chem. Abstr. 75:82049h (1971)

Hill, P., and Huefner, S« t Lineshift and Linewidth in Optical Spectra

of Europium Salts, Z. Phys. 240,, 168 (1970); Chem. Abstr. 74:47651f

(1971)

Rulin, D«, Benoit a la Gulllaume, C, and Hanus, J., Magnon Sidebands

: - ne scene Spectrum of SFterromagneUe JSuropiua teid@ n AIP (Amer. Inst. Phys.) Conf. Proc. 1972, No. 5 (Pt. 2), p. 850}

Chem. Abstr. 77:26858a (1972)

Hulin, D., Benoit a la Gulllaume, C., and Hanus, J., Lateral Magnon

Emission Bands in Ferroma^nets, C. R. Acad. Sci., Ser. B 27% . 1207

(1971); Chem. Abstr. 75:81792h (1971)

Joergensen, C. K., and Berthou, K., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides lodates, and Oxides, J. Fluorine

Chem. £, 425 (1973); Chem. Abstr. 78:130358u (1973)

160
Petru, F., and Muck, A. t Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of oxides of the Lanthanldes Eu. • .Lu,

Z. Chem. 7, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Ratinen, H., X-Ray Excited Optical Fluorescence of Nine Rare Earth Ions

in Yttrium Oxide, Gadolinium Oxide, and Lanthanum Oxide, Acta

Poly tech, Scand., Chem, Incl. Met, Ser. No, 107 (1971);

Chera. Abstr. 76:106021s (1972)

Ryl'nikov, A. S., IvanoY, G, A. t Marushenko, V, I., SmirnoY, A, I,,

and Sumbaev, 0. I., Isotopic Effect of the Hyperfine Broadening of

X-Ray Lines, Pis'ma Zh. Eksp. Teor. Fiz. 2£, 128 (1970) (ftiss);

Chera. Abstr. 73:125179d (1970)

Sinha, S. P., Reflection Spectra of Europium(II), Europium(IIl),

and Gadolinium(III) Oxides, Indian J. Chem. £, 451 (1967);

Chem, Abstr. 68: 109780J (1968)

Sumbaev, 0. I,, Smirnov, Yu. P., Petrovich, E, F., Zykov, V. S.,

Egorov, A, I., and Grushko, A, I., Chemical Shifts of X-Ray ia^

Lines during Oxidation of Rare Earth Metals, Role of f-Electrons,

Rentgen, Spektry Elektron. Strukt, 7eshchestYa £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Sumbaev, 0. I,, Smirnov, Yu. P,, Petrovich, E, V., Zykov, ?. S.,

Egorov, A. I., Grushko, A, I,, Chemical Shifts of the la^

X-Ray Lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. Fiz. £§, 536 (1969) (ftiss);

Chem. Abstr. 71:7985z (1969)

Trond, S. S., Martin, J. S., StranaYage, J. P., and Smith, A. L.,

Properties of some Selected Europium-Act 1y at ed Red Phosphors,

J. Electrochem. Soc. 1047 (1969); Chem. Abstr. 71:43407*

(1969)

Tsu, R«, and Esaki, L«, Luminescence Spectra of Europium Chalcogenides:

Europium Oxide, Europium Sulfide, and Europium Selenide, Phys. ReY.

Lett. ££, 455 (1970); Chem. Abstr. 72:126968b (1970)

Vftiite, V. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 2JL, 167 (1967); Chem. Abstr. 67:69158h (1967)

(c). Europium oxide fluorides

Batsanov, S. S., DerbeneYa, S. S., and BatsanoYa, L. R,, Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh, Prikl.

Spektrosk. lfl, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

Briffaut, J. P., Spectral Study of Eu3* in Rhombohedral EuOF,

C. R. Acad. Sci., Ser, B 262, 1281 (169); Chem. Abstr.

72:84615b (1970)

161
V, Gadoliniua

(a). Gadolinium fluorides

Batsanov, S. S., Derbenera, S. S,, and Batsanova, I*. R. , Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Batsanov, S. S., and Kustova, G. K. , Effect of Structural Defects on the

Infrared Spectra of Rare-Earth Metal Oxides and Fluorides, Spektrosk.

Tverd. Tela p. 249 (1969); Chen, \bstr 73:135527e (1970)

Gil'fanov, F. I., and Stolov, A, L. , Reflection Spectrum of and

GdF

3

Powders, Zh, Prikl. Spektrosk. 5, 511 (1967) (Russ);

Chera. Abstr 57 : 77559e (1967)

Hewes, R. A., Mult ipho ton Excitation and Efficiency in the Yb3+-i»3+t -Er3*, -Ta3* Systems, Proc. Int. Conf . Lunin. p 778 (1969);

F. Williams, Ed., No rtfr-Ho llano. Publ. Co., Amsterdam, Meth.,

(Publ. 1970); Chen. Abstr 74:17762a (1971)

Hewes, R. A., and Sarver, J. F., Infrared Excitation Processes for the

Visible Luminescence of Erbiun(III), Folnium(III), and Thulium(III)

in Ytterbium(III) Sensitized P.are-Earth Trifiuorides, Phys. Rev. 1R2.

427 (1969); Che a. Abstr 71:6.TClz (1969)

Joergensen, C. K., and Berthou, H., Measurements of Photoelsctron Spectra

and Charging Effects in Fluorides, Icdates, and Oxides, J. Fluorine

Chem. j>, 425 (1973); Chen. abstr. ^8:130353u (1973)

Low, N. M., and Major, A. L. , Effects of Preparation on the Anti-Stokes

Luminescence of Erblunr-Activated lUre-Barth Phosphors, J. Lunin.

357 (1971); Che*. Abs tr 76: 1337:'.6k (1972)

Taylor, M. D. , Chemjg, T. T., p.rd Hussein, K. A., Variations of the

Infrared Spectra with the l&ture and Struct-.ire of the Xvi 2artli

Metal Halides, J. Tnorj. Tlucl. Chem. 3^, 3073 (197^); Chen. Abstr.

77:132692b (197Z)

Wertheim, G. K., Cohen, R. I., P.osencwaig, A., and Guggenheim, H« J.,

Multiplet Splitting and Two-Electron Excitation in the TriTalent

Rare Earths, Electron, Spectrosc., Proc. Int. Conf. 1971, p. 813,

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530x (1972)

Wertheim, G. K«, Rosencwaig, S., Cohen, R. L., and Guggenheim, H. J.,

Exchange Splitting in the 4f Photoelectron Spectra of the Hare

Earths, Phys. Rer. Lett. 22, 505 (1971); Chem. Abstr 75: 103444a (1971)

162
(b). Gadolinium oxides

Batsanov, S. S. f Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. IS. 332 (1969) (Russ); Chen. Abstr. 70:101332k (1969)

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I, Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and None toichiome trie Praseodymium and Terbium Oxides,

J. Fhys. C 5, 123? (1972); Chem. Abstr. 77:54303j (1972)

Bonnelle, C., and Karnatak, R. C., Distribution of f States in

Rare Earth Metals and Oxides, Collq. Int. Cent. Nat. Rech.

Sci. 1971, No. 196, p. 230 (Fr); Chem. Abstr. 77:81451n (1972)

Bonnelle, C, and Karnatak, R. C, M Spectra [X-Ray] of Gadolinium in

the Metal and the Oxide, C. R. Acad. Sci., Paris, Ser. A,B 266 . 494 (1969) (Ft); Chem. Abstr 70:82492u (1969)

Bonnelle, C, and Karnatak, R. C, Distribution of f-States in

Rare-Earth Metals and Oxides, J. Phys. (Paris), Colloq. p. 230

No. 4 (1971) (Fr); Chem. Abstr. 77:26817m (1972)

Boulon, G., Photo luminescence Processes in Bismuth Ion Activated Polycrystalline Rare Earth Oxides and OrthOTanadates, J. Phys. (Paris) 32,

333 (1971) (Fr); Chem. Abstr 75:82137k (1971)

Datta, R, K., Luminescent Beharior of Bismuth in Rare Earth Oxides,

Electrochem. Soc. 1137 (1967); Chem. Abstr 68:64265b (1968)

Davidson, F. D., and Wyckoff , R. W. G., L and M X-Ray Spectra in the

Region 2-65 A, Advan. X-Ray Anal. 9., 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V. F., Platkov, A. I., and Iyubivaya, M. V., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 62., 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)

Fischer, D. V., and Baun, V. L., Self-Absorption Effects in the Soft

X-Ray Ma and MP Emission Spectra of the Rare Earth Elements,

J, Appl. Phys. 3j2, 4830 (1967); Chem. Abstr. 68:17303c (1968)

Gil'fanov, F. Z., and Stolov, A. L., Reflection Spectrum of G^03

and GdF

3 Powders, Zh. Prikl. Spektrosk. £, 511 (1967) (Russ);

Chem. Abstr 67 : 77559e (1967)

163
Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with symmetry. III. The Spectra of Hare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochlm. Acta, Part A £2, 1909 (1967); Chem. Abstr. 67:68968k (1967)

Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. £, 425 (1973); Chem. Abstr. 78.130358u (1973)

Karyakin, A. V., Davitashvili, E. G., and Kublashvlli, Zh. Sh.,

Infrared Absorption Spectra of Carbonates and Oxalates of some

Rare Earth Group Metals, Soobschch. Akad. Nauk Gruz SSR 55,

297 (1969) (Russ); Chem. Abstr 71:117990e (1969)

Low, N. M., and Major, A* L., Effects of Preparation on the Anti-Stokes

Luminescence of Erbium-Ac

t

It at ed Rare-Earth Phosphors, J. Lumin. 4,

357 (1971); Chem. Abstr 76* 133736k (1972)

McMahon, W. R., Hemispherical Spectral Omittance of Selected Rare Earth

Oxides, U. S. At. Energy Comm., IS-T-182, (1967); Chem. Abstr.

69s6796k (1968)

Matsubara, T.. Mixed Rare Earth Phosphors, Japan Kokai 73 26.685

(CI. 13(9)-C112), 7 Apr. 1973, Appl. 71 61,170, 11 Aug 1971;

4 pp.; Chem. Abstr 79i25573h (1973)

Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu. • «Lu 9 Z. Chem. 2. 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Ratinen, H., X^Ray Excited Optical Fluorescence of Nine Rare Earth Ions

in Yttrium Oxide, Gadolinium Oxide, and Lanthanum Oxide, Acta Poly tech.

Scand., Chem. Incl. Met. Ser. No. 107, 19 pp. (1971); Chem. Abstr

76s 10602 is (1972)

Sinha, S. P., Reflection Spectra of Europium(II), Europium(III), and

Gadoliniura(III) Oxides, Indian J. Chem. 5^ 451 (1967);

Chem. Abstr 68: 109780J (1968)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, Ete Y., ZykoT, V. S.,

Egoroy, A. I., and Grushko, A. I,, Chemical Shifts of X-Ray Ka^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Veshchestva £, 172 (1969);

Chem. Abstr. 74t 117626c (1971)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. V., Zykov, V. S.,

Egorov, A. I., Grushko, A. I., Chemical Shifts of the Ka.

X-Ray Lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. Flz. 5£, 536 (1969) (Russ);

Chem. Abstr. 71i7985z (1969)

164
Suarez, C. B., and Grinfeld, R., The Gadolinium Oxide Band Spectrum,

J. Chem. Phys. 52, 1110 (1970); Chem. Abstr. 73:60782y (1970)

Sweet, J. R., and Vfhite, W. B., Flame Excited Luminescence in Terbium

and Europium Doped Rare j-.arth Oxides, Proc. Rare Earth Res. Conf.,

9th 1971, 2, 452; P. £. Field, Ed.; Chem. Abstr 76:133834r (1972)

Trond, S, S. 0 Martin, J. S., Stranavage, J. P., and Smith, A. L.,

Properties of Some Selected Europium-Activated Red Phosphors,

J. Electrochem. Soc. 116 . 1047 (1969); Chem. Abstr. 71:43407*

(1969)

Weltner, W., Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. 7j>, 514 (1971);

Chem. Abstr. 74t 105048c (1971)

White, v B.» Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appll Spectrosc. g±, 167 (1967); Chem. Abstr. 67:69158h (1967)

Wittke, J. P., Ladany, I., and Yocom, P. N. , Erbium-Ytterbium Double

Doped Yttrium Oxide, J. Appl. Phys. 42, 595 (1972); Chem. Abstr

76:78978p (1972)

(c). Gadolinium oxide fluorides

Batsanor, S, S«, Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. IP., 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

VI. Holmlum

(a). Holmium fluorides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. IQ, 332 (1969) (Russ); Chen. Abstr. 70:101332k (1969)

Chase, E. W,, Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 40, 2512 (1969);

Chen. Abstr. 71: 34384j (1969)

Yakhidov, Sh. A., Kaipov, B. , and Tavshunskii, G. A., Luminescence

of CaF

2-LnP3

Crystals in a Cobalt-60 r-Ray Field, Opt. Spektrosk.

22, 949 (1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530x (1972)

165
Wertheim, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim, H. J. # Multiplet Splitting and Two-Electron Excitation in the Triyalent

Rare Earths. Electron Spectrosc, Proc. Int. Conf. 1971, p. 813

(Publ. 1972), Shirley D. A., Ed.; Chem. Abet. 77:158530x (1972)

(b). Holmium oxides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R. , Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1959) (Russ); Chen. Abstr. 70:101332k (1969)

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far- Infrared Spectra of the Rare-Earth Sesquioxides* Cerium

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides,

J. Phys. C 5, 1237 (1972); Chem. Abstr. 77:54303J (1972)

Da?idson, F. D., and Wyckoff, R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 344 (1966); Chem. Abstr.

66 s 99767c (1967)

Demekhin, V. F., Platko?, A. I., and Lyublvaya, M. ?., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 62, 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and BatsanoT, S. S., The Width of the Fbrbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 63:73735g (1968)

Fischer, D. ¥., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and Mp Emission Spectra of the Rare Earth elements

,

J. Appl. Phys. 3g. 4830 (1967); Chem. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross, S. D. , Factors Affecting the Infrared Spectra

of Some Planar Anions with D^ symmetry. III. The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A 22, 1909 (1967); Chem. Abstr. 67:68968k (1967)

Petru, F. , and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lan than ides Eu. • .Lu,

Z. Chem. 2, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Satybaev, N. M., and Ganlchenko, L. G., Photoluminescence of Some

Rare Earth Oxides, Dokl. Nauch.-Tekh. Konf. Itogam Hauch.-Issled.

Rab. 166-1967 gg. Mosk. Energ. Inst. Sekts. Elektron. Tekh.

Podsekts. Poluprov ProboroT, p. 150 (1967) (Russ); Chem. Abstr.

69:72576q (1968)

Sumbaev, 0. I., Smirnov, Yu. P., PetroTich, E. V., Zyko?, ?• S.,

Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Ka^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Veshchestfa £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

166
Weltner, W., Jr., and DeKock, H. L*, Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J, Phys. Chen. 25, 514 (1971);

Chera. Abstr. 74: 106048c (1971)

White, W, B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 21, 167 (1967); Chem. Abstr. 67:69158h (1967)

(c). HolDiura oxide fluorides

Batsanov, S, S., Derbeneva, S, S., and Batsano?a, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. j£, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

VII, Lanthanum

(a). Lanthanum fluorides

Azarov, V. V., and Skorobo/»atov, B. S., Photo- and X-Ray Luminescence

of Rare Earth Metal-Activated LaF sinple Crystals, Ukr. Fir. Zh.

(Russ. Ed.) li, 690 (1969); Chem. Abstr. 71: 107260c (1969)

BatsanoY, S. S., Derbeneva, S. S«, and BatsanoTa, L. R«, Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q. 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Batsanov, S. S., and Kustova, G. K. , Effect of Structural Defects on

the Infrared Spectra of Rare-Earth Metal Oxides and Fluorides,

Spektrosk. Tverd. Tela, p. 249 (1969) (Russ); Chem. Abstr.

73:135527e (170)

Bauman, R. P., and Porto, S. P. S., Lattice Vibrations and Structure

of Rare-Earth Fluorides, Phys. Rev. 161 . 842 (1967); Chem. Abstr.

67:112549a (1967)

Claudel, J., Hadni, A., and Strimer, P., Low-Frequency Vibration

of Lanthanide Fluoride Lattices, C. R. Acad. Sci., Ser. B 274 . 943

(1972) (Ft); Chem. Abstr. 77:40868k (1972)

Hadni, A., Striaer, P., and Vermillard, F., Far Infrared Absorption

Observation of the Low Frequency Lines of Praseodymium Fluoride

and Other Rare-Earth Fluorides, C. R. Acad. Sci., Ser. B £9,

1113 (1969) (Fr); Chem. Abstr. 72:49216a (1970)

Hewe3, R. A., Multiphoton Excitation and Efficiency in the Yb3+-H03+

, -Br3"*", -Tar5* Systems, Proc. Int. Conf. Lumin., p. 778 (1969);

Chem. Abstr. 74:17762a (1971)

Heves, R. A., and Sarver, J. F. , Infrared Excitation Processes for the

Visible Luminescence of Erbiun(III), Kolmiua(III), and Thuliun(IIl)

in Ytterbiuit(III) Sensitized Rare-Earth Trifluorides, Phys. Rev. 182 . 427 (1969); Chen. Abstr. 71:65731z (1969)

167
Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chen. £, 425 (1973); Chem. Abstr. 78:130358u (1973)

Krupke, W. F., Tr^sition Intensities between Jiicited States of Rare

Earth Ions in Crystals, IEEE (Inst. Elec. electron, teg.)

J, Quant. Electron. 2, 693 (1966); Chen. Abstr. 66:100077m (1967)

Lowndes, R. P., Parrlsh, J. F. , and Perry, C. H., Optical Aonons ana Symmetry of Tysonite Lanthanide Fluorides, Phys. Rev. 192 . 913

(1969); Chen. Abstr. 71:75340y (1969)

Rast, R. E., Casoers, H. H., and Miller, S. A., Infrared Dispersion

and Lattice Vibrations of Lanthanum Fluoride, Phys. ReT. 171 . 1051 (1968); Chem. Abstr. 69:47830k (1968)

Shenyavskaya, E, K. , Gurvlch, L. V. , and Mal'tsev, A. A., One Band

System in the Discharge Spectrum in Lanthanum Trifluoride Vapors,

Opt. Spektrosk. j&, 1025 (1968) (Russ); Chem. Abstr. 6d:56070q

(1968)

Sychugov, V. A., and Shipulo, G. P., Relaxation Rate from the Lower

Laser Level, Zh. Eksp. Teor. Fli. 58, 817 (1970) (Riss);

Chem. Abstr. 72:127157y (1970)

Taylor, M. D., Cheung, T. T., and Hussein, M. A., Variations of the

Infrared Spectra with the Nature and Structure of the Rare Earth

Metal Halides, J. Inorg. Nucl. Chen. 3£, 3073 (1972); Chem. Abstr.

77:132692b (1972)

Vertheim, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim, H. J.,

Multiplet Splitting and Two-Electron Excitation in the Trivalent

Rare Earths Electron Spectrosc, Proc. Int. Conf. 1971, p. 813

(Publ. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530x (1972)

(b). Lanthanum oxides

Bacis, R., High Resolution Molecular Spectra Obtained with a Fabry-Perotphotoelectric Spectrometer and a Hollow-Cathode Tube Made up of an Alloy; Lanthanum Oxide, C. R. Acad. Sci., Paris, Ser. A,B 266 . 1071 (1968) (Fr); Chem. Abstr. 69:6523u (1968)

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R. , Electronic Spectra

of Rare Earth Metal Fluorides, Oxyiluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Batsanov, S. S., and Kustova, G. N. , Effect of Structural Defects on the

Infrared Spectra of Rare-Earth Metal Oxides and Fluorides, Spektrosk.

Tverd. Tela, 249 (1969) (Russ); Chem. Abstr. 73:135527e (1970)

168
Bloor # D., and Dean, J. R., Spectroscopy of Rare-Earth Qilde Systems,

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichiometric Praseodymium ana Terbium Oxides,

J. Phys. C £, 1237 (1972); Chem. Abstr. 77:54303J (1972)

Boulon, G., Photo luminescence Processes in Bismuth Ion Activated Polycrystalline Rare Earth Oxides and Ort ho vanadates, J, Phys* (Paris)

3£, 333 (1971) (Fr); Chem. Abstr. 75:82137k (1971)

Boulon, G., and Gaume-Mahn, F., luminescence Properties of lanthanum

Oxide Activated by Bismuth, C. R. Acad. Sci., Paris,

Ser. A,B 264B . 1511 (1967) (FT); Chem. Abstr. 67:77215q (1967)

Carette, P., and Blondeau, J. H«, Analysis of the Rotation of the

Indigo System in the Emission Spectrum of the Lanthanum (II) Oxide

Molecule, C. R. Acad. Sci., Ser. B 268, 1743 (1969) (Fr);

Chem. Abstr. 71:75909c (1969)

Carette, P., and Houdart, R., High Resolution Study of the Vibration

Structure of the Ultraviolet System of the LaO Molecule Emission

Spectrum, C. R. Acad. ScU, Ser. B 271 . 110 (1970);

Chem. Abstr. 73:103901f (1970)

Carette, P., and Houdart, R., Rotational analysis of the D and F Ultraviolet Systems of the Emission Spectrum of the Lanthanum(II) Oxide

Molecule, C. R. Acad. Sci., Ser. B £7£, 595 (1971)

Chem. Abstr. 74:148613a (1971)

Chun, H. U., and Hendel, D., X-Ray Spectroscopic Study of Chemical

Bonds in Oxides, Z. Naturforsch. A £2, 1401 (1967) (Ger);

Chem. Abstr. 68:63941g (1968)

Datta, R. K., Luminescent Behavior of Bismuth in Rare Earth Oxides,

J. Electrochem. Soc. 1137 (1967); Chem. Abstr. 68:64265b

(1968)

Davidson, F. D., and Wyckoff, R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 9, 344 (1966); Chem. Abstr.

66:99767c (1967)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)

Fischer, D. W,, and Baun, V. L., Self-Absorption Effects in the Soft

X-Ray Ma and Mp Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 22, 4330 (1967); Chem. Abstr. 68: 17303c (1968)

Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar anions with D^ symaetry. III. The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A 25, 1909 (1967); Chem. Abstr. 67:68968k (1967)

16"
Green, D. W. t Rotational Analysis of the C

2n -> x2!* Electronic

Transition of Lanthanum Oxide. Can. J. Phys. 49, 2552 (1971);

Chen. Abstr. 75:155462m (1971)

Green, D. W,, Rotational Analysis of the C2

!^ -> A

2^

r Electronic

Transition in Lanthanum Oxide, J. Mol. Spectrosc. 38, 155 (1971);

Chem. Abstr. 74:117814n (1971)

Joergensen, C, K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. £, 425 (1973); Chera. Abstr. 78:130358u (1973)

Matsubara, T., Mixed Rare Earth Phosphors, Japan kokai 73 26,685

(CI. 13(9)-C112), 7 Apr 1973. Appl. 71 61,170, 11 Aug (1971);

Chem. Abstr. 79:25573h (1973)

Murthy, N. S., and Murthy, B. N. , Integrated Intensities of the GreenYellow System of Lanthanum Monoxide Bands, Hature 223, 181 (1969);

Chem. Abstr. 71:55132r (1969)

# Petru, F., and Muck, A,, Chemistry of Rare Earth Elements. XXIX.

Infrared Absorption Spectra of Sc

2o3t Y2O3, and ^2.QZ*

Z. Chem. £, 386 (1966) (Ger) ; Chem. Abstr. 66:89813a (1967)

Ratinen, H., X-Ray Excited Optical Fluorescence of Nine Rare Earth

Ions in Yttrium Oxide, Gadolinium Oxide, and Lanthanum oxide.

Acta Poly tech. Scand., Chem. Incl. Met. Ser., Mo. 107, 19 pp.

(1971); Chem. Abstr. 76:106021s (1972)

Satybaev, N. M., and Ganichenko, L. G., Photo luminescence of Some

Rare Earth' Oxides, Dokl. Nauch.-Tekh. Konf. Itogam Kauch.-Issled.

Rab. 1966-1967 gg, Mosk. Energ. Inst. Sekts. Elektron. Tekh.

Podsekts. Poluprov, Proborov, p. 150 (167) (ftiss); Chem. Abstr.

69:72576q (1968)

Suarez, C, B., Rotational Constants of the B-X System of Lanthanum

0xide-180 Band Spectrum, Chem. Phys. Lett. ,16, 515 (1972);

Chem. Abstr. 77:170753e (1972)

Suarez, C. B., Yibrational Analysis of the Green-Yellow System of La180,

J. Phys. B2, 729 (1970); Chem. Abstr. 73:50397n (1970)

Suibaev, 0. I., Smirnov, Yu. P., Petrovlch, E. V., ZykoT, V. S.,

Egorov, A. I., and Grushko, A, I., Chemical Shifts of X-Ray Ka^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. VeshchestTa 2, 172 (1969);

Chem. Abstr. 74:117626c (1971)

170
Sumbaev, 0. I., Smirnov, Yu. P. t Petrovich, E. V., Zykov, V. S.,

Egorov, A. I., Grushko, A. I. f Chemical Shifts of the Kc^

X-Ray lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp, Teor. Fix. 5§, 536 (1969) (Russ);

Chem. Abstr. 71:7985z (1969)

Sweet, J. R., and White, W, B. , Flame Excited Luminescence in Terbium

and Europium Doped Rare Earth Oxides, Proc. Rare Earth Res, Conf

9th 1971, 2, 452, Field, P. £, Ed.; Chem. Abstr. 76:133834r (1972)

Matsubara, T., Mixed Rare Earth Phosohors, Japan. Kokai 73 26,685

(CI. 13(9)-C112), 7 Apr 1973. Appl. 71 61,170, 11 Aug 1971;

Chem. Abstr. 79:25573h (1973)

Weltner, W., Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. 75, 514 (1971);

Chem. Abstr, 74:105048c (1971)

IX. Neodymlum

(a). Neodymlum fluorides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. P.., Electronic Spectra

of Rare Earth Metal Fluorides, Oxy fluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chea, Abstr. 70:101332k (1969)

Batsanov, S, S., and Kustova, &. N., Effect of Structural Defects on the Infrared Spectra of Rare-Earth Metal Oxides and Fluorides,

Spektrosk. Tverd. Tela, p. 249 (1969) (Russ); Chem. Abstr.

73:135527e (1970)

Bauman, R. P., and Porto, S. P. S., Lattice Vibrations and Structure

of Rare-Earth Fluorides, Phys. Rev. 161. 842 (1967); Chem. Abstr.

67:112549a (1967)

Chase, E. W., Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electroluminescence of Zinc Sulfide Luraocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Fhys. 40, 2512 (1969);

Chem. Abstr. 71: 34384j (1969)

Chen, Y. S., DePaolis, M. V., Jr., and Kahng, D., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IEEE 58, 184 (1970);

Chem. Abstr. 72:1153162 (1970)

Claudel, J., and Hadni, A., Low-Frequency Vibration of Ienthanide

Fluoride Lattices, C. R. Acad. Sci., Ser. B 27£, 943

(1972) (Fr); Chem. Abstr. 77:40368k (1972)

173
Hadni, A., Strimer, P., and Veraillard, F., Far Infrared Absorption

Observation of the Low Frequency Lines of Praseodymium Fluoride

and Other Rare-Earth Fluorides, C. R. Acad. Sci„, Ser.

B £2, 1113 (1969) (Fr); Chem. AbBtr. 72:49216a (1970)

Lowndes, R. P., Parrish, J. F., and Perry, C, H. # Optical Phonons and

Symmetry of Tysonite Lanthanide Fluorides, Phys. Rev. 182, 913

(1969) j Chem. Abstr. 71:75340y (1969)

Sumbaev, 0. I., Petrovich, E. ?., tykov, V. S # , Ryl'nikov, A. S. t and

Grushko, A. I., Isotopic Shifts of the Kc^ Lines in the Intermediate

Region between Spherical and Deformed Nuclei, Yad. Fiz 5, 544 (1967)

(Russ); Chem. Abstr. 67:68844s (1967)

Taylor, M, D. „ Cheung, T. T., and Hussein, H. A., Variations of the

Infrared Spectra with the Nature and Structure of the Rare Earth

Metal Halides, J. Inorg. Hucl. Chem. 3073 (1972); Chea. Abstr.

77s 132692b (1972)

Wertheim, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim, H. J»#

Multiplet Splitting and Two-Electron Excitation in the Trivalent

Rare Earths, Electron Spectre sc., Proc. Int. Conf. 1971, p. 313

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530* (1972)

o (b). Neodymiura oxides

Amosov, A. V., Zakharov, V. K., Petrovskii, G., T., ProkhoroTa, T. I.,

and Yudin, D. M., Optical Spectrum of Quartz-glass Containing

Neodymium, Zh. Prikl. Spektrosk. H, 742 (1969) (Russ);

Chem. Abstr. 72:24101w (1970)

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxy fluorides and Oxides, Zh. Prikl.

Spektrosk. J£, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

oy of Rare-Earth Oxide Systems.

I, Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides.

J. Phys. C 5, 1237 (1972); Chem. Abstr. 77: 54303J (1972)

Davidson, F« D.* and Yfyckoff, R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 9_, 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V. F., Platkov, A. I., and Lyubivaya, M. V., Multiplet

Structure of the L-Series Lines of Hare-Earth Elements, Zh. Eksp.

Teor. Fiz. K>, 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl.Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 6B:73735g (1968)

174
Fischer, D. V., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth Elements

,

J. Appl. Phys. 3£, 4830 (1967); Chem. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with Symmetry. III. The Spectra of Bare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A 23., 1909 (1967); Chea. Abstr. 67:689681c (1967)

Guazzoni, G. E,, and Shapiro, S. J., Spectral Emittance of Neodymlum,

Samarium, Erbium, and Ytterbium Oxides at High Temperatures,

Natl, Techn. Inform. Serv„, AD 708547 (1970); Chem. Abstr.

74:36594p (1971)

Haensel, R., Rabe, P., and Sonntag, B., Optical Absorption of Cerium,

Cerium Oxide, Praseodymium, Praseodymium Oxide, Neodymium, Keodyraiura Oxide, and Sanarium in the Extreme Ultraviolet, Solid

• State Comraun. £, 1845 (1970); Chem. Abstr. 74:58999b (1971)

Karyakin, A. V., Davitashyili , E, G., and Kublashvili, Zh. Sh.,

Infrared Absorption Spectra of Carbonates and Oxalates of Some

Rare Earth Group Metals, Soobschch. Akad. Nauk Gruz. SSR 55^

297 (1969) (Russ); Chem. Abstr. 71:117990e (1969)

Mak, A. A., MikhailoT, Yu. N. , Stepanov, A. I., and Yastrebova, L. S.,

Effect of the Microrelief of the Lateral Face of the Active Element

of a Solid-state Laser on Its Thermal Stability, Opt.-Mekh. Prom.

36, 73 (1969) (Russ); Chem. Abstr. 72:1 16667p (1970)

Petru, F., and Muck. A., Chemistry of Rare Earth Elements. XXXVII.

Infrared Absorption Spectra or Ce02| Pr^j^, ^03, and Sm^,

Z. Chem. 7_, 27 (1967) (Ger); Chem. Abstr. 67:27441q (1967)

Satybaev, N. M., and Ganichenko, L. G., Photo luminescence of some

Rare Earth Oxides, Dokl. Nauch.-Tekh. Konf. Itogam Nauch.-Issled.

Rab. 1966-1967 gg. Mosk. Energ. Inst. Sekts. elektron. Tekh. Podsekts.

Poluprov, p. 150 (1967) (Russ); Chem. Abstr. 69:72576q (1968)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. V., Zykov, V. S.,

Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Kc^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Veshchestva £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Sumbae\, 0. I., Smirnov, Yu. P., Petrovich, E. ¥., Zykov, V. S.,

Egorov, A. I., Grushko,A. I., Chemical Shifts of the Ko^

X-Ray Lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. Fiz. 56, 536 (1969) (Russ);

Chem. Abstr. 7l:7985z (1969)

175
Weichselgartner, H., Preparation of Laser-AcUte Liquids with High

Fluorescence Lifetime, Z. Naturforsch. A 24, 1665 (1969) (Ger);

Chem. Abstr. 72:26955b (1970)

Weltner, W., Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J, Phys. Chem. 75, 514 (1971);

Chem. Abstr. 74:105048c (1971)

White, W. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 21, 167 (1967); Chem. Abstr. 67:69158h (1967)

(c). Neodymium oxide fluorides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prlkl.

Spektrosk. Ifl, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

X. Promethiurn

(a) . Promethiua fluorides

Vertheim, G. K., Cohen, R. L., Rosencwalg, A., and Guggenheim, H. J.

Multiplet Splitting and Two-Electron Excitation in the TriTalent

Rare Earths, Electron Spectrosc, Proc. Int. Conf. 1971, p. 813.

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77tl58530x (1972)

(b) . Promethium oxides

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides,

J. Phys. C £, 1237 (1972); Chem. Abstr. 77:54303J (1972)

Fischer, D. W., And Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth elements,

J. Appl. Phys. 3£, 4830 (1967); Chem. Abstr. 68:17303c (1968)

Sumbaey, 0. I., Smirnov, Yu. P., Petrorich, E. v., Zykor, V. S.,

Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray fco^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. YeshchestTa 2., 172 (1969);

Chem. Abstr. 74: 117626c (1971)

XI. Praseodymium

(a). Praseodymium fluorides

Batsanov, S. S., Derbeneva, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. iQ. 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

176
Bauman, R. P., and Porto, S. P. S., Lattice Vibrations and Structure

of Rare-Earth Fluorides, Phys. Re?. 161. 842 (1967);

Chem. Abstr. 67:112549a (1967)

Chase, E. W., Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electro

luminescence of Zinc Sulfide Lumocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 40, 2512 (1969);

Chen* Abstr. 71: 34384J (1969)

Chen, T. S,, DePaolis, M. V., Jr., and Kahng, D., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IEEE 5£, 184 (1970);

Chem. Abstr. 72:1158162 (1970)

Claudel, J., Hadni, A., and Strimer, P., Low-Frequency Vibration of

Lanthanide Fluoride Lattices, C. R. Acad. Scl., Ser. B

2?4. , 943 (1972); Chem. Abstr. 77:40368k (1972)

Hadni, A., and Striraer, P., Low-Temperature Absorption and Dichroism in

the Far Infrared of a Praseodymium Fluoride Single Crystal,

C. R. Acad. Sci., Paris, Ser. A,B 2653. 811 (1967) (Fr);

Chem. Abstr. 69: 10964 lq (1968)

Hadni, A., and Strimer, P., Far Infrared Absorption Observation of tne

Low Frequency Lines of Praseodymium Fluoride and Other Rare-Earth

Fluorides, C. R. Acad. Sci., Ser B £9, 1113 (1969) (Fr);

Chem. Abstr. 72:49216a (1970)

Lee, P. L. , Seltzer, J5. C, and Boehm, F., Energy Shifts of K X-Ray

Lines from Tri- and Tetravalent Praseodymium, Phys. Lett. A 28,

29 (1972); Chem. Abstr. 76:92301u (1972)

Lowndes, R. P., Parrish, J. F., and Perry, C. H., Optical Phonons and

Symmetry of Tysonite Lanthanide Fluorides, Phys. Rev. 132, 913

(1969); Chem. Abstr. 71:75840y (1969)

Ovsyannikova, I. A,, and Nasonova, L. I., Ljjj x-Ray Absorption Spectra

of Praseodymium and Cerium and Effective Coordination Charges,

Zh. Strukt. Khim. H, 543 (1970) (Russ); Chem. Abstr. 73:32137u

(1970)

Vertheim, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim, H. J.,

Multiplet Splitting and Two Electron Excitation in the Trivalent

Rare Earths, Electron Spectrosc., Proc. Int. Conf. 1971, p. 813,

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530x (1972)

Wertheim, G. K., Hosencwaig, S., Cohen, R. L., and Guggenheim, H. J.,

Exchange Splitting in the 4f Photoelectron Spectra of the Rare

Earths, Phys. Rev. Lett. 27 , 505 (1971); Chem. Abstr. 75:133444a

(1971)

177
(b). Praseodymium oxides

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesouioxides, Cerium

Dioxide, and Nonstoichioraetric Praseodymium and Terbium Oxides,

J, Phys. C 5, 1237 (1972); Chem. Abstr. 77t64303j (1972)

Davidson, F. D., and Wyckoff, R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Advan, X-Ray Anal. £, 344 (1966); Chem. Abstr.

66? 99767c (1967)

Demekhin, V. F., Platkov, A. I., and Lyubivaya, M. v., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 6j>, 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chen. Abstr. S8:73735g (1968)

Fischer, D. and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 3J2, 4830 (1967); Chem. Abstr. 63:17303c (1968)

Goldsmith, J, A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with D^ symmetry. Ill* The Spectra of Hare

Earth Carbonates and Their Thermal Decomtwsition Products, Soectrochlm. Acta, Part A 23, 1909 (1967); Cheou Abstr. 57:63953k (1967)

Haensel, R., Rabe, P., and Sonntag, B. f Optical Absorption of Cerium,

Cerium Oxide, Praseodymium, Praseodymium Oxide, Neodymium, Neodymium Oxide, and Samarium in the Extreme Ultraviolet, Solid State

Commun. £, 1845 (1970); Chea. Abstr. 74:53999b 81971)

Kapfhammer, W,, Maurer, V., Wagner, F. E., and Kienle, P., Isomer Shifts

and Hyperfine Splitting of the 145 keV Moessbauer Line of Praseodymiu"t~141 , Ifyperfine Interactions Excited Nacl., Proc. Conf. 1970,

5, 839 (Pub. 1971), Goldring, G., ed.; Chem. Abstr. 77:68259m (1972)

Karyakin, A. V., Davitashvili , E. and kublashvili, Zh. Sh., Infrared

Absorption Spectra of Carbonates and Oxalates of Some Rare Earth

Group Metals, Soobschch. Akad. hauk Gruz. SSR 55, 297 (1969) (Russ);

Chem. Abstr. 71:117990e (1969)

Lee, P. L., Seltzer, 3. C, and Boehm, P. , Energy Shifts of K X-Ray

Lines from Tri- and Tetravalsnt Praseodymium, Phys. Lett. A 3^,

29 (1972); Chem. Abstr. 76: 9230lu (1972)

Ovsyannikova, I. A., Nasonova, L. I., Ljjj x-Ray Absorption Spectra

of Praseodymium and Ceriuc and Effective Coordination Charges,

Zh. Strukt. Khim. H, 543 (1970) (Russ); Chem. Abstr. 73:82137u

(1970)

178
Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XXXVII.

Infrared Absorption Spectra of CeO^ Pr6

0n, Nd203, and Sm203,

Shenyavskaya, E. A., Egorova, I. V., and Lupanoy, ¥• N., Electronic

Spectrum of Praseodymium Monoxide, J. Mol. Spect rose. 47,, 355

(1973); Chem. Abstr. 79:98743y (1973)

Sumbaev, 0. I. f SmirnoY, Yu. P., PetroYich, £• V., Zykov, V. S.,

Egorov, A. I., and Grushko, A, I., Chemical Shifts of X-Ray Ko^

Lines during Oxidation of Rare Earth Metals, Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. VeshchestYa g, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Yainshtein, E. E. t Blokhin, S. M., and BerteneY, V. M., X-Ray Spectrum

of Some Cerium and Praseodymium Compounds, Izv. Sib. Otd. Akad.

Hauk SSSR, Ser. Khim. Nauk p. 59 (1966) (Russ); Chem. Abstr.

66:41906f (1967)

Yenkltachalam, T. V., Krishnamurty, G., and Narasimham, N. A., Emission

Spectrum of Praseodymium Monoxide, Proc. Indian Acad. Sci.,

Sect. A 7£, 113 (1972); Chem. Abstr. 78:64845x (1973)

Warmkessel, J. M., Lin, S.-H., and Eyring, L., Optical Absorption Spectra

of the Ordered Phases in the Praseodymium Oxide-Oxygen System, Inorg.

Chem. 8, 875 (1969); Chem. Abstr. 70: 119822a (1969)

White, W. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 21, 167 (1967); Chem. Abstr. 67j69158h (1967)

Weltner, W,, Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. 25, 514 (1971);

Chem. Abstr. 74:105048c (1971)

(c). Praseodymium oxide fluorides

Ovsyannikova, I. A., and Nasonova, L. I., Ljjj X-Ray Absorption Spectra

of Praseodymium and Cerium and Effective Coordination Charges,

Zh. Strukt. Khim. JJL, 548 (1970) (Russ); Chem. Abstr. 73:82137u

(1970)

XII. Samarium

(a). Samarium fluorides

Batsanov, S. S., Derbeneva, S. S., and BatsanoTa, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. Ifi, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

179
Chase, E. W. e Hepplewhite, H. T., Krupka, D. C. # and Kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices Containing Hare-Earth

and Transition-Metal Fluorides, J, Appl. Phys. 4j), 2512 (1969);

Chen. Abstr. 71: 34384j (1969)

Chen, Y. S., DePaolis, M. V. , Jr., and Kahng, D., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IEEE 5g, 184 (1970);

Chem. Abstr, 72j115816z (1970)

DeKock, C. W. t Wesley, R. D., and Radtke, D. D., Infrared Spectra and

Geometries of Rare Earth Dihalides. Samarium(II) Fluoride,

Samarium(II) Chloride, Europium(II) Fluoride, Europium(Il) Chloride,

Ytterbiura(II) Fluoride, and Ytterbium(II) Chloride, High Temp. Sci. ±9 41 (1972); Chem. Abstr. 76sll9428e (1972)

Eadni, A,, Morlot, G. , and Strimer, P., Far-Infrared Electronic

Transitions in Solids, IEEE (Inst, Elec. Electron. Eng.)

J. Quant. Electron. 2, 111 (1967); Chem. Abstr. 67:86235y (1967)

Joergensen, C, K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. £9 425 (1973); Chem. Abstr. 78:130358u (1973)

Petrovich, E. V., SmlrnoT, Yu. P,, Zykov, V. S., Grushko, A. I,,

Sumbaev, 0, I., Band, I. M., and TrzhaskoTskii, M. B., Chemical

Shifts of the K

ffl ^2

^

3

and fyz^ X-Ray Lines in Heavy Elements

Due to s-, p-, d-, or f-Valency Electrons- Zh. ^ksp. Teor. Fiz. 6J,,

1756 (1971); Chem. Abstr. 76s65903k (1972)

Sumbaev, 0. I., Petrovich, E. V., Zykov, V. S., Ryl'nikov, A. S., and

Grushko, A. I., Isotropic Shifts of the la^ Lines in the Intermediate

Region between Spherical and Deformed Nuclei, Yad. Fiz. 5, 544 (1967)

(Russ); Chem. Abstr. 67:68844s (1967)

Taylor, M. D., Cheung, T. T., and Hussein, M. A., Variations of the

Infrared Spectra with the Nature and Structure of the Rare Earth

Metal Halides, J. Inorg. Nucl. Chem. 34., 3073 (1972); Chem. Abstr.

778132692b (1972)

Vertheim, G. K., Cohen, R. L., Rosencwaig, A., and Guggenheim, H. J.,

Multiple t Splitting and Two Electron Excitation in the Trivalent

Rare Earths, Electron Spectrosc, Proc. Int. Conf. 1971, p. 813,

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77: 158530x (1972)

(b). Samarium oxides

Batsanov, S. S., DerbeneTa, S. S., and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q. 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

180
Bloor, I)., and Dean, J* R. , Spectroscopy of Rare-Earth Oxide Systems*

I* Far-Infrared Spectra of the Rare-Earth Sesquioxides, Ceriua

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides.

J. Phys. C £, 1237 (1972); Chem. Abstr. 77:54303j (1972)

Chun, H. U., and Hendel, D*, X-Ray Spectroscopic Study of Chemical

Bonds in Oxides, Z. Naturforsch. A 22, 1401 (1968) (Ger);

Chem. Abstr. 68:63941g (1968)

Davidson, F. D., and Wyckoff , R. W. G., L and M X-Ray Spectra in the

Region 2-85 A, Ad?an. X-Ray Anal. 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V, F. , Platkov, A. I., and tyubivaya, M. ?., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. flap*

Teor. Fiz. 6j>, 49 (1972) (Russ); Chem. Abstr. 76U06015t (172)

Dental, A. G., Fluorescent High Alumina Ceramic Substrates, Aaer*

Ceram. Soc, Bull. £1, 681 (1972); Chem. Abstr. 77:143291* (1972)

Derbeneva, S. S., and BatsanoT, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Hauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)

Fischer, D. V., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and Mp Emission Spectra of the Rare Earth Elements,

J. Appl. Phys, 32, 4330 (1967); Chem. Abstr. 68:1730Bc (1968)

Goldsmith, J. A., and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with D^ Symmetry* III. The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochlm. Acta, Part A 23., 1909 (1967); Chem. Abstr. 67:6a968k (1967)

Guazzoni, G. E., and Shapiro, S. J., Spectral Emittance of Neodyaium,

Samarium, Erbium, and Ytterbium Oxides at High Temperatures, Nat.

Techn. Inform. Serv., AD 708547 (1970); Chem. Abstr. 74:36694p

(1971)

Kublashvili, Zh. Sh., Karyakin, A. V., and DavitashTili, E. G. # Infrared Spectra of some Samarium Compounds, Soobshch. Akad. Kauk

Gruz. SSR £2, 363 (1968) (Russ); Chem. Abstr. 70:119756m (1969)

McMahon, W. R., Hemispherical Spectral Emittance of Selected Rare

Earth Oxides, U.S. At. Energy Comm. 1967, IS-T-182, Nat. Techn.

Inform. Ser.; Chem. Abstr. 69:6791* (1968)

Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XXXVII.

Infrared Absorption Spectra of Ce(J2j ?r6

0llf Nd203, and Sm^o-^

Z. Chera. 7, 27 (1967) (Ger); Chem. Abstr. 67:27441q (1967)

181
Satybaev, 11. M. , and Ganichenko, L. G., Photo luminescence of Some

Rare Earth Oxides, Dokl. Hauch.-Tekh. Konf. Ito/jaa Hauch.-l59led.

Rab. 1966-1967 gg. Mosk. Ener*. Inst. Scktc. Elektron. Tekh.

Pod3ekts. Poluprov. Proborov p. 150 (1967) (Hass); Chem. Abstr.

69:72576q (1968)

Sumbaev, 0, I., Srairaov, Yu. P., Petrovich, E. V., Zykov, V. s.,

Egorov, A. I,, and Grushko, A. I,, Chemical Shifts of X-Pay Ka^

Lines during Oxidation of Rare Earth Metals. Rcle of f-31*ctrons,

Rentgen. Spektry Elektron. Strukt. Yeshchestv* 2, 172 (1969);

Chera. Abstr. 74: 117526c (1971)

Suabaev, 0. I., Smirnov, Yu. P.. Petrovich, S. V., Zykov, V. S.,

Egorov, A. I., Grushko, A. I., Chemical Shifts of the Kcc^

X-Rays Lines during Oxidation of Hare Earth Metals. Hole of

f-ElecIrons, Zh. Eksp. Teor. Fiz. 56, 536 (1969) (Russ);

Chera. Abstr. 71:7905z (1969)

Veltner, W. # Jr., and DeKock, R. L., Spectroscopy cf Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phi's. Chea. 25, 514 (1971);

Chera. Abstr. 74:105048c (1971)

White, W. B. , Piffuse-Re flee tan ce Spectra of Rare Earth Oxides,

Appl. Spectrosc. £JL, 167 (19H7); Chera. Abstr. 67:6915% (1967)

(c). Samarium oxide fluorides

Batsanov, S, S., i)erbeneva, S. S., and Batsanova, L. P.,, Nlpctronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides nnu Oxides, Zh. Prikl.

Spektrosk. 10., 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

XIII. Terbium

(a). Terbium fluorides

Batsanov, S. S. t Derbeneva, S. S. t and Batsanova, L. R« t Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Benoit, J., and Benalloul, P.,

^ ->

7Fj Transition in the Cathodolumine sconce of Terbium Trifluoride, Zinc Sulfide-Terbium

Trifluoride, and Terbium-(3+)-Doped Zinc Sulfide Thin Films, Phys.

Status Solidi A 15, 67 (1973) (Ft); Chem. Abstr. 78:90615s (1973)

Chase, E. V., Hepplewhite, R. T., Krupka, D. C, and Kahng, D., Electroluminescence of Zinc Sulfide Luroocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 40, 2512 (1969);

Chem. Abstr. 71:34384J (1969)

182
Chen, Y. S. t DePaolis, M. V,, Jr., and kahng, D., Characteristics of

Pulse-Excited Electroluminescence from Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IEEE 5§, 184 (1970);

Chem. Abstr. 72:115816z (1970)

Chun, H. U., and Hendel, D. f X-Ray Spectroscopic Study of Chemical

Bonds in Oxides, Z. Naturforsch. A 22, 1401 (1967) (Ger);

Chem. Abstr. 68:63941g (1968)

Krupka, D. C, and Guggenheim, H. J., Optical Absorption and

Fluorescence Spectra of Single-Crystal Terbium Trifluoride,

J. Chem. Phys. 51, 4006 (1969); Chem. Abstr. 72:7665r (1970)

Krupka, D. C, and Rochkind, M. M., Infrared Spectroscopic Study on Terbium Fluoride in Solid Nitrogen and on Electroluminescent Thin

Films of Terbium Fluoride-Doped Zinc Sulfide, J. Appl. Phys. 4£t 194 (1972); Chem. Abstr. 76:52239y (1972)

Vertheim, G. K., Cohen, R. L., Rosencvalg, A., and Guggenheim, H. J.,

Multiple t Splitting and Tvo Electron Excitation in the TriYalent

Rare Earths, Electron Spectrosc, Proc. Int. Conf. 1971, p. 813,

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77:158530x (1972)

Wertheim, G. K., Rosencwaig, S., Cohen, R. L., and Guggenheim, H. J.,

Exchange Splitting in the 4f Photoelectron Spectra of the Hare

Earths, Phys. Rev. Lett. 27_, 505 (1971); Chem. Abstr. 75:103444a

(1971)

(b). Terbium oxides

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichiometric Praseodymium and Terbium Oxides,

J. Phy.s. C 5., 1237 (1972); Chem. ADstr. 77;64303j (1972)

Davidson, F. D., and Wyckoff, R. W. G., L and H X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 9_. 344 (1966); Chem. Abstr.

66:99767c (1967)

• Demekhin, V. P., Platkov, A. I., and Lyubivaya, M. Y. , Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 62., 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Dental, A. G., Fluorescent High Alumina Ceramic Substrates, Amer.

Ceram. Soc, Bull. 51, 681 (1972); Chem. Abstr. 77:143291w (1972)

Derbeneva, S, S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR17_5»

1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)

L83
Fischer, D. W. f and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 3£, 4830 (1967); Chem. Abstr. 68:17303c (1968)

Goldsmith, J. A# , and Ross, S. D., Factors Affecting the Infrared Spectra

of Some Planar Anions with D3h Symmetry, III* The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A 22, 1909 (196V); Chem. Abstr. 67:68968k (1967)

ligam, A. N., and Garg, K. B., New Lines in the L-Spectrum of Terbium,

Naturwissenschaften 54., 641 (1967); Chem. Abstr. 68 : 55047e (1968)

Petru, F., and Muck, A,, Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu. • .Lu,

2, Chem. 2» 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Sumbaev, 0. I., Smirnor, Yu. P., Petrovich, E. V., Zykov, V. S.,

Egorov, A, I,, and Grushko, A. I., Chemical Shifts of X-Ray Ka^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. Veshchestra £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Veltner, W,, Jr., and DeKock, R. L., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. 2£. 514 (1971);

Chem. Abstr. 74:105048c (1971)

White, W. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 2J,, 167 (1967); Chem. Abstr. 67:69158h (1967)

(eh Terbium oxide fluorides

Batsanov, S. S., Derbenera, S. S., and Batsanora, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxy fluorides and Oxides, Zh, Prikl.

Spektrosk. JL£, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

XIV. Thulium

(a). Thulium fluorides

Batsanov, S„ S,, Derbeneva, S. S., and Batsanova, L. R. , Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. lfl, 332 (1969) (Russ); Chem. Abstr. 70: 101332k (1969)

Chase, E. W4 9 Hepplewhite, R. T., Krupka, D. C., and Kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices Containing Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 40., 2512 (1969);

Chem. Abstr. 71: 34384j (1969)

184
Chen. T. S., DePaolis, M. V., Jr., and Kahng, D., Characteristics of

Pulse-Excited Electro luminescence fron Zinc Sulfide Films

Containing Rare Earth Fluoride, Proc. IEEE 58., 184 (1970);

Chem. Abstr. 72:115816z (1970)

Wertheim, G. K., Cohen, R. L», Rosencwaig, A,, and Guggenheim, H. J.,

Multiplet Splitting and Two-Electron Excitation in the Trivalent

Rare Earths, Electron Spectrosc, Proc, Int. Conf. 1971, p. 813,

(Pub, 1972), Shirley, D. A. p Ed.; Chen. Abstr. 77:158530x (1972)

Wertheia, G. K., Rosencvalg, S. v Cohen, R. L«, and Guggenheim, H. J.,

Exchange Splitting in the 4f Photoelectron Spectra of the Hare

Earths, Phys. Rer. Lett. ZL* 505 (1971); Chea. Abstr, 75:103444a

(1971)

(b). Thulium oxides

Bloor, D., and Dean, J. R., Spectroscopy of Rare-Earth Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nons toichiometric Praseodymium and Terbium Oxides,

J. Phys. C 5, 1237 (1972); Chem. Abstr. 77:54303j (1972)

Demekhin, V. F., Platkoy, A. I., and Lyubiraya, M. V., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Flz. 6£, 49 (1972) (Russ); Chem. Abstr. 76:1060 15 1 (1972)

Derbeneva, S. S., and BatsanoT, S. S,, The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)

Fischer, D. W,, and Baun, W. L., Self-Absorption effects in the Soft

X-Ray Ma and M3 Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 2g, 4830 (1967); Chem. Abstr. 68:17303c (1968)

Goldsmith, J. A,, and Ross, S, D., Factors Affecting the Infrared Spectra

of Some Planar Anions with D

3h symaetry. III. The Spectra of hare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A jg, 1909 (1967); Chem, Abstr. 67:68968k (1967)

• McMahon, W, R,, Hemispherical Spectral Emittance of Selected Rare Earth

Oxides, U,S. At. Energy Comm. 1967, IS-T-182, Nat. Techn. Inform.

Ser.; Chem. Abstr. 69:6796k (1968)

Petru, F. , and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu. • .Lu,

Z. Chea. 7_, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Sumbaev, 0. I,, Smirnov, Yu. P., Petrovich, E. Y., Zyko?, V. S.,

Egorov, A. I., and Grushko, A, I., Chemical Shifts of X-Ray Ec^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. VeshchesUa £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

185
Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. V., Zykov, V. S.,

Egorov, A. I,, Grushko, A. I., Chemical Shift a of the mx X-Ray Lines during Oxidation of Hare Earth Metals. Hole of

f-KLectrons, Zh. Eksp. Teor. Fiz. 56., 536 (1969) (huss);

Chem. Abstr. 71:7985z (1969)

Weltner, W., Jr., and DeKock, R. 7,., Spectroscopy of Rare Earth Oxide

Molecules in Inert Matrices at 4°K, J. Phys. Chem. To, 514 (1971);

Chem. Abstr. 74: 105043c (1971)

White, W. B. , Diffuse-Reflectance Spectra of Rare Earth Or ides,

Appl. Spectrosc. Zl» 167 (1967); Chem. Abstr. 6?:6915dh (1967)

XV. Ytterbium

(a). Ytterbium fluorides

Batsanov, S. S., Derbeneva, S. S. t and Batsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, Oxyfluorides and Oxides, Zh. Prikl.

Spektrosk. 1Q, 332 (1969) (Russ); Chem. Abstr. 70:101332k (1969)

Chase, 5. W„, Hepplewhite, R. T., Krupka, D. C, and kahng, D., Electroluminescence of Zinc Sulfide Lumocen Devices Containing; Rare-Earth

and Transition-Metal Fluorides, J. Appl. Phys. 4J), 2512 (1969);

Chem. Abstr. 71: 34384j (1969)

Combley, F. H., Stewardson, E. A., and Wilson, J. E., The M X-Ray

Absorption of Ytterbium, Proc. Phys. Soc. I, 120 (1968);

Chem. Abstr; S3: 44307p (1968)

DeKock, C. W., Wesley, R. D., and RadtKe, D. D., Infrared Spectra and

Geometries of Rare Earth Dihalides. Samarium(II) Fluoride,

Samariura(II) Chloride, Europiuri(II) Fluoride, Europium (II) Chloride,

Ytterbium(II) Fluoride and Ytterbiira(II) Chloride, High Temp. Sci. £,

41 (1972); Chem. Abstr. 76:119423e (1972)

Hewes, R. A., Multiphoton Excitation and Efficiency in the Yb^-HO3*,

-Er3+

, -Tm-3+ Systems, Proc. Int. Conf. Lumin. 1969, p. 778

(Pub. 1970), Williams, F. , Ed.; Chem. Abstr. 74:17762a (1971)

Hewes, R. A., and Sarver, J. F. , Infrared Excitation Processes for the

Visible Luminescence of Erbium(III), Holciium(III), and Tliulium(IIl)

in Ytterbiuta(III) Sensitized Rare-Sarth Trifl uoride3, Phys. Rev. 182 . 427 (1969); Chem. Abstr. 71:65731z (1969)

Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. 2, 425 (1973); Chem. Abstr. 78:130358u (1973)

186
Taylor, M. D., Cheung, T. T. , and Ku^ein, M. A., Variations of the

Infrared Spectra with the Ifoturj i.A Structure of the Rare Earth

Metal Halides, J. Inonj. Hucl. Cham 'JA, 3073 (1972); Chem. Abstr.

77:132692b (1972)

Wertheira, G. K., Cohen, R. L. , Kosericwai^, A,, and Guggenheim, H. J.,

Multiplet Splitting and Two Electron Excitation in the Tri7alent

Rare Earths, Electron Spectrosc, ?jv.o. Int. Conf. 1971, 813.

(Pub. 1972), Shirley, D. A., Ed.; Chem. Abstr. 77: 153530x (1972)

(b). Ytterbium oxides

Batsanov, S. S,, Derbeneva, S. S., pri *V tsanova, L. R., Electronic Spectra

of Rare Earth Metal Fluorides, 0.:/f] uo rides and Oxides, Zh. Prlki.

Spektrosk. 10, 332 (1969) (3uss); Chen. Abstr. 70. :101332k (1969)

Bloor, D., and Dean, J. R. ,• Spectroscopy oi Rare-Earth Oxide Systems.

I. Far—Infrared Spectra of the Hare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichionetric Praseodymium ana Terbium Oxides,

J. Phys. C £, 1237 (1972); Chem. Abstr. 77:54303j (1972)

Chun, H. U., and Hendel, D., X-Ray Spectroscopic Study of Chemical Bonds

in Oxides, Z. Naturforsch. A 22, 1401 (1967) (Ger); Chem. Abstr.

68:6394lg (1968)

Combley, F. H. t Stewardson, E. A., and Wilson, J. E. , The M X-Ray

Absorption of Ytterbium, Proc. Phys. Soc. i, 120 (1968);

Chem. Abstr. 68:44307p (1968)

Davidson, F. D., and Wyckoff, R. W. G«, L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal. 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V. F., Platko?, A. I., and Lyubivaya, M. V., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 62., 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)*

Fischer, D. W., and Baun, W. L. , Self-Absorption Effects in the Soft

X-Ray Mot and Y$> Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 2Q, 4830 (1967); Chen. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross, S. D. , Factors Affecting the Infrared Spectra

of Some Planar Anions with DJh symmetry. III. The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A £3., 1909 (1967); Chem. Abstr. 67:68968k (1967)

187
Grass, L. L., Electronic Spectra of Solid Solutions of Erbium and

Ytterbium Oxides, Diss. Abstr. Int. B 21, 5902 (1971); Chem. Abstr.

76:8365n (1972)

Guazzoni, G. E., and Shapiro, S. J., Spectral Emittance of Neodymium,

Samarium, Erbium, and Ytterbium Oxides at high Temperatures, Ifet.

Techn. Inform. Senr. AD 708547 (1970); Chem. Abstr. 74:36594p

Joergensen, C. K., and Berthou, H., Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. £, 425 (1973); Chem. Abstr. 78:130358u (1973)

McMahon, W. R., Hemispherical Spectral Emittance of Selected Hare

Earth Oxides, U.S. At. tkiergy Comm. 1967, IS-T-182, Nat.

Techn. Inform. Ser.; Chem. Abstr. 69:6796k (1968)

Matsubara, T.. Mixed Rare Earth Phosphors, Japan. Kokai 73 26,685

(CI. 13(9)-C112), 7 Apr 1973. Appl. 71 61,170, 11 Aug 1971;

Chem. Abstr. 69:25573h (1973)

Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu. • .Lu,

Z. Chem. 7_, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Sumbaev, 0. I., Smirnov, Yu. P., Petrorich, E. V., Zykov, V. S. # Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Ka^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. S.pektry Elektron. Strukt. VeshchesUa £, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. V., Zykov, V. S#,

Egorov, A. I., Grushko, A. I., Chemical Shifts of the Ka^

X-Ray Lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. Fiz. E£, 536 (1969) (Russ);

Chem. Abstr. 71:7985z (1969)

White, W. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spectrosc. 21, 167 (1967); Chem. Abstr. 67:69158h (1967)

Chemical Kinetics Information Center

Institute for Materials Research

Prepared by: Francis Westle>, October 1974 USCOMM-NBS-DC

188
Taylor, M. D., Cheung, T. T. , and Hussein, M. A«, Variations of the

Infrared Spectra with the Natur-j ml Structure 02" the Rare Earth

Metal Halldes, J. Inor^. Hucl. Chora; 3£, 3G73 (1975S).; Chem. Abstr.

77:132692b (1972)

Vertheira, G. K. , Cohen, R. L. , Kosericwaig, A., ani Guggenheim, H. J.,

Multiplet Splitting and Two Electron Excitation in the Tri7alent

Rare Earths, Electron Spectrosc, °rr.r„ Int. Gonf. 1971, 813,

(Pub. 1972), Shirley, D. A., Ed. ; Che .-a, Abstr. 77: i.53530 x* (1972)

(b). Ytterbium oxides

Batsanov, S. S., Derbeneva, S. S., > tsanova, L. H., Electronic Spectra

of Rare Earth Metal Fluorides, 0 :/f3 no rides and 0xida3, Zh. Prlkl.

Spektrosk. 1Q, 3.32 (1969) (Russ); Chen. Abstr. 70:1013321c (1959)

Bloor, D., and Dean, J. R.,' Spectroscopy 01 Rare-Earuh Oxide Systems.

I. Far-Infrared Spectra of the Rare-Earth Sesquioxides, Cerium

Dioxide, and Nonstoichionetric Praseodymium' ana Terbium Oxides,

J. Phys. C 5, 1237 (1972); Chem. Abstr. 77:54303j (1972)

Chun, H. U., and Hendel, D., X-Ray Spectroscopic Study of Chemical Bonds

in Oxides, Z. Naturforsch. A 22, 1401 (1967) (Ger); Chem. Abstr.

68:6394lg (1968)

Combley, F. H. t Stewardson, E, A., and Wilson, J. E. , The M X-Ray

Absorption of Ytterbium, Proc. Phys. Soc. i, 120 (1968);

Chem. Abstr. 68:44307p (1968)

Davidson, F. D. , and Wyckoff , R. W. G«, L and M X-Ray Spectra in the

Region 2-85 A, Advan. X-Ray Anal, g, 344 (1966); Chem. Abstr.

66:99767c (1967)

Demekhin, V. F., PlatkoT, A. I., and Lyubivaya, M. V., Multiplet

Structure of the L-Series Lines of Rare-Earth Elements, Zh. Eksp.

Teor. Fiz. 62, 49 (1972) (Russ); Chem. Abstr. 76:106015t (1972)

Derbeneva, S. S., and Batsanov, S. S., The Width of the Forbidden

Zone for Rare-Earth Metal Oxides, Dokl. Akad. Nauk SSSR 175. 1062 (1967) (Russ); Chem. Abstr. 68:73735g (1968)*

Fischer, D. W., and Baun, W. L., Self-Absorption Effects in the Soft

X-Ray Ma and K£ Emission Spectra of the Rare Earth Elements,

J. Appl. Phys. 32. 4830 (1967); Chen. Abstr. 68:17303c (1968)

Goldsmith, J. A., and Ross, S.' D. , Factors Affecting the Infrared Spectra

of Some Planar Anions with D

3h symmetry. III. The Spectra of Rare

Earth Carbonates and Their Thermal Decomposition Products, Spectrochim. Acta, Part A £3.. 1909 (1967); Chem. Abstr. 67:68968k (1967)

187
Grass, L. L., Electronic Spectra of Solid Solutions of Erbium and

Ytterbium Oxides, Diss. Abstr. Int. B 31, 5902 (1971); Chem. Abstr.

76:8365n (1972)

Guazzoni, G. E., and Shapiro, S. J., Spectral Emittance of Neodymlum,

Samarium, Erbium, and Ytterbium Oxides at high Temperatures, ifet.

Techn. Inform. Sery. AD 708647 (1970); Chem, Abstr. 74:36594p

Joergensen, C. K., and Berthou, H. , Measurements of Photoelectron Spectra

and Charging Effects in Fluorides, Iodates, and Oxides, J. Fluorine

Chem. 425 (1973); Chem. Abstr. 78:130358u (1973)

McMahon, W. R., Hemispherical Spectral Emittance of Selected Hare

Earth Oxides, U.S. At. j-hergy Comm. 1967, IS-T-182, Nat.

Techn. Inform. Ser.; Chem. Abstr. 69:6796k (1968)

Matsubara, T.. Mixed Rare Earth Phosphors, Japan. Kokai 73 26,685

(CI. 13(9)-C112), 7 Apr 1973. Appl. 71 61,170, 11 Aug 1971;

Chem. Abstr. 69:25573h (1973)

Petru, F., and Muck, A., Chemistry of Rare Earth Elements. XL.

Infrared Absorption Spectra of Oxides of the Lanthanides Eu* • .Lu,

Z. Chem. 7_, 159 (1967) (Ger); Chem. Abstr. 67:27442r (1967)

Sumbaev, 0. I., Smirnov, Yu. P., Petrorich, E. V., Zykov, V. S. t Egorov, A. I., and Grushko, A. I., Chemical Shifts of X-Ray Ko^

Lines during Oxidation of Rare Earth Metals. Role of f-Electrons,

Rentgen. Spektry Elektron. Strukt. VeshchesUa g, 172 (1969);

Chem. Abstr. 74:117626c (1971)

Sumbaev, 0. I., Smirnov, Yu. P., Petrovich, E. V., itykov, V. S.,

Egorov, A. I., Grushko, A. I., Chemical Shifts of the Kcc^

X-Ray Lines during Oxidation of Rare Earth Metals. Role of

f-Electrons, Zh. Eksp. Teor. Fiz. 5£, 536 (1969) (Russ);

Chem. Abstr. 71:7985z (1969)

White, W. B., Diffuse-Reflectance Spectra of Rare Earth Oxides,

Appl. Spect rose. 21, 167 (1967); Chem. Abstr. 67:69158h (1967)

Chemical Kinetics Information Center

Institute for Materials Research

Prepared by: Francis Westle>, October 1974 USCOMM-NBS-DC

188

I