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national bureau of SIMM

OCT 2 8 1975

OCC

(5ci oo Crystal Structure Transformations

5’S' in Inorganic

Nitrites, Nitrates, and Carbonates

C , Ti— /V3S i'-c.C

C. N. R. Rao, B. Prakash, and M. Natarajan

Department of Chemistry,

Indian Institute of Technology,

Kanpur, India

U.S. DEPARTMENT OF COMMERCE, Rogers C. B. Morton, Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

Issued May 1975
Library of Congress Cataloging in Publication Data

Rao, Chintamani Nagesa Ramachandra.

Crystal structure transformations in inorganic nitrites, nitrates, and carbonates. (NSRDS-NBS 53)

Supt. of Docs. no. : C 13.48.53

1. Crystals. 2. Phase rule and equilibrium.

I. Prakash, Brahm, 1912- joint author.

II. Natarajan, M., joint author. III. Title. IV. Series: United States. National Bureau of Standards. National

Standard Reference Data Series, NSRDS-NBS 53. QC100.U573 no. 53 [QD921] 389\6’08s [548’.81] 74-18389

NSRDS-NBS 53

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 53* 48 pages (May 1975)

CODEN: NSRDAP

© 1975 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1975

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

(Order by SD Catalog No. C13.48:53). Price $1.1

5
Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a

variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in

need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically

evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects also establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned: nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials is a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Ill
Preface

Many inorganic solids undergo transformations from one crystal structure to another. Studies

of these phase transformations are of value in understanding the nature and properties of solids. Recent literature abounds with information on phase transformations of solids and it is often

difficult to obtain relevant data or references on the transformation(s) of any specific substance.

We, therefore, considered it worthwhile to collect the literature on the phase transformations of

various types of inorganic solids and present them in an organized manner. As part of this program,

we published monographs on binary halides (NSRDS-NBS-41) and transition metal oxides

(NSRDS-NBS-49) some time ago. In this monograph, we have reviewed the important data on

the crystal structure transformations of salts of three typical oxyanions, nitrites, nitrates and

carbonates. These salts exhibit several types of interesting transformations which have been

examined by a variety of techniques. We plan to publish reviews on inorganic sulfates and other

solids in the future. In preparing this monograph, we have surveyed most of the material abstracted up to June 1973

in Chemical Abstracts. We have listed the important references to the published literature after presenting the survey on each solid. In reporting the information on the transformations of a solid,

we have indicated the methods employed as well as the important data and conclusions. For each

solid, we have given the crystallographic data for the stable phase around room temperature and

at atmospheric pressure, making use of the standard data published by NBS whenever possible.

We are thankful to Mr. S. Chattopadhyay for his assistance in the literature survey.

IV
Contents

Page Preface IV

Introduction 1 Units, Symbols and Abbreviations 2

1. Nitrites 2

1.1. Alkali metal nitrites 2

1.2. Alkaline earth metal nitrites 9

1.3. Thallium nitrite 10

2. Nitrates 10

2.1. Nitric acid 10

2.2. Alkali metal nitrates 10

2.3. Ammonium nitrate 24

2.4. Thallous nitrate 30

2.5. 3d Transition metal nitrates 33

2.6. Silver nitrate 35

3. Carbonates 37

3.1. Alkali metal carbonates , 37

3.2. Alkaline earth metal carbonates 38

3.3. Thallous carbonate 45

3.4. 3d Transition metal carbonates 46

3.5. Silver carbonate 48

V
• . ;
Crystal Structure Transformations in Inorganic Nitrites, Nitrates, and

Carbonates *

C.N.R. Rao, B. Prakash, and M. Natarajan

A critical survey of the data describing crystal structure transformations in inorganic nitrites, nitrates and carbonates is compiled. Data on crystallographic, thermodynamic, spectroscopic, electrical, dielectric and other properties are given for each solid. Experimental techniques used to obtain

the data are given and comments on the data are included in the tables. The literature is surveyed up to June 1973. References have been selected on the basis of their pertinence to the data cited. Key words: Nitrites, nitrates, carbonates, crystal structure transformation, phase transformation,

x-ray diffraction data. Introduction

The area of phase transformations in inorganic

solids has been very active in recent years and the

subject has been reviewed recently by Ubbelohde

[1]

1 and Rao [2, 3]. The general features of crystal

structure transformations were described briefly

in an earlier NSRDS-NBS monograph from this

laboratory [4]. In this monograph we shall confine our attention to the crystal structure transformations

in inorganic nitrites, nitrates and carbonates. We

have chosen these systems as our first set of typical

oxyanion salts in view of their interesting properties

and transformations and also because the reviews

of the thermal decompositions of these salts have

been recently published by the National Bureau of

Standards [5, 6].

All the three oxyanions, nitrite, nitrate, and car- bonate, are sp

2 hybridized with bond angles close

to 120°. The N—O distance in ionic nitrites and

nitrates is close to 1.2 A and the C—O distance in

carbonates is 1.3 A. In some of the salts, these

anions form fairly strong covalent bonds particularly with the transition metals.

Inorganic nitrites, nitrates and carbonates show

a variety of interesting properties of particular

interest to the subject of this review. Thus, NaNC>2 exhibits a well-characterized ferroelectric transition near 438 K. NaN03 undergoes an order-disorder

phase transition associated with the rotation of the

* Supported by Project G-77 of the National Bureau of Standards under the Special

International Programs.

1 Figures in brackets indicate literature references at the end of each section.

nitrate ion. Many other ionic nitrates also exhibit

transitions determined by the orientation of NOt

ions. RbN03 , NH4 N03 , and T1N03 undergo several

transitions and the different phases are structurally

related. KN03 transforms from the orthorhombic

aragonite phase to the rhombohedral calcite phase

near 403 K, but on cooling, the calcite phase re- verts back to the aragonite phase through an intermediate ferroelectric phase. CaC03 with a critical

radius ratio of 0.67 exists as aragonite with a cation

coordination of 9 or as calcite with a coordination

of 6. The aragonite-calcite transformation proceeds

by a reconstructive mechanism and such transitions are also found in nitrates. While aragonite

transforms to calcite on heating, the latter reverts back to aragonite only under pressure. Impurities

affect phase transitions of several of the oxyanion

salts. Under high pressures, many of these oxyanion salts exhibit new phases of interest. We shall

now systematically review the phase transitions

of nitrites, nitrates and carbonates of the various

elements.

References

[1] Ubbelohde, A. R., Quart. Rev. (London), 11, 246 (1957).

[2] Rao, C. N. R., and Rao, K. J., in Progress in Solid State Chemistry, Ed. H. Reiss, Vol. 4 (Pergamon Press, Oxford,

1967).

[3] Rao, C. N. R., in Modern Aspects of Solid State Chemistry,

Ed. C. N. R. Rao (Plenum Press, New York, 1970).

[4] Rao, C. N. R., and Natarajan, M., Crystal Structure Transformations in Binary Halides, NSRDS-NBS-41, National Bureau of Standards, July 1972.

1
[5] Stern, K. H., and Weise, E. L., High Temperature Properties

and Decomposition of Inorganic Salts, Part 2, Carbonates,

NSRDS-NBS-30, National Bureau of Standards, No- vember 1969.

[6] Stern, K. H., High Temperature Properties and Decomposition of Inorganic Salts, Part 3, Nitrates and Nitrites, J. Phys. Chem. Ref. Data, 1, 747-772, 1972. Units, Symbols, and Abbreviations

P = Pressure; 1 atm., (~ 1 bar) = 101325 Nm_2 =

1013250 dyn cm-2 T = Temperature in kelvins

R = Gas constant = 8.3143 J mol-1 deg-1 =

1.98717 cal mol-1 deg-1 J —Joule

C = Coulomb

Hz = Hertz (cycle/second)

V = Volt

cal = Thermochemical calorie = 4.1840 J Tt = Transformation temperature

A T = Thermal hysteresis in a reversible trans- formation

A//tr = Enthalpy change accompanying the trans- formation

AS tr = Entropy change accompanying the trans- formation

Af ' = Entropy change accompanying the trans- formation

Tc = Curie Temperature

Tn = Neel temperature

Cp = Heat capacity at constant pressure

Cm — Magnetic heat capacity

cr = Electrical conductivity

p = Density (in grams per cm3

) e = Dielectric constant

tan 8 = Dissipation factor

Ps — Spontaneous polarization

Ec = Coercive field Ea = Energy of activation

A6 = Gibb’s free energy change

X = Magnetic susceptibility

r = Relaxation time

Z = Number of molecules per unit cell IR = Infrared

UV = Ultraviolet

DTA = Differential thermal analysis

NMR= Nuclear magnetic resonance NQR= Nuclear quadrupole resonance ESR = Electron spin resonance. 1. Nitrites

The nitrites of only the alkali metals (especially

Na and K) have been extensively studied and these

undergo phase transformations. The following is an account of the available information regarding the

phase transitions of inorganic nitrites.

1.1. Alkali Metal Nitrites

The transformation temperature, melting point,

dissociation point, and the heat of transition of alkali

metal nitrites are given below [1-3]:

Transitions in alkali metal nitrites

r„ k Melting

point, K

Dissociation

point, K

Afftr, cal mol-1

LiN02 367 493 503 —

NaN02 439 555 703 250

kno2 320 711 753 120 ±30

RbN02 348 695 793 500 ±50

CsN02 393 673 783 1100 ±100

The transformation temperature, Tt , does not show

any systematic trend. The transformations in LiNCU,

RbNC>2 , and CsNCU have not been studied in detail,

but a number of workers have investigated the trans- formation in NaNC>2 and KNO2 by a variety of

techniques.

Lithium Nitrite, LiNCU (No crystal data seem to be

available).

Protsenko and coworkers [3] have reported a phase transformation in lithium nitrite at 367 K.

The transformation has been characterized by the

anomaly in the DTA and electrical conductivity

measurements.

Sodium Nitrite, NaN02 , orthorhombic (bodycentered), Cf°-Im2m, z — 2, a = 3.570 A, 6 = 5.578 A,

c= 5.390 A at 299 K.

Sodium nitrite was found to be ferroelectric a number of years after the discovery of its phase

transition and the literature on the ferroelectric

transition of NaN02 up to 1962 has been reviewed

by Jona and Shirane [3a]. Ferroelectricity in

this compound was predicted by Zheludev and

Sonin [4] in 1957 from the changes in point group

symmetry due to the ferroelectric phase transition

and was independently observed by Sawada et al. [5]. During the past decade, this solid has attracted

considerable attention which has led to numerous

investigations of its various physical properties

such as dielectric constant [6—10], domain structure

[11-13], specific heat [14-16], thermal expansion

[14, 16-18], thermal conductivity [19], electrical

resistivity [20], NMR [21], x-ray diffraction [12, 17,

22, 23], and optical properties [24-27].

2
Sodium nitrite at normal temperature and pres- sure has a body-centered orthorhombic unit cell.

It is ferroelectric with the spontaneous polarization

parallel to the 6-axis and undergoes a first order

transformation to the paraelectric phase around

438 K. Between the ferroelectric (III) and paraelectric (I) phases, a sinusoidal antiferroelectric

phase (II) has been reported to exist over the nar- row temperature range of 436.8-438 K [10, 10a,

15, 16, 18, 21, 28]. In the ferroelectric phase, the NOf ions are

parallel in the a-planes; the ordering parameter of

the N02- ions in the a-plane changes sinusoidally

along the a-axis with a period of about eight layers

[28]. Sawada et al. [29] have studied the domain

reversal of NaN02 and discussed the “Himidashi”

(bulging out) phenomenon peculiar to this solid

caused by the variation of spontaneous polarization

(Ps ) and the coercive field (E c ) with the size of the

electrode. Recently, Fliigge and Meyenn [29a] have

studied the theoretical aspects of the order-disorder

transition in NaN02 in which a two sublattice model

of interacting dipoles is treated in. a molecular field approximation to describe the ferro- and paraelectric properties of NaN02 . Polarization values

thus calculated, are found to be in good agreement

with experiment for the narrow antiferroelectric

domain not resolved by the model. Yamada and

Yamada [29b] had pointed out earlier that the

long-range, dipole-dipole type interaction plays the

important role to initiate the phase transitions in

sodium nitrite. In addition to the transitions, III—» II and II —

>

I, some anomalies at 375, 451, and 488 K have also

been reported [17, 18, 30]. These anomalies are believed to be related to anisotropic vibrorotatory

states of the NO^ ions.

Gesi [31] has reported a new phase transformation (III- IV) in ferroelectric NaN02 at 178 K from

precise measurements of thermal expansion and

low frequency dielectric constant at normal pressure. Phase IV is a high pressure phase existing at 8 kbar and room temperature and is described in

detail later in this section. This III- IV transition

did not show any thermal hysteresis and is of second

order since no discontinuous change was found

either in dielectric constant or volume thermal

expansion measurements.

High Pressure Transformations: Bridgman [32]

detected a high pressure transition, probably of

the second order, as a break in the slope of the

compression curve of the solid. This transition was

also observed optically by Lippincott et al. [33] in

their high pressure anvil device. They measured the

bending vibration frequency v2 of NO;T in NaN02 at high pressure and found an abrupt change in v2 from 825 cm-1 at atmospheric pressure to 855

cm-1 after the III—IV transition at 14.5 kbar. This

indicates a change in the electronic structure (or

the shape of the N02- ion) during the III—IV transition. Rapoport [34] has determined the phase diagram of NaN02 up to 40 kbar and from room

temperature to 773 K. The phase diagram consists

of five solid phases abbreviated as I, II, III, IV, and

V. The I, II, and III phases are the paraelectric,

antiferroelectric, and ferroelectric phases, re- spectively. Phase IV is identical to the high pres- sure phase described by Bridgman [32] and is the

same found by Gesi [31] below 178 K. Phase V is another high pressure phase which exists just

below the melting point above 10 kbar. Rapoport

has indicated that the extrapolation of III—IV

phase boundary to atmospheric pressure gives a temperature of 168 K. The problem whether the

room-temperature phase III transforms to the

high pressure phase IV at atmospheric pressure or not is interesting. The ferroelectric Curie point,

Tc , (III—II phase transition) and the Neel point,

PN (I—II phase transition) were detected by DTA up

to 40 kbar. These results were found to agree well

with those of Gesi [31].

3
NaN02

Measurement technique Observations Remarks References

X-ray diffraction

.

X-ray investigation of the dis- ordered structure of NaN02 near Tc (~ 433 K).

Differential Thermal Analysis

Differential scanning calo- rimetry.

Specific heat measure- ments in an adiabatic

calorimeter.

Thermal conductivity in the range 343-463 K along a,

b, and c axes.

Thermal expansion and di- electric studies.

rt

, 436 K.

Tt , 433-435 K.

Ferroelectric NaN02 crystal transforms through the first order transition to an

antiferroelectric phase with a sinusoidal modulation of the moment in which the

antiferroelectric order is partially attained. The system transforms to a paraelectric

phase at a higher temperature. The suc- cessive appearance of these phases, the order of transition, the temperature de- pendence of the order parameter an<^ the anomalous volume expansion are ex- plained by a thermodynamic calculation on the basis of a molecular field approxi- mation.

The observed diffuse scattering, the satellites and the plate-like diffuse scatter- ing normal to the 6-axis around them can

be interpreted on the basis of a disordered

arrangement of two kinds of structural

units. The atomic positions in each structural unit were determined from the rela- tive intensity of the Bragg reflections and

that of the satellites. The structure factors and the corresponding Fourier synthesis were also calculated. It is concluded that at 423 K, about

15 percent of the N02 groups are in their centrosymmetric positions.

Enthalpy of phase transition, AHlr , 299

33 cal mol-1

.

The specific heat starts to increase anomalously at 373 K. At 436 K, there is a sharp peak in the curve. At 437 K a small peak appears after which the

specific heat decreases gradually with increasing temperature up to 453 K.

Thermal conductivities in the b and a

directions show a gradual decrease on

heating over a wide temperature range

of 50 K below the transition. This de- crease is^cjue to an additional thermal

resistivity. No anomaly is found in the temperature dependence of thermal conductivity in the c-direction.

A new phase transformation at 178 K in NaN02 (ferroelectric phase) is indi- cated by slight break in these properties both in dielectric constant versus temp,

and thermal expansion versus temperature curves.

[28],

[23, 35],

[36].

The first anomaly corresponds to the first order ferroelectric to antiferroelectric phase transition, while the second

anomaly is regarded to be due to an

antiferroelectric-paraelectric phase transition.

A tentative model of the order-disorder arrangement of the NO;T ions is pro- posed to account for the origin of the

additive thermal resistivity in which uneven interatomic forces, due to the disordered as scattering centers of phoThe transition is believed to be the III- IV

transition in which the ferroelectric NaN02 transforms to the high pressure phase which exists above 8 kbar at 298 K.

[37]

,

[38]

,

[15].

[19].

[31].

4
NaN02 — Continued

Measurement technique Observations Remarks References

Dielectric Studies, in dc bias

fields up to 3.5 kV cm-1 at 436-437 K.

The temperature range studied is between

Tc (Curie Temperature) and TN (Neel

Temperature).

It is difficult to conclude whether the ferro- electric phase to sinusoidal phase transi- tion becomes first order with increasing

bias fields. The sinusoidal state narrows

gradually and disappears at ~ 2.6 kV

cm'1 -

[39].

Dielectric and pyroelectric measurements (e measured along the ferro- electric b axis.

€* shows a distinct anomaly at Tc and obeys

Curie-Weiss law, below and above Tc

. The ratio of the Curie constants was

found to be 9.6: 1.

[6].

Experimental (dielectric constant, pyroelectric current

etc) and theoretical

studies.

e shows a peak at 437.2 K while heating

and 435.6 K while cooling. Dielectric dispersion exists in all axial directions Ps ~ 8.6 nC cm-2 estimated from pyroelectric current measurements, at room

temperature.

Ferroelectricity in NaN02 is discussed

phenomenologically taking account of the electrocaloric effect. It is concluded

that the transition in NaN02 is a first order one and that the main contribution to the spontaneous polarization comes from the relative displacement

between Na+ and NOf ions. Also the

ferroelectric NaN02 is half-way between

an ionic and a molecular crystal.

[9].

Electrical conductivity (poly- crystalline pellet). The conductivity-temperature curves showed discontinuities or change in slope

at or near the transformation temperature.

[40].

Infrared Spectra Transitions are associated with changes

in vibration frequency. NaNOi exhibits changes of all the parameters of the Urbach equation.

Transition in ferroelectric crystals can be

correlated with dynamic theories of the

crystal lattice of NaN02 .

[41].

Raman Spectra range: 303-

451 K. Raman lines show marked changes near thetransition points.

A group theoretical treatment of the vibrational spectrum of the NaN02 crystal is presented for the low and high temperature modifications of NaN02 .

[42].

Range: 313-493 K The temperature dependence of frequencies of hands at 119, 153, and 220 cm-1 shows an abnormal decrease in the fre- quency of the dipole vibration at 153 cm-1

.

The decrease in the dipole vibration fre- quency has been discussed on the basis of the Ginzburg-Anderson-Cochran

theory.

[43],

Range: 323-455 K Spontaneous polarization disappears above

the \-point.

The disappearance ofPs has been explained

partially by reorientation of some NOf

groups as a result of their rotation by 180° around the axis parallel to the line joining O-atoms. The forms of normal vibrations are considered on the basis of symmetry

coordinates and the intensity of lines. Recent studies [45a], however rule out any

major difference between the low and high

temperature spectra. It seems that crystal symmetry is not changed during the transformation.

[44, 45],

Ultraviolet Absorption spectra. A gradual shift of absorption hands is found

to accompany thermal expansion of the

crystal. An abrupt change in the absorption spectrum is observed at transformation points.

Tt ~ 313-323 K (II —

I) (marked hysteresis).

These two effects of temperature seem to be

correlated. In cases where crystal struc- tures are known, shifts in absorption max- ima due to changes in temperature have

been interpreted in relation to changes in the cation-anion distances.

[26],

5
NaN02 — Continued

Measurement technique Observations Remarks References

7, ~ 438 K The larger increase in fi x than in /ny

(/ll =

root-mean-square amplitude) for the N- atom might indicate the expected rotation about (001). /a of motion for O-atoms are ambiguous.

[46],

Nuclear relaxation A peak is observed in the Na23 nuclear

relaxation rates, at the ferroelectric

transition.

This effect is explained on the basis of the theory of the transition in terms of lattice dynamics. It is argued that nuclear-spinphonon relaxation can be a powerful tool of investigation for a ferroelectric transition.

[47].

Nuclear quadrupole reso- nance. N14 NQR lines have been observed in the ferroelectric-phase of NaN02 and the change of NQR frequencies with r be- tween 77 and 437 K has been investi- gated. The NQR frequency seems to begin to deviate from the rigid molecule

vibration model around III—IV transition.

The results can be explained by an order- disorder model where the NOf ions are

flipping between two equilibrium sites. Disappearance of ferroelectricity can be attributed to the onset of rotation of NOf ions above Tt (473 K).

[48, 49],

Effect of hydrostatic pres- sure on Tc and TN up to 10 kbar.

Both Tc and TN increase with increasing

pressure. The experimental results could be fairly explained on the basis of a phenomenological model developed by Gesi. The

model includes a three dimensional lat- tice strain and accounts for the dielectric constant variation in a bias field.

[50, 51].

Potassium Nitrite, KNO2 , rhombohedral, R3m,

Z = 1, a = 4.455 A, <* = 68°58' at 298 K (54).

The room-temperature structure of KNO2 was

first considered to have monoclinic symmetry

(space group C*-Am) [52], but recent studies

[52a-54] have established the structure to be

rhombohedral with a centrosymmetric space group

R3m. The unit-cell parameters for a disordered,

rhombohedral, room temperature phase according

to Solbakk and Strpmme [53] are: a= b = 5.011 A,

c = 10.153 A with Z — 3. The crystal structure of

KNO2 at low temperatures (253 K) has monoclinic

symmetry, space group, P2i/c, and the unit cell parameters a — 4.16 ± 0.02 A, b = 962 ± 0.05 A,

c = 6. 19 ±0.03 A, /3= 113± 1°,Z = 4. Above 313 K,

KNO2 is cubic (Fm3m), with a = 6.66 A, Z = 4 at 318 K (53).

Three transformations are known in KNO2 . Denoting the various phases as I, II, and III, the

transformations can be described as follows (55):

III 260 K v 313 K

11 XT (monoclinic) (rhombohedral) ^ I (cubic)

Another transition is reported at 343 K by Tanisaki

and Ishimatsu [54] who also report an appreciable

dielectric anomaly at ~ 230 K. Ray and Ogg [56]

report AHir ~ 1200 ± 200 cal mol-1 for the transition at 260 K. The nature of the transition around

313 K has been controversial and was considered

to be a ferroelectric-paraelectric transformation by

Rao and Rao [57]. Recently, Mansingh, and Smith

[55] in their studies of dielectric constant and electrical conductivity have concluded that there is no

ferroelectric phase in KNO2 up to its melting point.

At 313 K, there is only a crystal structure change

from the rhombohedral to the cubic form. This has

also been supported by the assignment of a centro- symmetric (R3m) space group to KN02 by Solbakk

and Strpmme [53]. Above 319 K, KN02 has the cubic

NaCl structure with a — 6.71 A [56]. Doucet and co- workers [58] have reported a hitherto unknown

transition in KN02 at ~ 402 K from x-ray and dielectric constant measurements.

High Pressure Transformations: Bridgman [59] re- ported a high pressure transition in potassium nitrite. He however, used a rather impure sample (~ 89%

6
purity). High pressure transitions at 260 K and

320 K have been reported by Ray and Ogg [56] and

Hazlewood et al. [60], respectively. A continuous

transformation starting at about 638 K has also

been observed. Rapoport [34] and Clark and

Rapoport [61] showed the phase diagram of KNO2 to consist of the six solid phases given below:

Phase diagram of KNO2

Phase Crystal structure Range of stability

I Cubic, NaCl type Above 323 K and below 10 kbar.

II Cubic, distorted Below 323 K and 8 kbar.

Ill NaCl type, (metastable phase) ... Below 273 K and 8 kbar. IV Cubic, distorted Above 273 K and 10 kbar. V

CsCl type. Cubic, CsCl type Above 345 K and 10 kbar. VI Around 373 K and ~ 35 kbar.

The I — II and IV— V phase boundaries determined

by DTA were found to rise very slowly with pressure.

The II— IV, I— IV and I— V boundaries were determined by the volume discontinuity method. In this

work two new high pressure phases, V and VI, were

discovered. The melting curve of KN02 exhibited a maximum at 7.0 kbar and 739 K, and meets the IV

boundary at a triple point at 15.2 kbar and 686 K and

then increases steeply with pressure. Clark and

Rapoport [61] report the pressure dependence of

KNO2 (III- II) transition by DTA in a pistoncylinder device [62-65]. They used a 97.5 percent

pure sample after two recrystallizations. The III- II transition was found to be from a completely ordered

(NaCl like) phase to a partially disordered phase,

whereas the II- 1 transition is from a partially disordered phase to a completely disordered NaCl

phase [61]. Larionov and Livshits [66] have studied

the polymorphic transformation (III- IV) at 15 kbar

and 77-488 K and described the phase diagrams

showing the relative disposition of the various

phases.

Rubidium Nitrite, RbN02 . RbN02 is reported to undergo an endothermic

phase transformation at ~ 348 K with A//tr =500 ±50

cal mol-1

[1]. The DTA and electrical conductivity studies of Natarajan and Hovi [70] indicate an anomaly in the temperature range 340-390

K due to the phase transformation. Richter and

Pistorius [69] have investigated the crystal structure

and the pressure transformations of RbN02 . According to them, RbN02 (phase I) at ambient

conditions is cubic (space group O^ — Fm3m,

with a — 6.934 A). It transforms at —261 K to monoclinic RbN02 (phase II) with a = 8.904 A,

6 = 4.828 A, c = 8.185 A, /3= 115.7° (determined at 271 K). RbN02 (II) appears to be ordered, whereas

RbN02 (I) has a configuration entropy of Rln 32.

The II/I transition line terminates at 0.3 kbar

with appearance of RbN02 (phase III), a phase

17.3 percent denser than RbN02 (I). The II/III

transition pressure increases with decreasing

temperature to a triple point at 1.2 kbar, 208 K

where a further dense phase IV appears. The

II/IV transition pressure rises slightly with decreasing pressure. The melting curve of phase I passes

through a maximum at 2.2 kbar, 663 K and is terminated at the III/I/liquid triple point at 5.2

kbar, 655 K. The melting curve of phase III rises

with pressure.

Cesium Nitrite, CsN02 , cubic, O* — Pm3m, a —

4.34 ±0.02 A at ambient conditions [2].

Cesium nitrite seems to undergo an endothermic

transformation at 393 ± 10 K with A//tr = 1100 ± 100

cal mol-1 [1]. Protsenko and Kolomin [71] reported

two phase transformations in CsN02 at 175 K and

353 K, respectively. The DTA and electrical conductivity studies by Natarajan and Hovi [70]

indicate a thermal anomaly in 350-380 K temperature range, which they attribute to a phase

transition. Richter and Pistorius [69] have reported

CsNC>2 (phase I) to undergo a transformation at 179 K to a rhombohedral CsN02 (phase II, space

group: D|d — R3m with a = 4.307 A, a = 87°22 ). The II/I transition line is found to rise with pressure

with an initial slope of 4.9 K/kbar.

7
KNO;

Measurement technique Observations Remarks References

X-ray diffraction A new anomaly in dielectric constant is re- ported at 230 K. The cubic phase also ap- pears just above 313 K. AV is very small during the 313 K transformation. The a- axis decreases while c increases at this point.

The absence of any superlattice reflections indicates some kind of disordered arrange- ment of the NO2 groups. Ferroelectricity or antiferroelectricity is possible only be- low the room temperature.

[53, 54].

After a thermal cycle traversing the trans- formation temperature to the high temp,

form I, a single crystal of KNO2 in phase

II is converted into a hybrid crystal composed of domains of structure II in specific orientations. Detailed interpretation

of some oscillation photographs of such a hybrid crystal in terms of composite re- ciprocal lattice demonstrates that the do- main orientations are related by the point group symmetry m3.

It is concluded that form I must have a cubic

structure. Consideration of the atomic dis- placements involved in the II ^ I trans- formation show these to be consistent with

a NaCl structure for form I; and also the lower cubic symmetry controlling domain

orientations arises because of the physical requirement for the domains to coexist within the envelope of a ‘single’ crystal.

[68]

Differential thermal analysis... KNO2 undergoes a transition around 313 K... AHtr — 120 ± 30 cal mol-1 {AT —

6

K). The observation was supported by studies

of the temperature dependent infrared spectrum and a dielectric constant ex- hibiting around 313 K. Electrical conductivity also shows a slight break at 313 K. Protsenko et al. (3) report the phase trans- formation at 320 K.

[57, 69],

Differential Scanning Calorimetry,

AHtr = 199 + 2 cal mol-1

[38].

Spectroscopic, dielectric constant, and electrical conductivity measurements.

Tc - 313 K

Ps = 2.8 fxC cm-2, Ec = 160V cm-1 at 298 K

Anomalies seen in e{T) and cr{T) plots [3, 57, 69],

Dielectric constant and electrical conductivity.Two clear transitions at ~ 260 K and 313 K

are shown by anomalies in e(T) and

cr(T) plots. The room temperature phase

is rhombohedral with R3c symmetry.

The magnitude of dielectric anomaly does

not suggest a ferroelectric-paraelectric

transition in KN02 at 313 K.

[55],

A new transition from orthorhombic (D1 ® - aragonite type at 298 K) to a trigonal

(close to D(jd -calcite type) structure is indicated by dielectric constant anomaly

and loss studies. Tt - 402 K.

The transformation was not reversible and

showed hysteresis.

[58].

References

[1] Natarajan, M., and Rao, C.N.R., unpublished results from

this laboratory.

[2] Ferrari, A., Cavalca, L., and Tani, M. E., Gazz. Chim. Itali. 87, 310 (1957).

[3] Protsenko, P. I., Bordyushkova, E. A., and Venerouskaya,

L. N., Ukr. Khim. Zh. 31, 1200 (1965).

[3a] Jona, F., and Shirane, G., Ferroelectric Crystals, Pergamon

Press (1962), p. 361.

[4] Zheludev, I. S., and Sonin, A. S., Izv. Acad. Nauk SSSR,

Ser. Fiz. 22, 1441 (1958).

[5] Sawada, S., Nomura, S., Fujii, S., and Yoshita, I., Phys. Rev. Lett. 1, 320 (1958).

[6] Sawada, S., Nomura, S., and Asao, Y., J. Phys. Soc. Japan

16, 2207 (1961).

[7] Sonin, A. S., Zheludev, I. S., and Dobrzhanskii, G. F., Izv. Nauk SSSR, Ser. Fiz. 24 , 1209 (1960).

[8] Sonin, A. S., and Zheludev, I. S., Kristallografiya 8 , 57

(1963).

[9] Nomura, S., J. Phys. Soc. Japan 16, 2440 (1961).

[10]

Takagi, Y., and Gesi, K., J. Phys. Soc. Japan 19 , 142

(1964); 22 , 979 (1967). [10a] Hamano, K., J. Phys. Soc. Japan 19, 945 (1964). 8
[11] Nomura, S., Asao, Y., and Sawada, S., J. Phys. Soc. Japan

16, 917 (1961).

[12] Tanisaki, S., J. Phys. Soc. Japan 16, 579 (1961).

[13] Suzuki, S., and Takagi, M., J. Phys. Soc. Japan 21, 554

(1966).

[14] Nomura, S., J. Phys. Soc. Japan 16, 1352 (1961).

[15] Hoshino, S., J. Phys. Soc. Japan 19, 140 (1964).

[16] Sakiyama, M., Kimoto, A., and Seki, S., J. Phys. Soc. Japan

20, 2180 (1965).

[17] Hoshino, S. and Shibuya, I., J. Phys. Soc. Japan 16, 1254

(1961).

[18] Naruyama, N. and Sawada, S., J. Phys. Soc. Japan, 20, 811

(1965).

[19] Yoshida, I. and Sawada, S., J. Phys. Soc. Japan, 16, 2467

(1961).

[20] Asao, Y., Yoshida, I., Ando, R., and Sawada, S., J. Phys.

Soc. Japan 17, 442 (1962).

[21] Betsayaku, H., J. Phys. Soc. Japan 21, 187 (1966).

[22] Shibuya, I., J. Phys. Soc. Japan 16 , 490 (1961).

[23] Tanisaki, S., J. Phys. Soc. Japan 18 , 1181 (1963).

[24] Sato, Y., Gesi, K., and Takagi, Y., J. Phys. Soc. Japan 16,

2172(1961).

[25] Greenberg, J. and Hallgren, L. J., J. Chem. Phys. 33, 900

(1960).

[26] Cleaver, B., Rhodes, E., and Ubbelohde, A. R., Proc. Roy.

Soc. A276, 453 (1963).

[27] Chisler, E. V., Sov. Phys. (Solid State) 7, 1825 (1966).

[28] Yamada, Y., Shibuya, I., and Hoshino, S., J. Phys. Soc. Japan

18,1594(1963).

[29] Sawada, S., Yanagi, T., and Tokugawa, Y., J. Phys. Soc. Japan 20, 834 (1965). [29a] Flugge, S. and Meyenn, K. V., Z. Phys. 2 5 3,369 (1972). [29b] Yamada, Y. and Yamada, T., J. Phys. Soc. Japan 21,

2167(1966).

[30] Mendiola, J., Canut, M. L., and Almoros, J. L., Acta Cryst. 16, A190 (1963).

[31] Gesi, K., J. Phys. Soc. Japan 26, 953 (1969).

[32] Bridgman, P. W., Proc. Amer. Acad. Arts Sci. 72, 45 (1937).

[33] Lippincott, E. R., Weir, C. E., van Valkenberg, A., and Bunting, E. N., Spectrochim. Acta 16, 58 (1960).

[34] Rapoport, E., J. Chem. Phys. 45, 2721 (1966).

[35] Hoshino, S. and Motegi, H., Jap. J. Appl. Phys. 6, 708 (1967).

[36] Mendiola, J., Electronica Fiz. Aplic. 10,5 (1967).

[37] Jaffray, J., J. recherches centr. natl. recherche sci. (Paris) 153

(1947).

[38] Adams, M. J. and House (Jr.), J. E., Trans. 111. State Acad.

Sci. 63, 83 (1970).

[39] Gesi, K., Japan J. Appl. Phys. 4, 817 (1965).

[40] Jaffray, J., Compt. Rend. 2 3 0 , 525 (1950).

[41] Myasnikova, T. P. and Evseeva, R. Ya., Krist. Fazorye

Prevrashch, 41, (1971), Ed. by N. N. Sirota, Nauka i tekhnika Minsk., Beloruss (USSR).

[42] Gorelik, V. S., Zheludev, I. S., and Sushchinskii, M. M.,

Sov. Phys. cryst. 11,527 (1967).

[43] Chisler, E. V. and Shur, M. S., physica status solidi, 17, 173

(1966).

[44] Chisler, E. V., Fiz. Tverd. Tela 7,2258 (1965).

[45] Chisler, E. V. and Shur, M. S., physica status solidi, 17 , 163

(1966). [45a] Asawa, C. K. and Barnoski, M. K., Phys. Rev. (B) 2, 205

(1970).

[46] Kaya, M. I. and Gonzalo, J. A., J. Phys. Soc. Japan Suppl.

28, 284 (1969): published 1970.

[47] Rigamonti, A., Phys. Rev. Lett. 19, 436 (1967).

[48] Oja, T., Marino, R. A. and Bray, P. J., Phys. Letters 26A,

11(1967).

[49] Kadaba, P. K., O’Reilly, D. E., and Blinc, R., physica status

solidi 42, 855 (1970).

[50] Gesi, K., J. Phys. Soc. Japan 20, 1764 (1965).

[51] Gesi, K., Ozawa, K., and Takagi, Y., J. Phys. Soc. Japan 20, 1773(1965).

[52] Ziegler, G. E., Z. Krist, (A) 94, 491 (1936). [52a] Chang, S. C., Dissert. Abstracts 24, 1668 (1963).

[53] Solbakk, J. K., and Strpmme, K. O., Acta Chem. Scand. 23,300(1969).

[54] Tanisaki, S. and Ishimatsu, T., J. Phys. Soc. Japan 20 , 1277

(1965).

[55] Mansingh, A. and Smith, A. M., J. Phys. D (Appl. Phys.)

4,560(1971).

[56] Ray, J. D. and Ogg, R. A., J. Phys. Chem. 60 1599 (1956).

[57] Rao, K. J. and Rao, C. N. R., Brit. J. Appl. Phys. 17, 1653

(1966).

[58] Doucet, Y., Morabin, A., Tete, A., and Rostini, P., Compt.

Rend. 261,3060(1965).

[59] Bridgman, P. W., Proc. Amer. Acad. Arts Sci. 51, 55 (1915).

[60] Hazlewood, F. J., Rhodes, E., and Ubbelohde, A. R., Trans. Faraday Soc. 59, 2612 (1963).

[61] Clark, J. B. and Rapoport, E., J. Chem. Phys., 49 , 2453

(1968).

[62] Boyd, F. R. and England. J. L., J. Geophys. Res. 65, 741

(1960). [63] Kennedy, G. C. and Newton, R. C. in “Solids Under Pres- sure” Ed. W. Paul and D. M. Warschauer, McGraw Hill, New York (1963).

[64] Jayaraman, A., Klement, W. (Jr.), Newton, R. C., and Kennedy, G. C., J. Phys. Chem. Solids 24,7 (1963).

[65] Klement, W. (Jr.), Cohen, L. H., and Kennedy, G. C., J. Phys. Chem. Solids 27, 171 (1966).

[66] Larionov, L. V. and Livshits, L. D., Izv. Akad. Nauk SSSR,

Fiz. Zemli. 11,21 (1970).

[67] Parry, G. S. and Schuyff, Acta Cryst. 21,303 (1966).

[68] Sakai. K., J. Chem. Soc. Japan 75, 182 (1954).

[69] Richter, P. W. and Pistorius, C. W. F. T., J. Solid State Chem. 5,276(1972).

[70] Natarajan, M. and Hovi, V., Ann. Acad. Sci. Fenn. Ser. A. VI (400) 3 (1972).

[71] Protsenko, P. I. and Kolomin, L. G., Izv. Vuz. Fiz. (USSR) 7, 105 (1971).

1.2. Alkaline Earth Metal Nitrites

(No crystallographic data seem to be available)

Polymorphic transformations in the nitrites of

calcium, strontium, and barium have been reported

from the anomalies in differential thermal analysis curves [1, 2] and electrical conductivity measure- ments [3]. Detailed studies, however, have not

been carried out. The transformation temperatures

for these nitrites are given below:

9
Nitrite 7t , K

Calcium 539, 633 Strontium 458, 547 Barium 476, 503

References

[1] Protsenko, P. I. and Venerovskaya, L. N., Izd. Rostov. Gos.

Univ. Rostov-on-Don 1960.

[2] Protsenko, P. I. and Brykova, N. A. Russ. J. Inorg. Chem.

8, 1130(1963).

[3] Kolomen, L. G. and Protsenko, P. I., Ukr. Khim. Zh. 36,

1228(1970).

1.3. Thallium Nitrite, T1N02 (No crystallographic data seem to be available)

Differential thermal analysis studies by Protsenko

and Brykova [1] show a polymorphic transformation

in TINO2 at 442 K. Earlier, Cuttica [2] reported the

transformation temperature to be 404 K. Detailed

studies, however, have not been made.

References

[1] Protsenko, P. I. and Brykova, N. A., Russ. J. Inorg. Chem.

8, 1130(1963).

[2] Cuttica, V., Alti. Acad. Lincei, Rend. Classe Sci. fis. mat.

nat. 29,289(1920).

2. Nitrates

Nitrates of many of the elements undergo phase

transformations. Among these, alkali-metal nitrates

and ammonium nitrate have been investigated ex- tensively. Thermal as well as pressure transformations of nitrates have been studied by observing

changes in crystallographic, thermodynamic, electrical, dielectric, magnetic and optical properties.

We shall review these phase transitions of nitrates

following the position of the element in the periodic

table.

2.1. Nitric Acid, HN03 A single crystal of HN03 in equilibrium with its own liquid grown at a pressure of about 4 kbar has

been found to exhibit a transition at room temperature and 8 kbar [1].References

[1] van Valkenburg, A., Appl. Optics 9, 1 (1970). 2.2. Alkali Metal Nitrates

As mentioned earlier, phase transformations of

alkali metal nitrates have been studied in great

detail and the subject has been reviewed by a few

authors [1-3]. The orthorhombic-trigonal transformations in NaN03 and KN03 , and the hexagonalcubic transformations in RbN03 and CsN03 are well characterized. In this section, we shall examine

the data on each of the alkali metal nitrates and pro- vide the information in a tabular manner.

Lithium Nitrate, LiN03 , rhombohedral (calcite

type), D§d —RSc, Z = 6 (for hexagonal cell) and 2

(for rhombohedral cell), a — 4.692A, c = 15.22 A at 298 K.

The crystal structure of LiN03 was reported to be calcite type by Zachariasen [4]. The unit cell dimensions were later confirmed by Swanson et al.

[5] at the National Bmeau of Standards. There is no evidence for changes in the thermodynamic

properties like specific heat and specific volume of

LiN03 between room temperature and the melting

point [6]. A study of the temperature variation of the

electronic spectrum of LiN03 by Rhodes and

Ubbelohde [7] shows that there is discontinuity in the absorption coefficient indicating a transformation. McLaren [1] concludes that if this is any indication of a transformation in LiN03 , it could only

be due to orientational disorder as in NaN03 (above ~ 458 K) or in NH4 N03 (in phase II). Fermor and

Kjekshus [8] have measured the electrical resistivity and dielectric constant of LiN03 from 203 K

to the melting point and report a transformation

at 263 K, besides another anomaly at 503 K. Morabin

et al. [9] have found the dielectric constant to in- crease linearly with temperature up to 483 K then

followed by a faster rate of increase.

Sodium Nitrate, NaN03 , rhombohedral, Dfd — R3c,

Z — 6 (for hexagonal cell and 2 (for rhombohedral

cell), a = 5.0696 A, c - 16.829 A at 298 K.

The structure of NaN03 was determined by

Wyckoff [10] and the unit cell dimensions for the

rhombohedral (calcite type) cell are a = 6.3247 A and

a = 47° 16' at 296 K. Sodium nitrate has been found

to undergo a phase transition from phase II, ordered

rhombohedral phase (calcite type), to I, a dis- ordered rhombohedral phase, around 548.5 K (1). Kracek et al. [10a] observed marked changes in the

intensities of the x-ray reflections from some of the

planes on heating NaN03 above —488 K. They

attributed this to the rotation of the N03 ions about

the trigonal axis. The investigations of Ketelaar and

Strijk [11] also show that the transition is caused by

internal rotation of the N03 groups in the crystal.

10
The most probable mode of rotation is that about an

axis through the N-atom and perpendicular to the

plane of the N03 group. Recently, Terauchi and Yamada [11a] have studied by x-ray scattering the phase

transition of sodium nitrate crystal associated with

the ordering of the orientation of NOj ions. They

have analysed the results on a microscopic basis and

have concluded that the pair interactions between

NO3 ions play an important role during the phase

transition.

Anomaly in thermal expansion, DTA and heat

capacity measurements were employed to study the

transformation in NaN03 [12]. Around 548 K, dc

electrical conductivity also shows a change in the

slope [13]. Protsenko et al. [14] found NaN03 to be

piezoelectric in the direction of the 6-axis with a Curie point at 537 K. The dielectric constant had

a sharp maximum in the vicinity of 437 K where the

value is more than 100 times higher than that at room temperature. Dilatometric measurements

showed the coefficient of linear expansion to be 10-4 per degree. Rhodes and Ubbelohde [7] noticed that

the high energy absorption peak in the electronic

spectrum of NaN03 shifted to lower wavelengths

above ~ 548 K. Raman spectrum due to the internal

vibrations of NOj ions was studied by Chisler [15] to investigate the transition in NaN03 . Earlier

spectroscopic studies have shown that NO^ does

not freely rotate above the transition temperature.

High Pressure Transformations: Polymorphic trans- formations at high pressure in alkali metal nitrates were investigated by Bridgman [16] up to 100 kbar.

Jamieson and Lawson [17] made some preliminary

but unsuccessful attempts to determine the crystal

structure of the high pressure form of NaN03. Rapoport [18] showed that the pressure dependence

of the transition in NaN03 could be described by

the equation, t = 275 + 6.076p — 0.038475p2

, where

t is temperature in degree centigrade and p is pressure in kbar.

NaN03

Measurement technique Observations Remarks References

X-ray diffraction A gradual transition (II^I) occurs by the formation of nuclei in the crystal matrix and their subsequent growth. Lattice constants for the two forms both of which

have rhombohedral unit cell are:

II a = 6.32 A, a = 47°14' at 298 K

I a = 6.56 A, a = 45°35' at 553 K.

The transition depends upon the number of nucleating centers. At high temperatures,

the nitrate groups seem to be statistically distributed between two twofold dis- torted, non-equivalent sets of position in rhomhedral unit cell.

[10a, 19-

21].

Diffuse x-ray Scattering The observed ellipsoidal distribution of

critical diffuse scattering in the re- ciprocal space has been explained by

taking the pair interactions up to second

nearest neighbours.

[Ha].

The temperature-dependence of critical scattering gives a reasonable agreement

with theoretical values in random phase

approximation in the temperature range

of r>rc + 4.5 K.

Both the temperature-dependence of long range order parameter and of anomalous

lattice expansion can be satisfactorily

explained by taking the strain de- pendence of pair interaction energy into account.

11
NaNOs—Continued

Measurement technique Observations Remarks References

Tt ~ 548 K Values of elasticity constants were deduced

from intensity data and compared with

elastic constants obtained by ultrasonic measurements. The diffuse maxima are believed to be a result of group-disorder.

The maxima show strong angular dependence which is incompatible with the rota- tional model. The data fit a twofold dis- order model for the nitrate groups pro- vided that the positions have an aragonite

type coordination with the surrounding

Na atoms, rather than the calcite coordi- nation found in the ordered structure.

[22,23].

High pressure X-ray up to Anomalous line intensity changes near 45 The data suggest a higher order transition [24], ~ 85 kbar. kbar are shown to be due to a transi- tion from R3c to R3c space group without any change in volume.

in which the nitrate groups in alternate

layers along the trigonal axis rotate in opposite directions under pressure, and

the nitrogen position is no longer planar

with oxygen atoms. The atomic configuration suggests a ferroelectric phase and

dielectric measurements indicate an anomaly at the transition point.

DTA and calorimetric meas- The specific heat curve shows a break begin- The behaviour of NaNOs has been discussed [6, 25-29a]. urements). ning around 443 K and reaching a peak

around Tt

. Tt = 549 K. AHtT — 1030 ± 90 cal mol-1

in terms of free rotation of nitrate ions. The transition is due to the transfer of NO§" from an ordered state to a dis- ordered state.

Thermal conductivity, spe- The abrupt change in thermal diffusivity 1 It is possible that above Tt the NO3 groups [12, 27, 30],

cific heat, thermal diffu- is influenced by the abrupt change in the 1 may be rotated by 180° about the trigonal

sivity, elasticity. elastic constant S33. axis by means of lattice vibration.

An impurity like calcium causes a decrease

in the values of thermal characteristics

of NaNOs near Tt. The decrease is pro- portional to the increase in calciumconcentration.

Thermal conductivity changes have been

explained by the presence of an order- disorder scattering mechanism.

[30a].

Thermal expansion A gradual transition ending to a peak value The transition occurring between 423 and [12, 27, of coefficient of expansion at Tt followed by a rapid decrease to a normal value. 551 K is more marked along the c-axis than along the a-axis. The coefficients of thermal expansion increase monotonically with temperature up to the melting

point.

31-32a].

Differential thermal analysis

(up to 40 kbar). The effect of pressure on the gradual

transition in NaNOs can be expressed

by the equation.

T= 275 + 6.076p - 0.038475p 2

. r=temp (K), p = pressure (kbar).

[18].

Permittivity measurements Anisotropy is observed and unusual in- Thermal properties like thermal con- [33], at 100 kHz. crease is seen in the ( 111 ) direction at 453 K and in the a-direction at 493 K. At

this temperature, orientational polarization begins. At 548 K, the fixed position of NO3 ions does not exist and permittivity again decreases.

ductivity and thermal diffusivity behave

in a similar manner.

12
NaN03—Continued

Measurement technique Observations Remarks References

Dielectric constant and resistivity measurements (from room temperature to melt- ing point).

Electrical conductivity measurements.

Infrared absorption spectra

at different temperatures.

Raman Scattering.

L ltrasonic and IR studies.

At transition temperature maxima is ob- served in e-T curve.

Conductivity-temperature curves show

discontinuities or changes in slope near

the transformation temperature.

Assignments of the bands in the region,

3000-5000 cm-1 are made as librational combinations with vibrational bands. These bands persist in the temperature

range between the Ilnd order transition and melting point, and disappear in the spectrum of the melt. The intensity of the NaN03 , 1385 cm-1

(i>3 ) band in the range of 483-553 K increased

rapidly (Tt — 549 K).

T, ~ 549.7 K

[9, 24, 34].

[13].

Garland relations applied

to the A-change in NaN03 .

Strong frequency dependent ultrasonic attenuation is observed at temperatures

immediately below and above the A-point.

The transition is essentially one dimensional; most anomalies in properties do show

up only in the c-direction.

The thermal behaviour observed completely eliminates the hypothesis of free

rotation of NO“ ions above the A-point.

The crystal structure above 548 K is disordered.

The strong asymmetric broadening of the

line is attributed to the superposition

of bands due to scattering by bound and

quasi-free anions. The results are interpreted on the basis that the ‘frozen’ elastic constant varies smoothly and monotonically with temperature throughout the transition region.

The intensity of the totally symmetric vibration Vi, forbidden in the ordered but

allowed, and weakly present, in the dis- ordered phase, shows no sharp change

in passing through the transition. This

i is consistent with the notion that short range order changes slowly with temperature in the transition region.

[35].

[15].

[36. 37],

[38],

Potassium Nitrate, KNO3, orthorhombic, D^-Pmcn,

Z = 4, a = 5.414 A, b = 9. 164 A, c = 6.431 A at 299 K.

Potassium nitrate, form II (aragonite type), is the

stable phase at 299 K and atmospheric pressure,

and changes to form I (calcite type) at 403 K. On

cooling, KNO3 transforms from phase I to a new

phase III at 397 K and from phase III to phase II at 383 K. The transformation in KNO3 can be shown

as follows [39].

(orthorhombic, II — — >1 (rhombohedral,

aragonite type) / calcite type)

383 K\ / 397 K

III (rhombohedral) ferroelectric

Fischmeister [39a] gave the unit cell dimensions

for KNO3 form I at 425 K as a = 5.42 A and c = 19.41

A which are in good agreement with the parameters

reported by Tahvonen [39b]. This hexagonal cell contains 12 molecules. On heating, the unit cell of form I expands anisotropically, the marked

expansion being along the c-axis (normal to the plane

of anions). The expansion along the o-axis is slightly

negative. This suggests that the linear vibration of

NCff is a more plausible form of disorder than the

rotation in the plane about the N-atom. Form III has been reported to be ferroelectric [40] and is rhombohedral with a = 5.43 A, c=9.112 A and

space group Cfv -R3m at 388 K. Leonhardt and

Borchert [41] as well as Kennedy et al. [42] have

13
studied the phase changes in single crystals of

KN03 by x-rays. Kracek [43] studied both moist and dry polycrystalline KNO3 by DTA and observed an endothermic transition in the moist sample beginning

around 403 K. On cooling, the sample gave an exo- thermic DTA peak beginning at 399 K. The forms

above and below 400 K are I and II, respectively.

The behaviour of the dry sample, however, was

different, at least while cooling, where two exo- thermic peaks at 397 K and 382 K were noticed. The

form stable in this temperature range is III. Oja [28]

reports the II—* I transformation at ~ 402.5 K from

calorimetric studies.

Conductance studies on compressed polycrystalline pellets of KNO3 were made by McLaren

[1] who found the II —> I transformation to occur at 399 K. The transitions were indicated by anomalous

change in conductivity with increasing temperature [44]. Meinnel and Clinet [45] in their dielectric

constant measurements found a sharp increase at ~ 400 K while heating and two distinct anomalies at ~ 380 K and ~ 368 K, while cooling.

Sawada et al. [40] showed that KNO3-III is fer- roelectric. The nature of ferroelectricity has been

examined by Chen and Chernow [46], who measured the unit cell parameters of KNO3 single crystals in the temperature region of the ferroelectric

transition. The changes in the cell parameters as the crystal undergoes paraelectric to ferroelectric

transition (I —» III) have been interpreted as being

due to the electrostriction effect. Ferroelectricity in KNO3 is due to the ordering of

permanent dipoles. The permanent dipole in the

paraelectric phase is believed to be due to the displacement of the nitrate ion from the center of the

unit cell. The amplitude of this oscillation is 0.4 A

along the c-axis. If we consider, instead, that the

structure is a disordered array of nitrate ions displaced from the center of the unit cell, the dipole

moment per unit cell would be ~ 9.8 /jlc cm -2

. This is very close to the value of spontaneous

polarization in KN03 . A double potential along the

c-axis is considered to be a good model for explaining

the NO3 ion displacement. A statistical theory

based on this model and on the assumption of

a lattice dependent internal field explains the origin

of the electrostriction effect and observed anomalies

at the ferroelectric transition. The statistical theory

is related to Devonshire’s thermodynamic theory of

ferroelectric transition and good agreement is obtained between the theoretically predicted and

experimentally determined coefficients of Devonshire’s free energy. Balkanski and Teng [47]

reported a normal vibration analysis of all the three

phases of KNO3 and found a close correspondence

between normal modes of different phases. They

also report a complete KN03 phase transition cycle

in Raman Scattering. On heating, all the ionic and

rotational modes in phase II were found to vanish

abruptly at 403 K suggesting that the transition

II—>1 is of a rather sudden nature. A notable and

continuous broadening of the rotational mode at 83 cm-1 was also observed near Tt

. Between 383

and 373 K, on cooling, the spectra suggest that the

limits between phase III and II may be less precise

and that the III—>11 phase transition probably occurs more gradually than the other phase transition.

High Pressure Transformations: The phase diagram

of KNO3 reported by Bridgman [48] in the pressure

range 0-12 kbar up to 473 K, revealed two rhombohedral (I and III) and two orthorhombic (II and IV)

phases. The polymorphs III and IV are the high

pressure forms. KNO3-III, however, could be at- tained metastably at atmospheric pressure and its crystal structure was reported by Barth [49] as rhombohedral with Z = 1 with the NO3 ion dis- placed some six percent above the cell center. Davis and Adams [50] studied the kinetics of the

phase transformations I ^ II and II ^ III at high

pressures in detail. Rapoport and Kennedy [51] have

examined the high pressure transformations in

KNO3 up to 40 kbar and 873 K employing DTA. They

found as many as seven polymorphs, phases V, VI,

and VII being entirely new. The phase diagram of

KNO3 above 15 kbar was found to closely resemble

that of RbN03 , CsN03 or T1N03 and it is suggested

that KNO3 VII encountered at 30 kbar is structurally

similar to the phases found by Bridgman [52] in

RbN03 at 24 kbar and in CsNCL at 27 kbar.

14
KNO;

Measurement technique Observations Remarks References

X-ray diffraction 77 = 401 K for orthorhombic to rhombohedral transformation. While cooling, the

solid obtains a mosaic character at 396 K

and at 386 K changes to a finely divided

material.

Single crystals preserve their nature with

very slow heating rates. The (110) plane

of the calcite-type crystal parallels the

(010) plane of the original aragonite-type

crystal. An incubation period averaging

4.1 minutes exists for the transformation. Structural transformations are completely reversible. The volume change at the phase boundary is 0.71 percent.

The changes at 396 K and 386 K are due to the I —III and III—II transformations in KN03 . Crystals of the high temperature

phase grow rhythmically from the low temperature phase to form discrete and

easily identifiable layers.

The c-axes of the two structures are not

parallel but differ by 26° both lying in the plane common to the two structures. In moist crystals, the 6-axis showr s a marked persistence with respect to original 6-axis. The a and c axes often undergo rotation about the original direction of the 6-axis. The direction of none of the original axes persists in rigorously dried crystals.

[41, 42, 53-55],

A new transition at 213 K was found,

showing marked hysteresis effects. From the new phase, the material slowly transformed to the stable, normal II phase at 299 K.

[56],

High Pressure x-ray dif- The structural information for the high

fraction. pressure phases III and IV are as follows: Pressure, Temp., Structural Phase kbar K information

[48, 50,

57, 58],

Differential Thermal Analysis.

III 2.5 406 Hexagonal

pseudo-cell.

Z = 6, a = 5.44o A,

c= 17.51 6 A

(AV ~ 0.036 cm3g'‘ at 410 K and 0.5 kbar)... IV 3.0 298 Ortho- rhombic

Z= 10 space

group Pmn2i

(for K" ions) a= 11.048 A.

6 = 8.367 A

c = 7.402 A.

Several diffraction patterns of the transi- tions I—II and III—II revealed preferred

orientation of grains in the resulting

aragonite type phase. Cell parameters

of KNO3-I and KN03-III (both modified calcite structures) taken in their

stability fields show a marked reduction

in the c-axis length going from phase- 1 to phase-III with increasing pressure at constant temperature.

Rate studies on the transition KNO3

II ^ IV showed an overall approach to

first order kinetics but in detail, reveal

several growth stages. The transitions are only partially manifested by an uneven change in the pressure. The change was found gradual, in many cases, over a temp, interval, and

the pressure curve before and after

rectilinear. In such cases the intersection of these two rectilinear portions

give the transition point.

AHXr . cal mol-1 Transition (approx.)

IM 1200 I—III 820

III^II 820

The thermal hysteresis. (AT), is linearly

Ea . kcal mol -1 related to the differences in volume of the transforming and the transformed

100 phases.

[25, 59-60a],

15
KNO3 — Continued

Measurement technique

Particle size effects in the II—»I transition by DTA.

Thermal analysis and dila- tometry, up to 300 Mbar.

High pressure DTA up to 873 K and 40 kbar.

Kinetics of III —^ II transition.

Dielectric constant,

Electrical conductivity,

dielectric constant and

dielectric loss.

Dielectric constant and

spontaneous polarization.

Observations Remarks References

Particle

size A//tr , /Lt(micron) T,, K cal mol-1

Tt decreases with the particle size while AHu also shows a progressive decrease. These effects are related to non-attain- ment of thermodynamic equilibrium and

surface energy factors. Effect of heating

rates on Tt is also discussed.

[61].

5.5 413 1450

49.5 413 1200

115.0 406 1000

137.0 403 1050 Tx for II—>1 change is affected by moisture. At 50 Mbar AF= 0.00484 cm3g

-1 for the II—>1 transition; at 151 Mbar, AV =

0.0087 cm3 g

-1 for II—>111 and at 251 Mbar AP= — 0.0091 cm3 g~ 1 for III—*1.

Conditions for metastability of KN03-

III at atmospheric pressure are dis- cussed.

[43].

The melting curve passes through a broad

maxima at 6.4 kbar, possibly through

a second maxima at 11 kbar and then

rises steeply with increasing pressure above 15 kbar.

Three new polymorphs V, VI, and VII were found. The phase diagram of KNO3 seems very similar to that of RbNC>3 or CSNO3 .

[51].

The III—>11 transition may be described

by two first order processes, and each

of these can be expressed by a single

rate constant.

The existence of ferroelectric behaviour

in the phase III polymorph permits direct recording of the rate of transition of the phase III —> phase II at temperatures

far removed from the normal Tt at at- mospheric pressure.

[63],

The real part of e varies from 4.45 to 12.10 and the losses from several thousandths

to 0.68 with increasing temperature. The

transition is reversible and exhibits hysteresis.

In samples subjected to gamma rays, the Ps shows substantial decrease and Ec values show increase. No double hysteresis loop was observed. Results show

phase III having two Curie points; the upper Tc increases while the lower Tc de- creases with increasing pressure up to ~ 1.38 kbar (20,000 psi).

[35,46,

64-68],

Anomaly is observed at ~ 403 K on heating

and at ~ 397 and 381 K on cooling.

The occurrence of a relaxation type of

dielectric dispersion in the microwave

region together with the contraction of the ferroelectric axis at the transition, suggests that ferroelectricity in KN03 is an order-disorder phenomena.

[48,69,70],

The isothermal and isobaric I —> III transition exhibited sharp dielec, peaks at all pressures, with e max increasing with

pressure. KNO3 -I obeys a pressure Curie-Weiss law, with

[71].

C(p)),

=p

c

*p" a,r= 433K’

C* = — 276 kbar and po — 4.68 kbar. The KNO3 II—>111 isobaric transition in- volves a small jump in e (from 5 to 7.5

at p=1.7 kbar) followed by a speedy

increase up to the III—>1 boundary.

Polarization loops were obtained in KNO3 -III with Ps (p ) reaching a maximum

of 8/j. coulomb/cm 2

. Metastable KNO3-

16
KN03 — Continued

Measurement technique Observations Remarks References

Electrical conductivity

III was observed at room temperature

and room pressure after specimens had

first been exposed to high pressures

( 1 . 7-4.0 kbar) while in region III. In KNO3-I, K' = dT0ldp is approximately

25 k/kbar.

All the transitions are shown by conductivity temperature curves. The II—M, III—>-1 and I—>111 phase transitions follow the kinetic equation

The phase transitions of KN03 are volume

reactions with a complete mutual dis- persion of both phases; the course of the

reaction is controlled by nucleation.

[72-74],

In a/( 1 — a)= kT + c.

Infrared spectroscopy

where a is the degree of conversion and

t is the time. The transitions of KN03 at 403,398, and

and 388 K are associated with changes

in the positions of bands at 720, 830, and

1055 cm-1 characteristic for the internal vibrations of N03. The temperature de- pendence is also given by the lattice vibrations along a, b, and c axes.

The analysis indicates that in the phase I the NOj ions are randomly oriented.

[75-79].

Far infrared reflectivity

spectra over the range 20-400 cm-1

.

The two infrared active lattice modes

observed are described by parameters

obtained from a classical oscillator analysis, which was confirmed by

Kramers-Kronig analysis.

From the temperature dependence of the mode parameters and their contribution

to their dielectric constant it was con- cluded that the paraelectric phase I is a disordered arrangement of electrical dipoles. Thus the paraelectric to ferro- electric transition is an order-disorder

transition.

[80].

Electron paramagnetic res- onance of Mn+2 in KNO3. KN03 .The hyperfine coupling constant, half width, and line intensity show sudden

changes at the Tt. The lines are much

sharper in the high temperature phase

of the crystal.

The observed changes are explained in terms of structural changes and NO 3 ion rotation. Indications of the presence

^ of a metastable y-phase (ferroelectric phase) has also been found.

[81].

Polarising microscope with

hot stage. On heating, the transition boundaryB//-/ starts from hot end of the crystal

and moves on to the other end making

the specimen somewhat polycrystalline. Further heating, brings about recrystallization. On cooling, the boundary B/./// appears on the cooler end subsequently

followed by Bm-n boundary.

The boundary Bm-n usually leaves many

cracks after its passage. However, the speed of the boundary Bi_m is rather small as compared with that of the boundary BIIHI, and shortly after their appearance the boundary Bm-n often catches up with the boundary BmhThereafter, the united boundary BMI pro- ceeds further to the hot end leaving no more cracks.

[82].

Ultraviolet spectroscopy A gradual shift of absorption bands is found to accompany thermal expansion

of the crystals and an abrupt change is seen at T{ , transformation showing

hysteresis at 313 K has been detected.

The technique proves a sensitive means

for the study of various thermodynamic

effects in phase transformations.

[83],

17
KN03 — Continued

Measurement technique Observations Remarks References

Raman Scattering In the ferroelectric phase a significant

intensity increase was noted for all the covalent modes. A broad band at ~ 120 cm-1

is observed in the ferroelectric phase, the half-width of this band

depends upon temperature. Two new

lines at 65 and 133 cm-1 are found in the room temperature phase.

Raman active modes in different crystal structures have been correlated.

Strong asymmetric broadening of the line may be regarded as the result of superposition of bands due to scattering by

bound and quasi-free anions. From the- oretical considerations it is concluded

that Qv is the most suitable space group

to describe KNO3 -I, the high temperature phase.

[15,84-86],

Raman Spectra study of

ferroelectric transition under pressure up to 800

bar (from room temperature to 418 K).

The lattice dynamical behaviour of the

direct high pressure II— III phase transi- tion is quite similar to that under atmospheric condition.

The structures of II and III phases are very

close to one another. Raman spectra of the ferroelectric phase reveals that at high pressure, KNO3 -III is more stable than at atmospheric pressure.

[87].

Neutron diffraction at high The pressure phase IV of KN03 at ~ 15

[88]. pressures. kbar is noticed.

Viscosity measurements Show evidence for II—* I transition.

[89]

,

[90]

, Change in grain size Number of grains per unit area increased

from 4 to 70 during transformation at 393 K.

Rubidium Nitrate, RbN03 , Trigonal, C|v =P31m,

Z = 9, a = 10.479 A, c = 7.452 A, at 298 K.

It has been established by x-ray diffraction

[91-95], DTA [25, 96], dilatometric [83, 91], calorimetric [97-99], electric conductivity [1, 100, 101]

and optical [83] measurements that RbN03 undergoes the following phase transformations:

IV 437 K III 492 K II 564 K I

(Trigonal) (Cubic) (Rhombohedral) (Cubic)

CsCltype NaCltype

Single crystal photographs at ~ 453 K suggest that

RbN03-III is cubic with a = 4.36 A containing only one molecule per unit cell. Korhonen [102] however,

assigns a value of a twice as this from his studies of

powder photographs, i.e., a = 8.72 A with Z — 8. X-ray photographs of RbN03 single crystals heated

through the IV —> III transformation indicate that

the trigonal triad [00.1] of IV is transformed to the

cubic triad [111] of III with the trigonal [10.1]

direction becoming the cube edge direction [100].

Thus, during the III —> IV transition any one of the

four equivalent cube diagonals can give rise to the trigonal c-axis. Hence, in the transformation

cycle, IV —> III —

>

IV, the crystals may come back

to form IV in any of four orientations [101]. All these

possibilities were observed. Accordingly, Finback

and Hassel [103] suggest that the NOj ions are in free rotation in form III. Korhonen [102] suggests

that the anion disorder is akin to the one in KN03 suggested by Fischmeister [39]. Form II is rhombohedral with a — 4.8 A, a. = 70°28' (around 520

K) having one molecule per unit cell. Form I is cubic with one molecule per unit cell; a = 7.32 A

at ~ 573 K.

The thermal transformations in RbN03 were

studied by DTA by Plyushchev et al. [96, 104]

and Rao and Rao [25]. The electrical conductance of

compressed powder pellets of RbN03 has been

reported by Brown and McLaren [101]. The IV—III transition is marked by an increase in conductance

by two orders of magnitude. After cycling, the con- ductance changes by a factor of 30 at the III— II transition in both the directions. Cycling also pro- duces a change by three orders of magnitude in the

18
IV— III transition in both the directions. These

results were reproducible. The II— I transition is characterized by a change in the slope of the

conductance curve. Meinnel and Clinet [45] found an anomalous in- crease in dielectric constant (e) at ~ 323 K. On

cooling, the fall in e was observed at ~ 313 K.

Finback and Hassel [105] reported that RbN03-IV

is pyroelectric. Dantsiger [34] concludes from dielectric and dilatometric studies that RbN03 has

ferroelectric properties between the first and

second phase transition points. Examination of

single crystals of RbN03 by an optical microscope

[1] shows that it crystallizes in the form of c-axis

needles which are anisotropic and show parallel

extinction. On heating, the IV—^ III change was

noticed at ~ 430 K with the crystals becoming

isotropic. It is interesting to note that while cooling

(i.e. Ill— IV transition) the crystals retained their

external shape as well as their single crystal character. Further heating results in the cracking of

single crystals through the III—» II transition at ~ 500 K, and the crystals also become anisotropic.

Around 563 K, the crystals become isotropic without

further distortion.

High Pressure Transformations: Bridgman [52,

106] reported new polymorphs in RbN03 in the

pressure and temperature ranges 0-50 kbar and

194-473 K, respectively, by his piston displacement method. Later he extended his measurements

up to 100 kbar [16]. In his earlier work, Bridgman

found similarity in the phase diagrams of RbN03 and CsN03 [48]. Rapoport and Kennedy [51, 107]

also showed that the phase diagram of RbN03 above 2 kbar is quite similar to that of KN03 above 15 kbar and of CsN03 . The corresponding

phases have been found to be isostructural.

RbNOs

Measurement technique Observations Remarks References

X-ray diffraction Transition Tt , K

IV—>111 437 III^II 492 II^I 564

Structures IV, III, and II are related to one

another while II and I are not related. Transitions between IV, III, and II appear to involve changes of positional

randomization of Rb+

. No evidence was

available for such randomization in

II —* I transition. RbN03-II is rhombohedral and not tetra- gonal as suggested earlier [97]. This is confirmed by data from x-ray and dilato- metric studies. The polymorphism in RbN03 seems to be sensitive to a temperature dependent effective ionic radius of the anion. X-ray and optical studies on single crystals of RbN03 indicate incomplete randomization of the NO- ion orientations.

[93, 95, 101-

103, 108-

110],

Differential thermal analysis

and thermoanalytical measurements.

Calorimetric measurements..

Transition AHtr cal mol -

1

Ea

1 kcal mol -

1

AS,r cal mol -1 deg-1

AF

%

IV-III 950 165 2.11 2.1 III-II 650 50 1.53 10.0

II1300 55 0.42 1.0

The measurements under improved conditions revealed five endotherms for RbN03 .

The transition energies have been reported...

The thermal hysteresis is related to the differences in volume of the transforming

and transformed phases.

The first four endotherms at 440, 509, 563,

and 575 K respectively are due to crystal transitions and the fifth one at 587 K is due to fusion. No phase transition was observed below room temperature as reported earlier by Fermor and Kjekshus [70].

[2, 25, 96, 104, 108, 111].

[ 112]. [97, 99,

113].

19
RbN03 — Continued

Measurement technique Observations Remarks References

Electric conductivity Discontinuities in the plot of log cr versus

1 IT are observed at all the transition

points. IV- III transition at 431 K is marked by an increase in cr by a factor

of 1000; the III —* II transition at 495 K is accompanied by a decrease in cr by a

factor of 100; finally the II—* I transition

at 559 K is indicated by a change in the

slope. Cerisier and Guitard [114] find the

results different from Brown and

McLaren [101].

The conductivity behaviour is explained in terms of the crystal structure changes in RbN03 .

[1, 74, 100-

102, 114,

[115].

Dielectric and dilatometric measurements.

J At 434 and 471 K RbN03 undergoes considerable shrinkage and its dielectric constant increases considerably; at 471 K, Curie-Weiss law is followed with a Curie constant of 4.7 X 103

. Dependence

of e and tan S on field intensity (50Hz)

of an alternating electric field at 370 and

428 K are given. As the point of phase

transition is approached, the nonlinearity increases.

It is hypothesized that RbN03 has ferro- electric properties below the point of the

first phase transition and above the point

of second phase transition. No trans- formation below room temperature was

observed.

[37, 40]

The hysteresis energy of the III ^ IV

transition (77 — 437 K) is a few thou- sandth of the AHlr . It varies with the

purity of the sample.

(AU — 0.903 cm3 mol -1 at 77.)

The transition in RbN03 is a symmetry

controlled transformation. The transi- tion is discontinuous and the expansion

coefficient of the cubic form is normal

and positive.

[94, 116].

Optical measurement The temperature dependence of the v$ vibration frequency as well as that of

lattice vibration along a, b, and c axes

are studied.

[78, 101,

117].

Ultraviolet spectroscopy The ultraviolet absorption bands shifts are observed at 77. AU have been

reported for various transformations.

The shifts in absorption bands are abrupt

in cases where a crystal structure change

accompanies the transition. In the cases of known crystal structure, these

shifts have been correlated to changes

in interatomic distances between cations and anions.

[83],

Nuclear magnetic resonance Nuclear electric quadrupole coupling

constants, assymmetry parameters of the N-nuclei and the orientation of groups with respect to the crystallo- graphic axis are determined.

[118]. spectra of 14 N nuclei

Cesium Nitrate, CsNC> 3 , hexagonal, C§v — P31m,

Z = 9, a = 10.87 A, c = 7.76 A below 434 K [118a].

Cesium nitrate undergoes a phase transformation

around 434 K from phase II (hexagonal) to phase I (cubic) [103, 105, 119]. The reverse transformation

(I—>11) takes place at a lower temperature (—422 K)

showing considerable hysteresis. Phase I has been

reported to be cubic with a = 4.499 A at ~400 K

and Z = 1 [103]. Ferroni et al. [119] have, however,

suggested that the true unit cell should have eight

such cubic units i.e. Z = 8 with a — 8.98 A. This

doubled cell parameter agrees well with the one

given by Korhonen [120], who reports the space

group for this phase to be Pa3. Finbak and Hassel

[103] observed that the single crystals of CsNO.3

when heated above 473 K, were not destroyed.

20
Single crystal photographs of CsNOs taken at 298,

473, and again at 298 K show that the Cs + ion

sub-lattice is very similar in both the structures. This indicates that the structure of CsNOs (I) is a

slightly distorted version of the CsNCh (II) structure. According to Ferroni and others, the difference in structures of phases I and II is due to changes in

the orientation of the NO3" ion, the Cs + ion position

being practically the same. Cini and Cocchi [121],

from magnetic measurements, have shown that

the high temperature phase is a centrosymmetric

one. and is cubic.

DTA anomalies are reported by Plyuschev et al. [96, 104], Rao and Rao [25] and others. Sato [124]

found a specific heat anomaly in 418-434 K range.

Electrical conductivity measurements on polycrystalline pellets were made by McLaren [1] who

found a rise in conductivity at Tt and a decrease

in conductivity at 427 K on cooling. The conductivity changes by a factor of 3 on heating as well

the dielectric constant of CsN03 and found an anomaly at 393 K both on heating and cooling.

Finbak and Hassel [105] report from single crystal

studies that CSNO3 -II is pyroelectric. Single

crystals of CSNO3 under a polarizing microscope

showed no destruction of these crystals on cycling

through the transition. There was, in general, no

appreciable change in the orientation of form II after thermal cycling (i.e. II—> I—>11) [ 1 , 104].

High Pressure Transformations: Bridgman [52,

106] reported new polymorphs in CsN03 in his high

pressure investigations up to 50 kbar in 193-473 K

range. He showed a similarity between the diagrams

of RbN03 and CsNOs [48]. The phase diagrams

of CsN03 were found to be quite similar to those of

KNO3 , above 15 kbar, and RbN03 , above 2 kbar

by Rapoport and Kennedy [51, 107], who found

the corresponding phases to be isostructural.

Structural information on the high pressure polymorphs has not been reported in the literature. as on cooling. Meinnel and Clinet [45] measured

CsN0 3

Measurement technique Observations Remarks References

X-ray diffraction Above 434 k (Tt ) the structure due to Cs + ions is rhombohedral with a = 4.45 A

and a = 89°40'. However, the NOj- ions within the various “Cs"- only” rhombohedral cells are not equivalent. Consequently. the unit cell for CsNOs is larger containing nine of the smaller

units and with a =10.87 A and c = 7.76

A.

The form below 434 K, is cubic with

a = 4.49 A with one CsNOs per unit cell

[55]. However. Ferroni et al. [117] believe

that the unit cell must include 8 of the smaller units with a = 8.98 A. Free rota- tion of NO;f ions is a questionable hypothesis since the diameter of a freely

rotating spherical NO3" is larger than Cs-Cs distance along the ternary axis. The two structures differ only in NO^

ion orientation.

[103, 105, 119, 120].

Differential Thermal Analy- r„ 434 k. The thermal hysteresis is linearly related [25, 96.

sis. A//tr ~ 350 cal mol-1

. Ea ~ 75 kcal mol-1

. with the change in volume of the trans- forming and the transformed phases.

104. 122].

Calorimetric measurements.. Tt is reported to be 424.5-425 K. No phase

transformation below room temperature was observed (also see ref. 66). AHtr = 893±80 cal mol-1

. The molecular specific heats of CsNOs up

to the transition point were found to be

represented by the following equation:

Cp = 9.84 + 46.4 x 10 -3T for T= 273-373

K.

Free rotation of NO^ in CsN0 3 is reduced

from the variation of molar heat with temperature.

[113. 123,

124].

Dilatometry Transition at 434 K is first order. The expansion coefficient of the cubic form is nor- mal and positive.

Hysteresis effects are sensitive to recrysstallization and aging of the sample.

[94].

Electrical conductivity The transformation is marked by a sharp

change in conductivity.

[1. 125],

Dielectric constant and resistivity (193-303 K). Anomaly is observed at point of phase

transformation.

[70],

21
CsNOs— Continued

Measurement technique Observations Remarks References

Optical examination in polar- The spectra of single crystals of CsN03 -II Raman spectra of the lattice vibrations are [105, 126, ized light, polarized infra- red and laser induced Ra- man spectroscopy.

in the region of the internal vibrations of N03" indicate that these ions are posi- tioned at sites having Ci symmetry and

the unit cell symmetry of the trigonal space group is C^(C3 ).

presented. 127],

Ultraviolet spectra Ultraviolet absorption band gradually shifts accompanying the transition at ~ 426 K. The shifts in absorption maxima due to changes in temperature are interpreted in relation to changes in interionic distance.[83],

Magnetic investigations Single crystals of CsN03 when held in a magnetic field behave anomalously while being heated carefully. This effect known

as polyelectricity disappears at 437 K. By

a technique in which powder CsN03 is held in a sphere suspended in a uniform

magnetic field, the anisotropic packing of

the magnetically anisotropic cesium ni- trate causes a torque which is constant up

to 437 K at which point it is completely

nullified.

The observations confirm the centrosymmetry and cubic classification of the high temperature phase.

[121].

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2.3. Ammonium Nitrate, NH4 N03 (orthorhombic, D^-Pnmm, Z = 2, a = 4.942 A,

6 = 5.438 A, c = 5.745 A at 298 K)

Ammonium nitrate has five modifications below

the melting point (442 K). The transformations

between the various phases designated as I, II, III, IV, and V can be described as follows [1-6]:

255 K

V —-

tetragonal orthorhombic

A metastable transition, orthorhombic (IV) ^

tetragonal (II) at 318—323 K has also been reported

by many workers [4-8] particularly when single

crystals of NH4 N03 phase IV were grown from

aqueous solution. The water present in the specimen greatly affects Tt and the velocity of this metastable transition which also depends upon the max- imum temperature reached and the time of heat

treatment [5], The occurrence of this transition

between modifications IV—II was found to be

associated with special drying of the sample or its immersion in a nonsolvent [9, 10]. The metastable

transition has been observed when the melt is cooled at a rate greater than 2 K per minute and

does not show up on heating [11]. Brown and

McLaren [12] from their study using various techniques showed that all the transformations were

observed in the dry solid except the IV ^ III, which was only found to take place in the presence

of moisture. The structures I, II, IV, and V were

found to be mutually related, forms II, IV, and V

being distorted versions of form I. Form III does

not bear any structural similarity to other stable

forms.

Transitions in ammonium nitrate have been found

to be largely time independent [13] and therefore, a well defined Tt can be specified. The presence of

the metastable phases, however, gives rise to some

complication in the mechanism of transformation.

From x-ray analysis, the phase transitions have been

interpreted as rotation-disorder transitions. Kamayashi and Yamakani [14] have reported all the transitions of NRiNOs showing anomalies in the dielectric

measurements and DTA. Some of these transitions were found to follow large thermal hysteresis.

Existence of a low temperature modification, VII,

of ammonium nitrate below 103 K has been substantiated by microscopy, x-ray diffraction and

thermal analysis [11], NfLNOs quenched at 77 K

was found to consist of modifications IV and VII

[11]. Specific heat measurements showed an anomaly at ~ 212 K [15] which, however, was not

verified by DTA [16] and x-ray diffraction [16a]. In the low temperature rotation photographs, superstructure lines were found. Jaffray [17] repeated

this work using a copper block with one hole and a copper block with two holes (NaCl as reference)

398 K

•••—c l tetragonal cubic

and showed an anomaly between 208 and 216 K.

The sample was cooled below 173 K and the meas- urements were made from this temperature upward

IV: 305 K

Til

357 K

II orthorhombic

24
keeping a suitable warming rate. These studies

indicated a new transformation at a lower temperature. It is concluded from J affray’s results that it is to this new polymorphic transformation at 113

123 K that the modification in Raman Spectrum

observed by Volkringer et al. [18] between 81 and

198 K can be attributed.

No major effect was observed on the transitions

of NH4 NO3 if small amounts of Na, Li, Ag, or T1 ni- trates were present, but the transition characteristics were found to change in the presence of K, Rb

or Cs-nitrates [19-21]. Addition of KN03 has a re- markable effect on the condition of NH4 NO3 . It de- creases the density of NH4 NO3 slightly, lowers the

transition temperatures, lowers the expansion on

transition, reduces the hygroscopicity and reduces

the number of contact points as well as caking. It, however, does not affect the degree of hydration [22]. Effect of other impurities like Cu(N03 ) 2 , Mg(N03 ) 2 , ZnfNCLL, MnSCL, and Na2 B4 07 on the transitions was also studied [23]. Stabilization of the cubic phase was observed when CsCl and other halides were

added. With NaN02 and CsN02 , the tetragonal

phase was stabilized [24]. Stabilization of the polymorphs of NH4 NO3 as crystallized on a mica cleavage surface seemed to be a consequence of the close

correspondence between the parameters of the sta- bilizer and those of the ammonium nitrate polymorph

concerned [24]. All the mixtures from pure NH4 NO3 to as far as 8 percent NH4 C1 were found to crystallize as homogenous mixed crystal phases of isometric (cubic) symmetry [25]. The cubic phase (I)— tet- ragonal (II) inversion changes from 398.5 K for pure

NH4 NO3 to 382 K for the solid solution containing

2.5 percent NH4 C1. At 382 K, the curve of unmixing

of solid solutions was encountered and along this curve, the phenomena of mixing and unmixing of

solid solutions was found to take place and could be

observed directly [25]. Addition of (NH4 ) 2 S04 affects

the IV ^ III phase transition of ammonium nitrate.

With increase in sulfate content from 2 to 30 wt percent, the Tt of NH4 NO3 increases from 310 to 311.5

K. At higher concentrations of (NH4 ) 2 S04 , double

salts are formed and there is no phase transition in

the 298-323 K range [26, 27]. Nagatani [10] added

octadecylamine, its nitrate or acetate to NH4 NO3 in

aqueous or cyclohexane solution in such a way that

the additives precipitated on the surface of ammonium nitrate particles. DTA and x-ray diffraction

showed that the effects of these additives between

0.03 and 0.3 wt percent was to extend the temperature region of stable existence of phase IV and to eliminate the transition III —» IV at 305 K.

Deuterated Ammonium Nitrate, ND4NO3.

Hovi et al. [28] measured the deutron magnetic resonance fine-widths in ND4NO3 between 100 and

403 K. They obtained values of 255, 308.5, 366, and

400.5 K with a maximum uncertainty of ±2 K for

the transformation temperatures of V —* IV, IV —

III, III —^ II and II—* I phase transformations

respectively. Niemela and Lohikainen [29] studied

the spin-lattice relaxation times of deutrons in

ND4NO3. The modification III of this substance

could not be observed by them, similar to the

results of Brown and McLaren [12] and Nagatani

et al. [30] for dry samples of NH4NO3. Pohyonen

et al. [31] employed a modified DTA technique for a study of the various transformations in deuterated

ammonium nitrate. The equilibrium temperature in

the transformations IV ^ III, III —> II and II ^ I were observed as, 302.8, 361.52 ±0.06 and 400.58

0.04 K, respectively. The melting point of ND4NO3

was found to be 1.2 K greater than that of NH4NO3

due to the isotope effect. In the I ^ II transformation, thermal hysteresis was not observed as indicated earlier by a number of workers in the case of

NH4NO3 [ 12 , 32]. Superheating of modification II was not found to take place at the transformation

II—* I, while supercooling of the modification I was

observed at the transformation I—* II. Considerable

superheating and supercooling proved characteristic of the III and II phases at the II ^ III trans- formation. Small thermal hysteresis was observed

during this transformation. The III ^ IV transformation was also found to be associated with small

thermal hysteresis. Modifications III and IV of

ND4NO3 supercooled by 0.7 and 0.5 K. respectively. Consideration of the effect of deuteration on

the Gibbs function of various modifications of

ammonium nitrate indicated that the interaction of

the NH^ group with the lattice seemed to be

strongest in modification III. High Pressure Transformations: Janecke [33] found

all the known transformations of NH4NO3 at higher

pressures with his electrically heated pressure

apparatus. The transitions were found only partially

manifested by an uneven change in the pressure.

In many cases, the change was found to be gradual over a temperature interval, and the pressure curves were rectilinear before and after the transition.

The intersection of these curves corresponded to

25
the transition point. Phase diagrams between 273

and 473 K were determined by Bridgman [34] at pressures between 0.98 bar (1 kg cm-2

) and 11.77

kbar (12000 kg cm-2

). These show a new modification of ammonium nitrate. Recently, Rapoport and

Pistorius [35] have also found a new modification

VI during their study of the phase transformation

of ammonium nitrate by DTA at high pressures;

the pressure and temperature ranges of their study were 0-35 kbar and 223-623 K, respectively. The

univarient lines of the I—VI, IV—VI, and I—IV

transitions were found to meet at a triple point near

9.5 kbar and 529 K.

Leskovich [36] studied the effect of pressure on

the polymorphic transformations of ammonium

nitrate between stable modifications V (T < 255 K),

IV(255-305.1 K) and 111(305.1-357.2 K). The average value for the increase in the volume expansion

for the IV —* III transition at normal pressures was

found to be 6.5 percent. The temperature for the

start of the IV—III transition was 316 K at a pressure

of 392.24 bar. Leskovich [37] further found that

modification IV does not show relaxation of pres- sure because of a minimum molar volume. The

modification III possesses the largest molar volume

of all known crystal modifications of this salt and

easily transforms to modification IV at 323 K.

Cerisier [38] studied the electrical conductivity of

dehydrated NH4NO3 (polycrystalline pellet) at 1-600 bar and 355-442 K. In this temperature

range, ammonium nitrate exists in two different

forms. Measurements under increasing and decreasing temperatures showed a hysteresis loop related

to a structural transformation.

NH4 NO3

Measurement technique Observations Remarks References

X-ray diffraction

.

Dilatometric measurements..

Transition Tt

, K (approx.

IV IV ^ III

III ^ II

II ^ I

255 305

357 398

The structural information for various phases are:

I, cubic, Z = 1, a = 4.36 A at 403 K

II, tetragonal, Z = 2,a = 5.712 A

c = 4.924 A at 363 K

III, orthorhombic, Z = 4, a= 7.197 A

6 = 7.716 A

c = 5.845 A at 323 K

IV, * orthorhombic, Z = 2, a = 5.756 A

6 = 5.452 A

c = 4.931 A at 296 K

*The room temperature structural informations given in the heading is from the NBS monograph.

V, tetragonal.t a = 7.925 A

c = 9.820 A at 255 K

tAlso reported pseudo-hexagonal, Z = 6, a = 5.75 A, c = 15.9 A below 255 K [2].

The transitions have been found to be asso- ciated with considerable thermal hysteresis. 77s by several authors do not differ by more than ±1.5 K.

A metastable transition at 323 K has also been reported. In pulverized samples containing octadecylamine, its nitrate etc., complicated thermal hysteresis effects in the V-II phase change are observed. The

transition involves a new reversible phase

V* between V and II. Tt , V^±V* is 315 K and Tt , V*^II is 318 K, both being X-type transitions.

Water present in the specimen greatly af- fects the transition temperature and velocity. In dry samples the transition often proceeds as a single crystal transformation without any appreciable change in orientation. The kinetics of the transition IV ^ III has been studied in detail.

[ 1 -8, 12 , 39-46],

[6, 7, 43, 47-50],

26
NH4 NO3 — Continued

Measurement technique Observations Remarks References

Grinding of NH4 NO3 increased the rate The equations similar to those describing [51-58], da/dt. Recrystallization in smaller crys- topochemical reaction were used to cal- tals had similar effect. Lattice defects culate the curves of (IV-III) transforma- present in the surface of phase III probably belong to a higher melting

tion isotherms.

modification rather than to lower

melting phase IV. The volume change (AF) is as follows:

In (1 — a) =— ktn and —dcy =Bam= (l-a)2/3,

dt

III ^ II -0.0148 cm3

II ^ I 0.0220 cm3 where a = degree of transformation

t = time in minutes

k & n are constants and

k

lln is the reaction rate constant. For III-II transformation, a is given by

In (1 — a) =— (kt) 3

, the rate constant k

rapidly increased when the temperature was further removed from Tt

.

Differential Thermal Analy- The transition II III, III ^ IV and The conditions for the appearance and [ 6 , 12,14,

sis. IV ^ V were found to show consid- disappearance of the metastable transi- 59-62].

erable hysteresis. Dry NH4 NO3 was not tion around 318 K (II —* IV) and the shift found to show IV —

III transition but a of Tt by the heat-treatment were studied

direct transition IV —> II. in detail. The Tt shows a linear change with the The adsorbed water in the samples gave

logarithm of water content. rise to a sharp large peak. heat of transitions IV-V 0.13 kcal mol-1

III—IV 0.42 kcal mol-1 II—III 0.32 kcal mol-1 I—II 1.03 kcal mol-1 Rotation disorder transition of NH4NO3 NH4 NO3 can be used as a temperature [13]. have been investigated. standard because the transition reactions are not time dependent. Metastable phases, however, make the mechanism of transition slightly complicated.

Calorimetric measurements. For a carefully dried sample, the V ^ IV An analysis of the heat capacity below [63-66].

specific heat etc. transition was found to occur at 265 K. 100 K yielded estimates for the fre- An anomalous increase in heat capacity quencies of torsional oscillation of above 190 K was observed. NOj ion and NH| ion in phase V. The direct transition between V and II is NH| ion is found to rotate freely in phase

observed in NH4NO3 treated with some III in contrast to fully excited torsional surface active agents. For this transition oscillation in phase IV. AHtr ~ 777.7 cal mol -1 The transition V—II is considered to A5tr ~2.61 cal mol - 1 K

-1 occur as a combined phenomena of The AHtr and AStr for other transitions are orientational order-disorder of the two

as follows: ions NH+, and NO3

.

Afftr AStr The small anomaly at 156 K seems to be

Transition cal mol -1 cal mol _ 1 K

_1 due to the existence of a new phase VII

as reported earlier [ 11 ]. V-IV 113.1 ±1.5 0.430 ±0.004

IV-III 406.3 ±2.4 1.331 ±0.007

III- II 322.7 ±3.6 0.90 ±0.01

II-I 1060 ±7.0 2.66 ±0.02

IV-II 444.6 ±5.0 1.37 ±0.02

(metastable) 27
NH4NO3 — Continued

Measurement technique Observations Remarks References

Dielectric constant and dis- All the transitions have been found to show Polymorphic transitions appear distinctly [14,67-70],

persion etc. considerable hysteresis. The measure- in capacitance-temperature curves. ments did not show any transition near The dielectric constant of the phase II was

213 K. found to be much higher than that of The phase transition IV ^ III ^ II gave phase III, which is associated with the no significant effect on the nature of the two abnormal dielectric dispersions ob- tained between 25Hz and 50kHz.

motion of the NO3 groups in the unit cell.

Ionic conductivity measure- Abrupt changes in conductivity were found [12,67,71, ments. at TVs. 72], Microscopic observations on Three different facet planes (010), (Oil), The splitting during the II —

>

IV transition [73, 74], single crystals at high and (001) were studied. In the II —» IV occurs so as to reduce the stress due to temperatures. transition, the single crystal splits into change in the lattice constants. The II two kinds of crystallites with a common phase grows in the (230) plane of the IV

c-axis but exchanged a- and b-axes. The phase in the IV—II transition whereas

interface between the split crystallites the IV phase grows in the two equivalent

is parallel to the ( 110) plane which could planes (230) and (320) of the tetragonal

be a twin plane. II phase in the reverse transition. The

In the IV —» II transition the split crystal- metastable transition IV ^ II proceeds

lites rejoin into a single phase. The result- according to a rearrangement mechanism.

ant phase in both transitions is needle No crystals of phase III were produced

shaped. from a saturated solution of NH4 NO3 The transformations IV ^ III and III ^ II even at its optimum temperature of were found to reconstruct and proceed formation. Crystals of II and IV produced

according to a mechanism of distortion from the same solution transformed into and recrystallization in the presence of III when given a needle shock, which

water vapour or drops of a saturated indicates the necessity of crystal nuclei

solution of NH4NO3. due to lattice distortion. Birefringence The transitions were recorded by change [48]. in birefringence at 77s.

Optical studies 77s 318.3 K (IF -IV) The orientation relations in the different [75], 320.8 K (IV-II) phase transitions were also studied. AddiA phase II' of tetragonal or lower sym- metry was observed as the samples were

tion of KNO3 lowers the II '-IV transition

tion temperature and decreases the 2V

values. annealed in the stability range of NH4NO3 (HI). Some optical properties of NH4N03(III) were revised resulting in a positive

optical sign and the optical axis angle

2Vy = 86 ± 1

°.

Ultraviolet spectroscopy A gradual shift of absorption bands has The shifts in absorption maxima due to [32], been found to accompany the thermal temperature change have been inter- expansion of the crystals. At Tt 's more preted in relation to changes in the dis- abrupt changes in absorption spectra

have been observed.

tance between cations and anions.

Transition AV, cm3

II III +1.77

III -» II -0.64

II ->I +1.04

Density measurements The III ^ IV transition is found to accom- pany gradual change of the density and

[76],

occurs over a temperature interval of approx. 3 K. 28
XH4XO3— Continued

Measurement technique Observations Remarks References

Change in grain size is reported during the 360 K (III ^ II) transformation in XH4XO3. The number of grains per unit area increased from 2 to 36.

[77].

References

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[2] Hendricks, S. B., Posnjak. E.. and Kracek. F. C.. J. Am.

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[3] Early, R. G. and Lowry. T. M.. J. Chem. Soc. 115, 1387

(1919).

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[6] Fukuyama. I.. J. Ind. Explosives Soc. Japan 16, 2 1 1955).

[7] Shinnaka. Y.. J. Phys. Soc. Japan 11, 393 (1956).

[8] Tiemeyer. R. . Z. Krist. 97. 386 1 1937 ).

[9] Whetstone. J.. Acta Cryst. 7, 697 (1954).

[10] Xagatani. M. . Kogyo Kagaku Zasshi 68, 424 il%5).

[11] Vol'fkovich. S. I.. Rubinchik, S. M.. and Kozhin. V. M.,

Izv. Akad. Nauk SSSR. Otdel Khim. Xauk 209 1 1954).

[12] Brown. R. X. and McLaren. A. C.. Proc. Roy. Soc. 266,

329(1962).

[13] Heide. K.. Z. anorg. allgem. chem. 3 44, 241 (1966).

[14] Kamivoshi. K. and Yamakami. T., Sci. Repts. Res. Inst. Tohoku Univ. Ser. A, 1 1, 418 1 1959).

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(1932).

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2061 (1937). [16a] Amoro’s Portole’s. J. L., Alonso, P.. and Canut. M. L., Pubis, dept, crist. mineral. (Madrid) 4, 30(1958).

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455 (1934).

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93 (1946).

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I. D.. and Larina. L. M.. Zh. Prikl. Khim. (Leningrad) 43,

732 (1970).

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Zasshi 67, 1342 (1964).

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Soc. A2 7 6, 453 (1963).

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44, 1514 (1966).

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[41] Amoro’s Portole’s. J. L.. .Alonso. P.. and Canut, M. L., Pubis, dept, crist. mineral. (Madrid) 4, 38 (1958).

[42] Florke. ^ .. Z. Physik. Chem. lunterricht) 40, 71 (1927).

[43] Behn. L .. Proc. Roy. Soc. (London) A80, 444 1 1909).

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[45] Canut. M. L.. Ayllon, M., and Amoro’s Portole’s. J. L., Estud. Geol.. Inst. -Invest. Geol. “Lucas Mallada’’ (Madrid)

20,57(1964).

[46] Shinnaka. Y., J. Phys. Soc. Japan 14, 1707 (1959).

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[48] Vogt. K.. Physik. Z. 12, 1129 (1912).

[49] Paulik. F.. Paulik. J.. and Erdey, L., Mikrochim. Acta, 894

(1966).

[50] Everett. D. H. and Watson. A. E. P.. Trab. reun. inter, react.

solid. 1 Madrid), 1 , 301 1 1956) l published 1957).

[51] olf. F. and Scharre. W.. Zesz. Xauk. Lniv. Poz. (11). 3

(1967).

[52] ’ft olf. F. and Scharre, W., Zesz. Xauk. Univ. Poz. (11), 25

(1967).

[53] Erofeev. B. \ . and Mitskevich, X. I., Zh. Fiz. Khim. 24,

1235 (1950).

[54] Erofeev, B. V. and Mitskevich, X. I., Zh. Fiz. Khim. 26,

848 (1952).

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1631 (1952).

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Akad. Xauk. Beloruss. S.S.R. Inst. Khim. (5), 3 (1956).

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118(1953).

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[59] Sowell. R. R.. Karnowsky, M. M., and Waltero, C. L., J. Thermal Anal. 3,119 (1971).

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2010(1964).

[61] Hioki. Y. and Mori, S., Xatl. Tech. Rept. (Matsushita Elec. Ind. Co. Osaka) 11,1 (1965). 29
[62] Goto, M., Asada, E., Uchida, T.. and Ono, K., Yukagaku 18,

299 (1969).

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(1950).

[64] Stephenson, C. C., Bentz, D. R., and Stevenson, D. A.,

J. Amer. Chem. Soc. 77,2161 (1955).

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160 (1965).

[66] Nagatani, M., Seiyama, T., Sakiyama, M., Suga.H., and

Seki, S., Bull. Chem. Soc. Japan 40, 1833 (1967).

[67] Verzhbitskii, F. R. and Ust-Kachkintsev, V. F., Uch. Zap.

Permsk. Gos. Univ. (Ill), 24 (1964).

[68] Makosz, J. J. and Gonsior, A., Acta Phys. Pol. A39, 371

(1971).

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(1963).

[70] Fermor, J. H. and Kjekshus, A., Acta Chem. Scand. 22,

2054 (1968).

[71] Kamatsu. H., Rept. Inst. Sci. Technol. Univ. Tokyo 5, 15

(1951).

[72] Srinivasan, S., Proc. Nucl. Phys. Solid State Symp. (13th), 3,500 (1968).

[73] Seiyama. T. and Yamazoe, N., Kogyo Kagaku Zasshi 70,

821 (1967).

[74] Noboru, Y. and Tetsuro, S., Kogyo Kogaku Zasshi 70,613

(1967).

[75] De Saenz, I. M., Tessore, J. C., and Leone, R., Schvociz.

Mineral. Petrogr. Mitt., 50, 209 (1970).

[76] De Saenz, I. M., Amonini, N., and Presa, S., Z. Physik.

Chem. 43, 119 (1964).

[77] Tamman, G. and Boehme, W., Z. anorg. allgem. chem. 223,

365 (1935).

2.4. Thallous Nitrate, TINO3 (orthorhombic, Z — 8, a = 6.287 A, 6 = 12.31 Au

c = 8.001 A at 298 K)

Ferrari et al. (1) and Hinde and Kellet [2] have

reported that the room temperature structure of

thallous nitrate (form III) is orthorhombic and

belongs to one of the two possible space groups,

DJ®-Pbnm or C® -Pbn2i. The unit cell constants of

the room temperature structure given by these

authors agree well with those of Brown and McLaren

[3] and Swanson et al. [4]. Hinde and Kellet [2] suggested that the true unit cell may be regarded

as being equivalent to the stacking in the direction

of the c-axis, of two smaller cells possessing the

c-parameters equal to half the true value.

Thallous nitrate shows two phase transitions:

(orthorhombic) (hexagonal) (cubic)

Phase II is hexagonal with a = 10.543 A, c = 7.431 A,

sp.gr. P31m and Z = 9 [5]. Phase I is cubic with a = 4.326 A at 443 K in agreement with the value

reported by Finbak and Hassel [7]. Brown and

McLaren [3] have also pointed out that the unit

cells of phases II and I are related in the same

manner as forms IV and III of RbNCL. Finbak and

Hassel [7] suggested that the NO3 ion in form I is spherically symmetrical, being in a state of free

rotation. Phase transitions of thallous nitrate have

been reviewed by Newns and Staveley [6] and

McLaren [8], who have discussed the results from

thermodynamic, electrical, magnetic, optical and

crystallographic measurements.

High Pressure Transformations: Bridgman [9, 10]

studied the phase diagram of thallous nitrate up to 50 kbar and 473 K and later extended the study

up to 100 kbar [11]. He pointed out that the phase

boundary between phases I and II has very nearly

the same slope in the pressure-temperature plane

as that between phases II and III of RbNCL and

phases I and II of CsNCL. The one atmosphere

transition temperatures for the above phases are very close suggesting a similarity between the

corresponding phases [12].

30
T1N0;

Measurement technique Observations Remarks References

X-rav diffraction 77s, 348 and 416 K for the phase transitions

III ^ II and II ^ I. respectively.

[1-5, 8],

Dilatometric studies Both the transitions are followed by increase

in volume. AF being 0.0034 and 0.0156 of

[13].

unit volume at 273 K. respectively.

Direct differential calorimetry A7/tr for II —» I transition has been observed This value is somewhat higher than that de- [14]. to be 907 ±1.5 percent cal mol-1

. termined by indirect methods.

Heat capacity and thermal co- 77s, 352 and 416 K (on heating) and 416 K After cooling from the first heating immedi- [8]. efficient measurements. on cooling. No sharp transformation was ate reheating again showed the transition observed on further cooling, although at 352 K thereby giving a positive evidence

there was some indication of a very slug- gish transformation in 353-293 K range.

of III—* II transformation.

Heat capacity measurements. Mean heat capacities of T1N03 has been The results confirm that thallous nitrate is [15, 16]. measured as a function of temperature. capable of existing in 3 allotropic modifi- The molar heats between 273-373 K. can be cations. expressed by Cp = 10.95 + 42.66 x 10 -3 T. Free rotation of NO-f in T1N03 has also been

Extrapolation to 273 K gave the specific confirmed by the measurements of varia- heat C0 at that temperature. The specific heat Ct at any temperature (t in °C) was

then calculated by the equation, Cm — ( C0 + Ct )/2; a sudden increase in Ct was found

at 77

tion of molar heat with temperature.

Measurements of entropies AS,r AF It seems unlikely that the III —* II transi- [ 6 , 14,17]. of transition. 77 K cal mol-1 K

-1 % increase tion in TIN03 involves orientational dis- 348 0.7 0.4 order. This is contrary to previous find- 416 2.18 1.4 ings of McLaren [ 8].

High pressure DTA meas- Phase diagram of TINO 3 has been studied It is possible that orthorhombic phase (III) [18]. urements (up to 45 kbar). up to 923 K and 40 kbar. of TINO 3 may be isostructural with 77 352 and 417 K. No DTA signals cor- RbN03-V and CsN03-II. The II ^ III responding to the III —* II transition transition in TINO 3 is quite sluggish just could be observed possibly due to the like RbN03 IV ^ V and CsN03 II ^ III extreme sluggishness and small latent

heat. Experimental points on the II/I phase boundary can be fitted by the

relation.

phase transitions.

t (°C ) = 144.6 + 7.91P - 0.062P2

.

Electric conductance meas- Transition II —* I was accompanied by a Conductivity measurements of Brown and [3, 19]. urements (dc & ac conductivity.

Dielectric constant and re- sistivity.

large increase in conductivity.

Small maxima occur at the high temperature transitions. A low temperature

McLaren showed a drop in the cr values

at 353 K (III—II transition point). Recycling showed that the fall in conduct- ance at this transition is probably asso- ciated with the removal of moisture and

that in perfectly dry samples little or no change at this temperature may be

observed.

[20 , 21].

transition has also been demonstrated at 238 ±5 K by the anomalous dependence

of dielectric constant and resistivity on

temperature. f 31
T1N03 — Continued

Measurement technique Observations Remarks References

Ultraviolet spectroscopy A gradual shift of absorption bands is found to accompany the thermal expansion of the crystals.

In cases where crystal-structures are known, shifts in absorption maxima due

to changes in temperature have been

interpreted in relation to changes in dis- tances between cations and anions. UV

absorption spectroscopy provides a sensitive means for studying various thermo- dynamic effects in phase transformation.

[22].

Grain size measurements — The number of grains per unit area de- creased from 2 to 1 in TINO3 at III —* II* transformation 345.8 K.

[23].

NMR studies No abrupt changes in line-width at the

transition temperatures were found. Immediately above and below the melt- ing point, the magnetic resonance line was of the order of one tenth of a gauss

wide. The line-width increased very rapidly as the temperature was lowered and was

too large to be observed at room temperature.

It is suggested that the low temperature

line-width is determined predominantly

by nuclear spin exchange taking place

among the nuclear moments present.

[24].

Optical measurements

•

Single crystals grown from aqueous solution, when examined under the polarizing

microscope, were found to be anisotropic. On heating the III —> II trans- formation at ~ 353 K was observed. Form

II was also found to be anisotropic. II—5 I transformation was observed at ~ 423 K, the crystal changing to be

isotropic. On cooling, I —> II transformation was observed at slightly lower

temperature.

The crystals retain their external shape

and also their crystallographic orientations even after being taken through

four II —> I —> II cycles. The extinction angle was usually less definite, suggesting some randomization of orientation

| around a mean value.

[3].

References

[1] Ferrari, A., Cavalca, L., and Tonelli, M. G., Gazz. Chim.

Ital. 80,199(1950).

[2] Hinde, R. M. and Kellet, E. A., Acta Cryst. 10, 383 (1957).

[3] Brown, R. N. and McLaren, A. C., Acta Cryst. 15, 977 (1962).

[4] Swanson, H. E., Gilfrich, N. T., and Cook, M, I., National Bureau of Standards Circular 539, Vol. 6, p. 58 (1956).

[5] Patterson,!. H., Microscope Cryst. Front 13, 291 (1962-63).

[6] Newns, D. M. and Staveley, L. A. K., Chem. Rev. 66 , 267

(1966).

[7] Finbak, C. and Hassel, O., Z. Phys. Chem. B35, 25 (1937).

[8] McLaren, A. C., Rev. Pure Appl. Chem. 12, 54 (1962).

[9] Bridgman, P. W., Proc. Amer. Acad. Arts Sci., 51, 581

(1916).

[10] Bridgman, P. W., Proc. Amer. Acad. Arts Sci., 72, 45 (1937).

[11] Bridgman^P. W., Proc. Amer. Acad. Arts Sci. 76, 1 (1945).

[12] Rapoport, E. and Kennedy, G. C., J. Phys. Chem. Solids 26, 1995 (1965).

[13] Bellati, M. and Finazzi, L., Atti r. ist. Veneto 69, 1151 (1910).

[14] Arell, A. and Verteva, M., ann. Acad. Sci. Fenn., Ser. A VI

(98), 6 (1962).

[15] Sato, S., Bull. Inst. Phys. Chem. Research (Tokyo) 21, 127

(1942).

[16] Sato, S., J. Sci. Res. Inst. (Tokyo) 48, 59 (1954).

[17] Bridgman, P. W., Proc. Am. Acad. Arts Sci. 51, 603 (1915).

[18] Rapoport, E. and Pistorius, C. W. F. T., J. Chem. Phys.

44, 1514(1966).

[19] Kamatsu, H., Reports Inst. Sci. Tech. Univ. Tokyo 5, 15

(1951).

[20] Dantsiger, A. Ya., Nauchn. Konf. Aspirantov 75 (1962).

[21] Fermor, J. H. and Kjekshus, A., Acta Chem. Scand. 22,

2054 (1968).

[22] Cleaver, B., Rhodes, E., and Ubbelohde, A. R., Proc. Roy.

Soc. A2 76, 453 (1963). [23 Tammann, G. and Boehme, W., Z. anorg. allgem. chem.

223,365(1935).

[24] Rowland, T. J. and Bromberg, J. P., J. Chem. Phys., 29,

626(1958).

32
2.5. 3d-Transition metal nitrates

The limited information available in the literature

on the phase transitions of 3c/-transition metal

nitrates is summarized below.

3 (f-Transition metal nitrates

Substances and Observations Remarks Refer- measurement technique ences

Chromium {III) nitrate (hydrated), Cr(N03 ) 3 -9H2 0, monoclinic, P2i/c, a=13.915 A, 6 = 9.681 A, c=10.983 A and 0 = 84°16' [1]

Specific heat Cr(N03 ) 3

• 9H20 undergoes a second order The transition has been attributed to the [2]. transition at 158 K. onset of partial rotation of the water

molecules wdthin the crystal.

Dielectric measurements Transition at 158 K has not been found [31- to have any observable effect on polarizability.

Cobalt(II) nitrate (hydrated), Co(I\T 03 )2 • 6H2 0

Specific heat Co(N03 ) 2

• 6H2 0 undergoes a second order The transition has been attributed to the

transition at 158 K. onset of partial rotation of the water

molecules within the crystal. Thermal analysis and dilatom- - Curves were obtained showing the varia- Addition of water causes thermal anometry in liquid media. tion in volume as a function of tempera- alies (heat evolution) at some definite ture (in the range 93 K-room tempera- temperatures, the extent of which deture). pends upon the quantity of water added.

After several thermal cycles, a new The thermal anomalies when the water

thermal anomaly was found accom- is absorbed was also detected even

panied by a contraction of the crystal when the water of hydration was lost by

in the 253-275 K region. dessication. When the samples were kept in diethyl- ether, the anomaly shifted from 239 to 252 K. On complete evaporation after the first thermal cycle, the transition temperature was found to shift and

return to 239 K in a third thermal cycle.

Immersion of the crystals in petroleum

ether or toluene caused no modification

in thermal curves. X-ray diffraction at low’ temper- These measurements confirm the existence Crystal was found to disintegrate at 198 K

atures. of three forms I. II and III hexahydrates

of cobalt nitrate.

I. monoclinic, a = 15.09 A, 6 = 6.12 A, c= 12.67 A, 0=119°

II. a= 12.58 A, 6 = 6.29 A, c= 12.24 A

III. Structure could not be ascertained.

transformations.

Nickel (II) nitrate (hydrated). Ni(N03) 2

- 6H2 0

triclinic a = 7.694 A, 6=11.916 A,

c = 5.817 A a= 102.3° 0=102.4 A, y= 105.9°

[10].

and Z = 2, sp.gr.Pl

Thermal measurements. Heat ca- Ni(N03 h-6H2 0 shows a second order at The transition is attributed to the onset of [2. 11]. pacity etc. 150 K. partial rotation of the water molecules

within the crystal. The transition temperature is dependent on the no. of w ater molecules in the crystal. 33
3 ^-Transition metal nitrates — Continued

Substances and measurement technique

Observations Remarks Refer- ences

Dielectric measurements The transition at 150 K was found to be

unassociated with any dielectric anomaly.

[3],

Nickel (II) nitrate (hydrated), Ni(N03)2 * 2H£)

Heat capacity It showed a sharp \-anomaly at 4.105 + The anomaly is characteristic of a transition [12]. 0.005 K. to a magnetically ordered state at 7V

Copper (II) nitrate , Cu(N03 ) 2

Spectroscopic studies Transition from phase II to phase I was The unsublimed sample was found to be a [13]. observed. Infrared spectra of anhydrous

unsublimed cupric nitrate samples

showed that metal-nitrate vibration is lower in energy for the low temp, phase

II than for the high temp, phase I.

mixture of both forms.

Copper (II) nitrate (hydrated), Cu(N03) 2 •2.5H20

Proton magnetic resonance (up to The copper ions form pairs with an ex- The phase transformation at 0.16 K is [14]. magnetic field 50kOe at tern- change interaction —J/k of about 5 K. characterized by a spontaneous comperature below 1 K). In magnetic fields around 36 kOe, the ponent of the time averaged magnetic

much weaker inter-pair exchange J

moment of the copper ions perpendicular

lead to short- and long-range order to the external field and disappears

below 0.55 and 0.16 K, respectively. below 29 and 42 kOe. Heat capacity (Temp, range: 0.5 In zero applied field, Cp , exhibited a The data are quantitatively described by [15]. K-4.2 K).- Schottky anomaly having the maximum assuming that Cu+2 ions exist in this value of 0.51R at 1.82 K. salt as isolated pairs (binary clusters) coupled by isotropic antiferromagnetic

exchange with —J/k = 5.18 K. Magnetic susceptibility (powdered A broad maximum was found at 3.2 K; The behaviour is quite unlike that of a [16]. sample). measurements down to 0.4 K suggest that typical three dimensional antiferromagXp vanishes as T goes to zero. The net. There is a possibility that Cu+2 susceptibilities of needle like monoclinic moments in this salt might be coupled by

crystals of this salt exhibit small nearly isotropic antiferromagnetic exchange

uniaxial anisotropy about the b or needle interaction either in isolated pairs (binary

axis. The temperature variation of Xu and Xx is similar to \pclusters) or in extended linear chains.

Zinc(II) nitrate (hydrated), ZN(N03 >2’6H2 0

Dilatometric studies When up to 0.8 extra mole of water is [17]. present in this compound, an expansion

is observed after the expected contraction during the cooling cycle. If as

little as 0.08 mole of water is absent from

the stoichiometric 6, little or no volume

change is observed during cooling and a contraction followed by an expansion,

is observed during the heating cycle.

34
References

[1] Kannan, K. K. and Viswamitra, M. A., Acta Cryst. 19, 151

(1965).

[2] Vasileff, H. D. and Grayson-Smith. H., Can. J. Res., 28A,

367 (1950).

[3] Grayson-Smith, H. and Sturrock, R. F., Can. J. Phys. 30,

26 (1952).

[4] Pouillen, P. and Saurel. J., J. Phys. (Paris) 24, 572 (1963).

[5] Pouillen, P. and Saurel. J., Compt. Rend. 2 5 5 , 61 (1962).

[6] Pouillen. P. and Saurel, J., Compt. Rend. 2 5 6, 145 (1963).

[7] Pouillen. P. and Saurel. J.. Compt. Rend. 255, 269 (1962).

[8] Pouillen. P. and Saurel, J.. Compt. Rend. 2 5 8, 188 (1964).

[9] Pouillen. P., Bernard. M. J.. and Massause, M., Compt.

Rend. 260,6861(1965).

[10] Bigoli, F., Braibanti. A., Tiripicchio, A., and Tiripicchio.

C.M., Acta Cryst. B27, 1427 (1971).

[11] Pouillen. P. and Saurel, J.. Compt. Rend. 256, 1740

(1963).

[12] Polgar. L. G. and Friedberg, S. A., Phys. Rev. B4, 3110

(1971).

[13] James, W. D. and Kimber, G. M., Inorg. Nucl. Chem.

Letters 5 , 609 ( 1969).

[14] Van Tol. M. W., Heukens, L. S. J. M.. and Poulis, N. J., Phys. Rev. Lett. 27, 739 (1971).

[15] Friedberg, S. A. and Raquet, C. A., J. Appl. Phys. 39,

1132(1968).

[16] Berger, L., Friedberg, S. A., and Schriempf, J. T., Phys. Rev. 132, 1057(1963).

[17] Pouillen, P. and Saurel, J. Compt. Rend. 256, 3056 (1963). 2.6. Silver Nitrate, AgN03 (orthorhombic, space group: one of the four D|,

Dl, Df and D|, Z = 8, a = 6.995 A, 6 = 7.328 A,

c= 10.118 A, at 299 K)

Lindley and Woodward [1] reported the unit cell dimensions to be a = 6.997 A, 6 = 7.325 A, c= 10.118

A with space group Pbca and Z = 8. This orthorhombic phase of silver nitrate (II) transforms at 432.5 K to a rhombohedral phase I which has

a hexagonal unit cell with a = 5.203 ±0.005 A,

c= 8.522 — 0.005 A (space group R3m) at 437 [2]. McLaren [3] has reviewed the phase transition of

silver nitrate and has discussed the changes

observed in crystallographic, thermodynamic, electrical and optical properties. Newns and Staveley

[4] have described the II —^ I transition in AgN03 as a first order phase change which is followed by

a volume contraction of about 1 percent [5] and an

entropy change of 1.37 eu [6]. A metastable phase,

III, with rhombohedral structure has also been

reported to be formed on cooling AgN03 I from well

above 433 K [7]. Davis et al. [9] have reported the

volume change at the transition around 432 K to be

too sluggish to become apparent, but a marked

change in slope was observed above 438 K. This

result does not agree with the previous results of

volume change at the transition [5,9a] of silver nitrate

as a function of temperature. On cooling a sample

chilled from melt, the conductance decreased

sharply at about 438 K, although such a discontinuity was not observed while reheating. Optical studies

of Ubbelohde and coworkers [10, 11] show a sharp

change in the absorption spectrum at Tt

. Fermor and

Kjekshus [12] have found that AgN03 exhibits

another transition at 238 ±5 K, which was demonstrated by an anomalous dependence of dielectric

constant and resistivity on temperature.

Fischmeister [8] found that on heating polycrystalline samples of AgN03 , the II —> I transition

takes place around 432 K. The transition was re- ported to involve excessive fragmentation of the

crystal so that satisfactory x-ray fines could only

be obtained after prolonged recrystalfization near

the melting point.

Mauras [13] found that the transformations

II—*1 and I—HI in silver nitrate do not occur at the

same temperature. There is a difference in the trans- formation temperatures which is caused by the

volume change accompanying the transformation.

Kennedy and Schultz [14] reported that the trans- formations at ~ 432.4 K becomes quite sluggish on undercooling the sample to room temperature.

Maziers’ and Van’t Hoff [7] reported that silver

nitrate forms a metastable phase at 353 K on cooling.

This modification can persist for hours before it changes to the stable orthorhombic form. They also

found that single crystals of silver nitrate nucleated

spontaneously at the transition point. A maximum

superheating of 14 K was noted.

High Pressure Transformation: Janecke [15]

studied the II —^ I transition at high pressures.

Bridgman [16] studied the change in volume, latent

heat of transition, difference in compressibility,

thermal expansion and specific heat up to 12 kbar,

which was later extended to 50 kbar [17, 17a].

Four high pressure polymorphic forms were re- ported. Extending the measurements up to 100

kbar did not yield new polymorphic forms [18,

18a]. Rapoport and Pistorius [19] determined the

phase diagram of silver nitrate by means of DTA

and volumetric methods up to 45 kbar. In addition

to the four phases, metastable AgN03 -Y could

also be obtained by suitable manipulation above

21 kbar at temperatures below 323 K. The metastable AgN03 1 —

V transition is reversible. AgN03-V

reverts to stable AgN03-II. if left under pressure

overnight. Genshaft et al. [20] measured the volume

change with increasing pressure in the temperature range 73-673 K for pressures up to 40 kbar.

35
AgNO;

Measurement technique Observations Remarks References

X-ray diffraction T,. 433 K. Microscopic and x-ray methods establish [2,3,21]. Transition from orthorhombic to rhombo- that II —> I and I —> II transitions take

hedral. place by formation of a seed in the crystal matrix and subsequent growth of this seed. Depending on the number of nascent crystallization centres, transi- tions of two types occur:

(i) single crystal —* single crystal type

(ii) single crystal —polycrystal type. There is no mutual crystallographic link between new and matrix crystalssssssf

between new and matrix crystals during

the II ^ I transition.

Calorimetry Tt . 432.4 K A//,r, (approx.) 0.58 kcal mol-1 Heat capacity data differ from those re- [6, 22-25].

ported by Janz et al. [23, 24] from drop

calorimeter measurements.

Differential thermal Analysis... Examination of the cooling curves showed Grinding the sample gives a Tt 5.5 K higher [7, 26, 27]. that either a direct reconversion to the than that of the unground sample. Effect orthorhombic variety took place or a new of the grinding seems to be kinetic. metastable phase appeared below 353 K; namely the formation of a barrier to the

the latter was more easily formed when

the sample had been heated well above

433 K and consisted of microcrystalline

powder instead of one single crystal.

transition.

Ultraviolet spectroscopy A gradual shift of absorption bands is By means of the techniques described. [11].

Change in grain size and

number.

found to accompany thermal expansion

and more abrupt changes in absorption

spectra are observed at transformation

points from one crystal structure to another. The number of grains per unit area de- creased from 7 to 4 for AgN03 at 433

K.

ultraviolet absorption spectroscopy

proves a sensitive means for studying

various thermodynamic effects in phase

transformations.

[28].

Kinetic study of AgN03 It was found that the transformation is The rate of I —» II transformation reaches a [14,29]. (between 243 K and 444 K). faster in larger crystals. The trans- maximum at 375 K. The peak of this forming crystals suffer plastic deforma- rate curve is shifted to higher temperation and the growth rates depend on tures by addition of 0.225 atom percent

crystallographic direction. of Cd.+2 Empirical relations governing

the growth have been discussed.

Activation energy in the temperature Theory of rate process was applied by range 303-373 K has been found to be 21.14 kcal mol-1

. At higher temperatures below the equilibrium point

(433 K), the apparent activation energy approaches zero. It is suggested that a

different process limits the rate in this

Eyring et al. [29].

region.

Lowt temperature dielectric An anomalous dependence of e and p The hysteresis suggests the existence of [12]. and resistivity measure- on temperature at Tt is observed. disorder within the room temperature ments (193-303 K). phase on heating.

36
References

[1] Lindley. P. F. and Woodward. P.. J. Chem. Soc. A 123 (1966).

[2] Stroemme. K. 0.. Acta Chem. Scand. 24, 1477 (1970).

[3] McLaren. A. C.. Rev. Pure Appl. Chem. 12, 54 (1962).

[4] Newnx, D. M. and Staveley. L. A. K.. Chem. Rev. 66, 267

(1966).

[5] Bridgman. P. W.. Proc. Amer. Acad. Arts Sci. 51,603 (1915).

[6] Arell. A., Ann. Acad. Sci. Fenn. Ser. A VI (100), 3 (1962).

[7] Mazieres. C. and vant'Hoff. J.. Compt. Rend. 256, 2620

(1963).

[8] Fischmeister. H. F.. J. Inorg. NucL Chem. 3. 182 (1956).

[9] Davis. W. J.. Rogers. S. E.. and Ubbelohde. A. R., Proc. Roy. Soc. (London). A220, 14 <1953).

[9a] Guinchant. M., C.R. Acad. Sci. Paris 149 , 569 (1909).

[10] Rhodes. E. and Ubbelohde. A. R.. Proc. Roy. Soc. (London)

.4251,156(1959).

[11] Cleaver. B., Rhodes. E.. and Ubbelohde. A. R., Proc. Roy.

Soc. 4276,453 (1963).

[12] Fermor. J. H. and Kjekshus. A.. Acta Chem. Scand. 22, 2054

(1968).

[13] Mauras. H., C.R. Acad. Sci. C272, 973 (1971).

[14] Kennedy. S. W. and Schultz. P. K.. Trans. Faraday Soc. 59, 156 (1963).

[15] Janecke. E., Z. Physik. Chem. 90, 280 (1915).

[16] Bridgman. P. W.. Proc. Amer. Acad. Arts. Sci. 51, 581

(1916).

[17] Bridgman. P. W., Proc. Natl. Acad. Sci. 23,202 (1937). [17a] Bridgman. P. W., Proc. Amer. Acad. Arts Sci. 72,45 (1937).

[18] Bridgman. P. W.. Rev. Mod. Phys. 18, 1 (1946). [18a] Bridgman. P. W.. Proc. Amer. Acad. Arts Sci.. 76,1 (1945).

[19] Rapoport. E. and Pistorius, C. W. F. T.. J. Chem. Phys.,

44,1514(1966).

[20] Genshaft. Lu. S.. Livshits, L. D., and Ryabinin. Yu. N., Sov. Phys. Tech. Phys. 12, 126 (1967).

[21] Asadov, Y. G., Sov. Phys. -Crystallography 12, 357 (1968).

[22] Reinsborough. \ . C. and Wetmore. F. E. W., Aust. J. Chem.,

20, 1 (1967).

[23] Janz. G. J.. James. D. ^ .. and Goodkin. J.. J. Phys. Chem.,

64,937(1960).

[24] Janz. G. J. and Kelly. F. J.. J. Phys. Chem. 67, 2848 (1963).

[25] Adams. M. J. and House, J. E. (Jr.), Trans. ILL State Acad.

Sci. 63,83(1970).

[26] Berg. L. G. and Yasnikova. T. E.. Zh. Neorg. Khim. 11, 886

(1966).

[27] Negishi. A. and Ozawa, T., Thermochim. Acta 2, 89 (1971).

[28] Tamman. G. and Boehme. W., Z. anorg. allgem. chem. 223,

365 ( 1935).

[29] Eyring, H., Cagle. F. W. (Jr.), and Christensen, C. J., Proc. Natl. Acad. Sci. (US), 44, 120(1958).

3. Carbonates

The carbonates of alkali metals, alkaline earth

metals, thallium, some of the ^-transition metals

and silver have been reported to undergo phase

transformations. Of these, the alkaline earth metal

carbonates have been investigated extensively.

3.1. Alkali Metal Carbonates

Alkali metal carbonates are highly reactive even

at low temperatures and undergo varying degrees

of dissociation at higher temperatures. This results

in contamination of specimens complicating studies

of these compounds. There is not much work

reported on phase transformations of these solids

in the literature. Following is an account of the

available information on individual carbonates.

Lithium Carbonate , Li2 C03 , monoclinic, I2/c, Z = 4, a = 8.11 A, b = 5.00 A, c = 6. 21 A and0 = 109°41' [1]. Reisman [2] reported a phase transformation in

this compound at 683 ±3 K from his DTA studies. In the absence of C02 , an additional heat effect

appeared at 623 K. The 683 K transformation is not

affected by the 623 K heat effect which indicates

that the latter is due to either a phase transformation

in Li2 0 or more probably to the eutectic solidifica- tion in the high carbonate region of the system

Li2 0-Li2 C 03 , obtained on dissociation [3]. Semenov

and Zabolotskii [3] from their DTA, electrical

conductivity and gas volumetric studies show a new

phase transformation in Li2 C03 at 439 K.

Sodium Carbonate, Na2 C03, monoclinic, Z = 4, a = 8.90 A, 6 = 5.24 A, c = 6.04 A and 0 = 101.2° at 296 K [4]. There are two solid state phase transformations

in Na2 C03 below melting point [4]:

III «34K

n M j c-centered c-centered primitive

monoclinic monoclinic hexagonal

The crystal data for phases II and I are as follows:

II, Z = 4, a = 9.000 A, 6 = 5.24 A, c=6.31 A, and

0 = 96.9° J713 K); I, Z = 2, a = 9.01 A, 6 = 5.20’A,

c = 6.50 A, and 0=90° (773 K). y-0 transition is gradual and (2a -F 6) a = a#, aa = ba = bp, and

Ca C$.

Dubbeldam and DeWolff [5] show that phase III

is a deformed version of hexagonal phase I. Thermal measurements of Popov and Galchenko

[6] show that the transition III—MI is of second

order with AHtT ~~200 cal mol-1

, while II ^ I

is of first order with \Htr ~ 450 cal mol-1

. Jaffray

and Martin [7] however, reported that III —> II transition is not accompanied by any change

in latent heat or modification. Thermodynamic

investigations [8] in the temperature range 15-300 K

did not show any anomaly.

Potassium Carbonate , K2 CO3 , monoclinic, a —

5.658 A, 6=9.858 A, c = 6.916 A and 0 = 98.30°

at 386 K [9].

37
Makrov and Shul’gina [10] on the basis of their

DTA studies reported that K2CO3 undergoes trans- formations at 523, 703, and 898 K. Jaffray and Martin

[7] found second order transitions in K2CO3 at 683 and 738 K accompanied with thermal hysteresis.

Reisman [2] from DTA studies differentiated

between the results obtained in air and carbon

dioxide. He concluded that potassium carbonate

undergoes only one phase transformation (at 695 K±

2 K) and that other thermal effects occurring in atmospheric conditions are due to the impurities

such as KOH and KC1 . Schneider and Levin [ 9 ] studied the phase transformation in this solid by

x-ray, DTA and differential scanning calorimetry.

They substantiated Reisman’s result that K2CO3

undergoes one reversible transformation and that

other heat effects in air must be associated with

impurities. High temperature x-ray diffraction and

differential scanning calorimetry [9] show Tt to be 693 ±5 K. Schneider and Levin [9] concluded

that the monoclinic to hexagonal transformation is of second order. The crystal data for the hexagonal

phase is as follows: at 698 K a = 5.705 A and

c = 7.169 A. Rubidium, Carbonate (No crystallographic data

seem to be available).

Reisman’s DTA studies [2] show a second order

phase transformation (II—» I) in Rb2 C03 at 576±2 K.

No new heat effects were observed in the presence

of air. High pressure DTA studies of Pistorius and

Clark [11] showed no transition up to 40 kbar at 298 K. The I/II transition line rises with pressure to the triple point at 9 kbar, 675 K, where the I/II

transition line splits up into two separate transition

lines with the appearance of a new phase III. The

DTA signals associated with the new transitions

become somewhat smaller with increasing pressure

and are not observed beyond 27 kbar. Decompression retraces the behaviour in the reverse direction.

References

[ 1 1 A.C.A. Monograph, No. 5, Ed. J.D.H. Donnay and G. Donnay, 198 (1963).

[2] Reisman, A., J. Am. Chem. Soc. 80, 3558 (1958).

[3] Semenov, N. N. and Zabolotskii, T. V., Izv. Sibirsk. Otd. Akad. Nauk SSSR. 58 (1962).

[41 Brouns, E., Visser, J. W., and DeWolff, P. M., Acta Cryst.

17 , 614 (1964).

[5] Dubboldam, G. C. and DeWolff. P. M., Acta Cryst. (B) 25,

2665 (1969).

[6] Popov, M. M. and Galchenko, G. L., J. Gen. Chem. (USSR)

21 , 2489 (1951).

[7] Jaffray, J. and Martin, P., J. Physiq. Rad. 14, 553 (1953).

[8] Waterfield, C. G., Linford, R. G., Goalby, B. B., Bates, T. R., Elyard, C. A., and Staveley, L. A. K., Trans. Faraday

Soc. 64, 868 (1968).

[9] Schneider. S. J. and Levin, E. M., J. Amer. Ceramic Soc. 56, 218 (1973).

[10| Makarov, S. Z. and Shul'gina, M. P., Izv. Akad. Nauk SSSR,

Otd. Khim. Nauk (5), 691 (1940).

[11] Pistorius, C. W. F. T. and Clark, J. B., Z. Physik. Chem.

(Frankfurt) 68, 157 (1969).

3.2. Alkaline Earth Metal Carbonates

Thermal as well as pressure transformations are known in CaCCL, SrCCL and BaCCL. Pauling [1] has shown that the different structures of these

carbonates are determined by the cation-anion

radius ratio; thus, for values of 0.67 or below, the

favourable structure is calcite type with a primary

cation coordination of 6. MgC03 crystallizes in the

calcite structure and the radius ratio in this case

is 0.47. When the radius ratio is above 0.67 but

below 0.85, the aragonite phase with a pseudohexagonal-orthorhombic structure (where the ligancy of

cations is 9) is favoured. It is interesting that the

critical value of radius ratio of 0.67 is the exact value

for CaCC>3 which is dimorphous. Above a radius

ratio of 0.85, other structures are possible just as

in RbNCL or CsN03 , where the primary cation

coordination is likely to be 12. Calcium carbonate, CaC03 , hexagonal (calcite),

D|d — R3c, Z — 6, a — 4.989 A and c= 17.062 A at 299 K. Other than calcite, CaC03 exists as aragonite

(orthorhombic, D^-Pbnm (Pnma), Z — 4, a = 4.959

A, 6=7.968 A and c = 5.741 A at 299 K) [2] and

vaterite (hexagonal, Z = 12, a — 7. 16 A and c— 16.98

A at 298 K) forms [3, 4, 5]. Meyer [6] reported vaterite to have a pseudohexagonal form with space

group D^-Pbnm and Z = 4, the plane of the CO3

group being parallel to the c-axis. Both aragonite and

vaterite forms transform to the stable calcite phase

on heating [7]. Preparation of aragonite and its transformation to calcite have been the subject

of investigation by many workers [8]. Presence of

small amounts of strontium stabilizes the aragonite

phase. Attempts to prepare very pure aragonite

(without traces of Sr+2

) have not been very successful

[7,9].

Transformation of aragonite to calcite (A—» C)

takes place in the range 753-773 K, the actual Tt varying with the nature and amount of impurities

present [7]. The A—» C transformation is irreversible

at normal pressures and proceeds by a reconstruc38
tive mechanism involving a change from 6 to 9 in

the primary coordination [8]. Thus, the A—» C

transformation is sluggish and is associated with

a large energy of activation. The effect of various

impurities on the enthalpy and temperature of

transformation as well as on the dissociation of

calcite have been reported in detail by Rao and co- workers [7]. Meyer [6] and Kamhi [5] proposed the

Cs and Cav symmetry, respectively, for the car- bonate ion. Infrared spectroscopic investigations

by Sato and Matsuda [10] as well as Sterzel [11]

have confirmed the C2 V symmetry of the C03 -2 ion as proposed by Kamhi [5]. Yaterite transforms to calcite either directly or through the aragonite phase as an intermediate

[12, 13]. Transformation of vaterite takes place in

the region 623-673 K with an enthalpy of —200

cal mol-1

[6, 7]. The kinetics of the vaterite —» calcite

transformation have been reported by Xorthwood

and Lewis [14]. Xorthwood and Lewis observed

x-ray line broadening of vaterite samples which

were ground; the line broadening was attributed to the existence of microstrains in the vaterite lattice.

High pressure TransformationsCalcite transforms

to the aragonite phase under pressure, the aragonite

phase being stable at high pressures. In addition

to calcite and aragonite phases, two other phases,

II and III. were discovered by Bridgman [15] under

isothermal compression of ordinary calcite at room

temperature. Discontinuities in the isothermal compressibility values were detected at 14 and 18 kbar

corresponding to calcite—» CaC03-II and CaC03-

II—* CaC03-III transitions, respectively. The

existence of these phases was confirmed by independent powder x-ray diffraction studies of Jamieson

[16] and Davis [16a], although with divergent structural inferences. According to Jamieson [16], the

phases I, II, and III of CaC03 are characterised

by varying degrees of orientational disorder of the

carbonate ion and are related to the normal calcite structure. Davis [16a]. however, doubted the anion

rotation mechanism of calcite—» CaC03~II transition. The results of Jamieson [16]. Davis [16a] and

Rapoport [17] indicate that CaC03 -II is isostructural with the ferroelectric KA03 phase III or with

the high temperature anion disordered phase of

XaX03 and that CaC03—III is isostructural with

the high pressure orthorhombic phase I\ of KX03 . Fong and Aicol [17a], from their Raman spectral

studies, however, disagree with the above results

that show isostructural relations between CaC03 and alkali metal nitrates.

Calcite, on grinding, is known to produce aragonite [18]. Leiserowitz and coworkers [18a] have

reported a shock-induced calcite-aragonite trans- formation. Xorthwood and Lewis [14] have examined

the effect of microstrains on the calcite^ aragonite

equilibrium. The transformation is initiated by the

nucleation of the aragonite phase at these microstrain sites and is followed by growth of the aragonite phase. The kinetics of the calcite-aragonite

pressure transformation have been studied by

Davis and Adams [19] employing x-ray diffraction.

CaCC>3

Measurement technique Observations Remarks References

x-ray diffraction rjiaragonite-calcite). 723 K During the transformation the [001] direction in aragonite changes to [111] direction in calcite structure. Single crystal

aragonite breaks into calcite as polycrystalline aggregate in the course of the phase transition.

[20-29],

Vaterite changes progressively to calcite and aragonite structures during ball milling.

The vaterite to calcite and/or aragonite

transition is affected by air or water vapour.

The samples of vaterite during ball milling

develop microstrains and this is indicated by line broadening in diffraction patterns.

The structure of vaterite can be described

by a disordered stacking sequence of

single layers of trigonal symmetry,

mostly related by glide reflections, sometimes by screws parallel to the c

axis.

[12-14. 30].

X-ray diffraction under high The rates of transformation are both tempera- Extrapolation of experimental data indi- [19.31]. pressures (up to 773 K ture and pressure dependent. Around 673 cates that the transformation rate would

and 15 kbar). K. the rate of calcite-aragonite change at be negligible at 298 K. Phase diagram of 39
CaCOs — Continued

Measurement technique Observations Remarks References

~ 15 kbar is similar to the reverse transfor- mation at 1 bar. Ea , 106 kcal mol-1 at 1 bar. Metastable forms of calcite, I, II and III are possible intermediate phases during calcite- aragonite transformation.

calcite-aragonite in the range 10 to 12.7 kbar and 683 to 848 K is presented.

Aragonite is the stable form at 20 kbar and

298 K, with respect to calcite II and III. Aragonite and vaterite showed no transi- tion up to 24.4 kbar. Calcite undergoes

changes in agreement with the thermo- dynamic evidence that calcite II is an

anion-disordered form of normal calcite.

[16,32].

Transition

Anneal mol-1

AS tr cal mol-1 K-*

AG

(1 ,T)

cal mol-1

I-*II +10 0.032 46

II -> III -381 -1.28 438

I —> aragonite -370 -1.24 273

Crystals with calcite structure in quenched

assemblages are uniaxial indicating that the biaxial nature of inverted calcite is not due to pressure. Hence the constraint imposed by aragonite morphology during

the quenching and inversion to calcite has been sufficient to strain the calcite structure.

[33],

Shock induced calcite Implosion of pure calcite leaves only CaO as the product. If, however, 10 percent water

is present in calcite, implosion gives a good

yield of aragonite as detected by x-rays.

Effect of grinding calcite Aragonite is obtained in small yields for samples. small duration of grinding. With greater

periods of grinding substantial proportions

of calcite are converted to aragonite.

Mechanical grinding of calcite in ball mills

for up to 90 hrs. yields 70 percent aragonite

and 30 percent calcite in an equilibrium

mixture.

Since it is known that a combination of shear with hydrostatic pressure accel- erates the rate of phase change in the di- rection allowed by the pressure-temperature relationship of the compressed

phases, the transformation of calcite to aragonite should take place, in shock

loaded calcite. The transformation may

be considered to be an ionic displace- ment from a distorted FCC to a distorted HCP arrangement which must involve shear since it cannot be expected to re- sult from mere compression.

The calcite-aragonite transformation may

be compared to the process of ‘slip’ fre- quently observed in metal crystals.

Transformation is reported to be characteristic of nucleation-growth process. The

nucleus is probably formed by atomic

movements produced by microstrains during grinding.

[16,35,35a].

Differential thermal

analysis.

Tu 660-761 K (aragonite-calcite)

AHlr , 50 cal mol-1 (for pure aragonite)

Ea , 100 kcal mol-1 AHtr , 230 cal mol-1

is the maximum value en- countered with 1 atom percent Sr+2 impurity.

Effect of varying amounts of Sr+2 and other

cations on Tt and AHtr as well as Ea has been investigated. Smaller cations like

like Li +

, Na+

, Mg+2, Cd+2 show rela- tively low Tu but Ea is unaffected except

by Cd+2 . It is likely that cations like Na+ or Cy+3 may produce some anion or cat- ion vacancies which affect such trans- formations.

[7, 28,

.36-39],

40
CaC03 — Continued

Measurement technique Observations Remarks References

Kinetic study of A-C

transformation.

Dilatomatry.

High pressure experiments on C-A transformation by volume change

method.

Electrical conductivity at various pressures.

Refractive index measure

ments.

Infrared spectroscopy.

Tt , 623-673 K (vaterite-calcite transformation) AHlr , 200 cal mol-1

The transformation of aragonite to calcite was accompanied by a change in crystallite size around Tt

. A marked contraction

in the unit cell volume of aragonite, before

it got transformed to calcite, was reported. Isothermal expansion at Tt , is ~ 2.5 percent

at the aragonite-calcite transformation. The transformation is always preceded

by an induction period, which is affected by

i) mixing of fine calcite crystals with ara- gonite phase

ii) rapid cooling of the sample

iii) atmosphere, e.g., when atmosphere is rich in C02 , the induction period is considerably short. Temp.

range

(K) 639-679

683-723

Ea (transfor- mation)

(kcal mol-1

) 60

84

£’

a (nucleation) (kcal mol-1

) 90

72 The molar volume of vaterite decreases during

its transformation to calcite or aragonite.

The transition takes place around 4.35 kbar

and at 373 K.

Equilibrium points for calcite-aragonite from

conductivity experiments:

T, K P, kbar

302.1 3.980 311.2 4.130

325.6 4.500

350.1 4.800 Complexly twinned calcite results from a quenched assemblage of CaCC>3 , liquid

and vapour. These inverted calcite crystals are biaxial with optic axial angles ranging

from nearly 0 to 20° (for aragonite, the optic axial angle is 18°). The isogyres appear

to remain just as sharp as those in a uni- axial calcite crystal, but the crystals exhibit undulose extinction. This phenomena was

noted in the range 673-1073 K and 8-20

kbar. IR absorption spectra show changes at ~ 4 kbar and is strongly suggestive of the cal- cite-aragonite transformation.

A model based on surface nucleation and

progress of the reaction by interfacial growth is found to explain satisfactorily the complete course of the transformation of aragonite to calcite. Hysteresis of about 5-8 K was noticed. For samples purified by zone-refining, the

hysteresis was maximum. The Tt differs slightly with the process of preparation

of the sample. Speed of the transformation is proportional to time up to about 50

percent transformation for natural ara- gonite.

The kinetics of vaterite-calcite transformation is similar to that of aragonite-calcite transformation. The effect of various impurities on the cal- cite-aragonite equilibrium is discussed. Aragonite is a metastable phase of CaC03 at 1 bar and 298 K.

All normal natural occurrences of aragonite must be due to metastable formation

rather than equilibrium, since the geo- thermal gradient lies completely in the

calcite field.

The uniaxial crystals with calcite mor- phology in quenched assemblages in- dicate that the biaxial nature of inverted

calcite is not due to pressure.

However, x-ray diffraction studies on un- loading do not confirm this transition. The change in IR-absorption spectra may

be associated with minor structural

distortions in calcite.

m-

[39a].

[40-44].

[41].

[45-49],

[50],

[33],

41
CaCOa— Continued \

Measurement technique Observations

V

Remarks References

Electron diffraction The diffraction patterns showed the follow- ing orientation relalioi^:

[ 1 10] arauonite II [ 12 10^ calcite [001] ara(!onite II [0001] calcite

The orientation relation suggests that the transformation is martensitic type shear being on the (001) aragonite plane.

[52].

Electron microscopy Aragonite undergoes a sudden and violent transformation to calcite when heated by

the electron beam.

Twins and dislocations disappear leaving a strained crystal of aragonite or occasionally calcite structure.

[28, 53].

Kinetics of aragonite to calcite transformation in solution.

The transformation proceeds by subsequent

nucleation and growth of calcite on

aragonite surface. Ea , 57.4 kcal mol-1

.

The fraction of aragonite transformed to calcite at 323-440 K is proportional to the reaction time. The Ea value is dis- cussed in terms of a loosely hydrated

calcium bicarbonate ion pair. Effect of ions like Ba++

, Sr++, Pb++, or SO=

on the calcite-aragonite equilibrium is discussed.

[54-57],

The transition from vaterite involves nucleation and growth of aragonite in vaterite.

Geologically common ions have specific

effects on the transformation.

[58].

Kinetics study (by Hahn

emanation).

The rate of transformation (aragonite-calcite)

is quite large above 723 K at the heating

rate of 6 K min-1

. Around 783 K the trans- formation is maximum. Calcite dissociates

at ~'1183 K at atmospheric pressures.

Results by this technique are confirmed by

x-ray diffraction measurements.

[59, 60].

Ultrasonic studies (up to 38 kbar). Longitudinal velocities decrease sharply

from 5.3 km sec

-1 at a mean pressure of 4 kbar to minimum of 4.8 km sec

-1 at 8

kbar. Transverse velocities decrease from

3.1 to 2.9 km sec

-1

. Bulk and rigidity moduli

also show a 10 percent decrease as the minimum density increases by about 1.7 percent.

These observed changes are attributed to calcite aragonite transformation. The

low and high pressure phases possibly

coexist over a considerable pressure

range. The maximum and minimum in the in- vestigations have also been attributed to the formation of metastable forms of

calcite viz. calcite I, II etc.

[61,62].

42
Strontium carbonate, SrC03 , orthorhombic, D|£-

Pmcn, Z — 4, a = 5.107 A, 6 = 8.414 A and c —

6.029 A at 299 K.

Strontium carbonate undergoes a phase transition

around 1200 K from the orthorhombic (aragonitetype) structure to a hexagonal (calcite-type) struc- ture [63]. The transformation was first pointed out

by Boeke [64]. In the hexagonal structure, the lattice

constants are a = 5.092 A and c = 9.53 A [63]. The

transformation is similar to the aragonite-calcite

transition of CaC03 . The AHtT of the transition is 4.0 kcal mol~ 1 [65] typical of a first order transition.

Lander [63] could not detect any other transition

in SrCC>3 up to 1575 K in his x-ray diffraction studies.

However, Baker [66] reports that under careful

conditions a second endothermic transition occurs

at 1690 K. This change takes place from the hexagonal to a cubic modification. The transitions in

SrC03 are believed to be the result of anionrotational disorder.

SrC03

Measurement technique Observations Remarks References

x-ray diffraction 7\, 1185 K (orthorhombic-hexagonal) The transition is related to the rotational

activity of the C03~ 2 ions

[63],

Calorimetry Tt , 1197 K (orthorhombic-hexagonal);

AHtr , 4.0 kcal mol-1 1690 K (hexagonal-cubic);

AHtr , 0.800 kcal mol~ 1 (calculated).

The hexagonal-cubic transition (Tt , 1690 K) was observed in an atmosphere of C02 (at ~ 20 bar pressure), to prevent the SrC03 decomposition. Tt is slightly reduced (by — 6 K) by the presence of impurity.

[65, 66],

DTA (at high pressures) Tt , 1203 K (orthorhombic-hexagonal)

AHir , 4.7 kcal mol-1 AV, 1.49±0.1 cm3 mol-1

Hexagonal-cubic transition was not detectable. AV calculated from the slope of P—T

curves agrees well with the experimental

data.

[67].

Hahn emanation method

(coprecipitation with ThX).

Tt , 1198 K (orthorhombic-hexagonal) Changes in crystal structure show an in- crease or a decrease in emanation power

due to loosening of crystal structure and

consequent increase in surface area and/

or diffusion rate.

[59, 60, 68].

43
Barium carbonate, BaC03 , orthorhombic, D*®-

Pmcn, Z = 4, a = 5.314 A, 6 = 8.904 A and c =

6.430 A at 299 K.

Two transformations have been reported in

BaC03 [63]. At 1076 K, BaC03 transforms to a

calcite type hexagonal phase (a = 5.206 A, c= 10.55

A). Around 1249 K, a transition to a cubic phase

takes place. These transformations are believed to be due to the onset of rotational disorder of anions.

The pressure dependence of the transitions have

been reported by Rapoport and Pistorius [68]

employing high pressure DTA.

BaC03

Measurement technique Observations Remarks References

X-ray diffraction Tt (orthorhombic—* hexagonal), 1076 K. Tt (hexagonal—* cubic), 1249 K. For cubic phase, a = 6.96 A at 1233 K.The transformations are discussed in terms of rotational disorder of COf 2 ions and by analogy to alkali nitrate trans- formations. No new phases are known

above the cubic phase up to 1573 K.

[63],

Transition AT, K A//tr Orthorhombic to 50 kcal mol -1 hexagonal (Tt , 3.880 1079 K)

[65].

Hexagonal to 20 0.700 cubic (Tt , 1241 K)

DTA (at high pressures) Tt , 1072 K; A//tr , 4.49 kcal mol" 1

; AV,

1 .25 ± 0.09 cm3 mol~ 1

.

Tt , 1233 K.

No new phases are known. The AV calculated from the slope with Clausius- Clapeyron equation agrees well with experimental values. Studies on the higher transition were subjected to limitation because of incipient decomposition of BaC03 . Doubtful indications of

a higher order transition in the range 673-773 were noticed.

[15, 67].

Hahn emanation (coprecipitation with ThX).

Tt , 1083 K (orthorhombic-hexagonal) Changes in crystal structure show an

increase or a decrease in emanation

power due to loosening of crystal struc- ture and consequent increase in surface area and/or diffusion rate.

[59, 60, 68].

References

[1] Pauling, L., “Nature of Chem. Bond”, Cornell University

(I960).

[2] “Standard x-ray Diffraction Powder Patterns”, National Bureau of Standards (US) Circular 539, Vol. Ill, 53 (1954).

[3] McConnell, J. D. C., Min. Mag. 32, 535 (1960).

[4] Gibson, R. E., Wyckoff, R. W. G., and Merwin, H. E., Amer.

J. Sci. 10,325(1925).

[5] Kamhi, S. R., Acta Cryst. 16, 770 (1963).

[6] Meyer, H. J., Fortschr. Mineral. 38, 186 (1960).

[7] Subba Rao, G. V., Natarajan, M., and Rao, C. N. R., J. Amer. Cer. Soc. 5 1 , 179 (1968).

[8] Rao, K. J. and Rao, C. N. R. in “Progress in Solid State Chemistry”, Ed. H. Reiss, Vol. 4, 131 (1967).

[9] Subba Rao, M. and Yoganarasimhan, S. R., Amer. Mineral. 50, 1489 (1965).

[10] Sato, M. and Matsuda, S., Z. Krist. 129, 405 (1969).

[11] Sterzel, W., Z. anorg. allg. Chem. 368, 308 (1969).

[12] Gammage, R. B. and Glasson, D. R., Chem. Ind. (London)

1466 (1963).

[13] Matsuda, S., Nemori, M., Shiroma, A., and Sato, M.,

Kobutsugaku Zasshi 9, 30 (1968).

[14] Northwood, D. O. and Lewis, D., Amer. Mineral. 53, 2089

(1968).

[15] Bridgman, P. W., Amer. J. Sci. 2 3 7, 7 (1939).

[16] Jamieson, J. C., J. Geol. 65, 334 (1957). [16a] Davis, B. L., Science 145, 489 (1964).

[17] Rapoport, E., J. Phys. Chem. Solids 27, 1349 (1966). [17a] Fong, M. Y. and Nicol, M., J. Chem. Phys. 54, 579 (1971).

[18] Burns, J. H. and Bredig, M. A., J. Chem. Phys. 25, 1281

(1956). [18a] Leiserowitz, L., Schmidt, G. M. J., and Shamgar, A., J. Phys. Chem. Solids 27, 1453 (1966).

[19] Davis, B. L. and Adams, L. H., J. Geophys. Res. 70, 433

(1965).

[20] Dasgupta, D. R., Mineral. Mag. 33, 924 (1964).

[21] Gruver, R. M., J. Amer. Cer. Soc. 33, 171 (1950). 44
[22] Shoji, H., Z. Krist. 84, 74 (1933).

[23] Kleber, W., Neues Jahrb. Mineral. Geol. Beilage Bd. A75,

465(1940).

[24] Kleber, W., Neues Jahrb. Mineral. Montash 368 (1964).

[25] Shoji, H., Bull. Inst. Phys. Chem. Res. (Tokyo) 11, 896

(1932).

[26] Rinne, F., Z. Krist. 59, 230 (1924).

[27] Kozu, S. and Kani, K., Proc. Imp. Akad. (Tokyo) 10, 222

(1934).

[28] de Keyser, W. L. and Dugueldre, L., Bull. Soc. Chim. Belg.

59,40(1950).

[29] Metzger, W. J. and Barnard, W. M., Amer. Mineral. 53, 295

(1968).

[30] Meyer, H. J., Z. Krist. 128, 183 (1969).

[31] Clark, S. P., Amer. Mineral. 42, 564 (1957).

[32] Boettcher, A. L. and Wyllie, P. J., Nature 213, 792 (1967).

[33] Boettcher, A. L. and Wyllie, P. J., Amer. Mineral. 52, 1527

(1967).

[34] Dachille, F. and Roy, R., “Very High Pressure Techniques”,

Butterworths (London) 174 (1962).

[35] Schrader, R. and Hoffmann, Br., Z. Chem. 6, 388 (1966). [35a] Northwood, D. O. and Lewis, D., Can. Mineral. 10, 216

(1970).

[36] Faust, G. T., Amer. Mineral., 35, 207 (1950).

[37] Kulesko, G. I., Vop. Mineral. Osad. Obrazov 7, 189 (1966).

[38] Laschenko, P. N., J. Russ. Phys. Chem. Soc. 43, 793 (1912).

[39] Laschenko, P. N., Proc. Don. Polytech. Inst. 2, 46 (1913). [39a] Subba Rao, M., Indian J. Chem. 1 1 , 280 (1973).

[40] Pruna, M., Faivre, R., and Chaudron, G., Compt. rend Akad.

Sci. (Paris) 227, 390 (1948).

[41] Pruna, M., Faivre, R., and Chaudron, G., Bull. Soc. Chim.

France, D204 (1949).

[42] Chaudron, G., Mondange, H., and Pruna, M., Proc. Intern. Symp. React. Solids, Gothenberg 9 (1952).

[43] Mondange-Dufy, H., Ann. Chim. 107 (1960).

[44] Hazlewood, F. J., Rhodes, E., and Ubbelohde, A. R., Trans. Faraday Soc. 52, 2612 (1963).

[45] Crawford, W. A. and Fufe, W. S., Science 144, 1569

(1964).

[46] Macdonald, G. J. F., Amer. Mineral. 41, 744 (1956).

[47] Sclar, C. B., Carrison, L. C., and Schwartz, C. M., Amer.

Soc. Mech. Engr. Paper No. 62-WA-248, 7 (1962).

[48] Simmons, G. and Bell, P., Science 139, li97 (1963).

[49] Bridgman, P. W., Proc. Amer. Acad. Arts Sci. 72,45 (1937).

[50] Jamieson, J. C., J. Chem. Phys. 21, 1385 (1953).

[51] Schock, R. N. and Katz, S., Amer. Mineral. 53, 1910 (1968).

[52] Hiragi, Y., Kachi, S., Takada, T., and Nakanishi, N., Nippon Kagaku Zasshi 87, 1308 (1966).

[53] Burrage, B. J. and Pitkethly, D. R., physica status Solidi. 32,399 (1969).

[54] Bischoff, J. L., Ambr. Mineral. 54, 149 (1969).

[55] Brown, W. H., Fyfe, W. S., and Turner, F. J., J. Petrol. 3, 566 (1962).

[56] Fyfe, W. S. and Bischoff, J. L., Soc. Econ. Paleont. Mineral.

(Special) 13,3 (1965).

[57] Bischoff, J. L. and Fyfe, W. S., Amer. J. Sci. 2 66, 65 (1968).

[58] Bischoff, J. L., Amer. J. Sci. 2 66, 80 (1968).

[59] Zimens, K. E., Z. Physik, Chem. B37, 231 (1937).

[60] Zimens, K. E., Naturwiss. 25, 429 (1937).

[61] Ahrens, T. J. and Katz, S., J. Geophys. Res. 68 , 529 (1963).

[62] Gordon, R. B. and Vaisnys, R. J., J. Geophys. Res., 69,

4920 (1964).

[63] Lander, J. J., J. Chem. Phys. 17, 892 (1949).

[64] Boeke, H. E., Chem. Zentr. I., 1909 (1913).

[65] Lander, J. J., J. Amer. Chem. Soc. 73, 5794 (1951).

[66] Baker, E. H., J. Chem. Soc. 2525 (1962).

[67] Rapoport, E. and Pistorius, C. W. F. T., J. Geophys. Res. 72,6353 (1967).

[68] Zimens, K. E., Z. Physik. Chem. B37, 241 (1937).

3.3. Thallous Carbonate, T12 C03

(monoclinic, I2/m-C|h, Z = 4, a =7.55 ±0.02 A,

6 = 5.38 ± 0.02 A, c= 10.58 ±0.02 A and 0 =

94°47'[1])

Vorlander et al. [2] reported a single transition

at 501 K. Tranquard et al. [3], however, showed that

this transition occurs only when commercial material is used. TI2CO3 purified by fractional crystallization is reported to show two new transitions at 473 and 536 K instead of the above phase transition

[3], These transitions between the phases III —» II and II —

I, were also confirmed by Pistorius and

Clark [4] at transition temperatures 485.5 ±2 and

533.5 ± 1 K, respectively.

High Pressure Transitions: Pistorius and Clark [4] failed to detect any high pressure transformation at 293 K up to 44 kbar. In their phase diagram studies,

Pistorius and Clark [4] found that the II/I transition

line falls with pressure to the I/III/II triple point at 3.4 kbar, 525 K. The resulting III/I transition slowly

rises with pressure, passes through a broad maximum at 18.7 kbar, 536.8 K and then falls with in- crease of pressure. The III/I transition terminates at a triple point I/IV/III at 29 kbar, 532 K. A weak DTA

signal observed at 34.9 kbar, 478 K is attributed to the III/IV phase transition, IV being a high pressure

phase. The IV/I transition line rises with pressure

and terminates at a triple point I/V/IV at 35.1

kbar, 501 K. The IV/V transition point was ascer- tained only be a considerable increase in slope at this point. Phase V is also a high pressure phase.

The DTA signals associated with the IV/I and V/I

transitions seem to be very similar to those associated

with the III/I transition.

References

[1] Mitchell, R.S.,Z. Krist. 123,399(1966).

[2] Vorlander, D., Hollatz, J., and Fischer, J., Ber. 65 , 536

(1932).

[3] Tranquard, A., Lacassagne, C., Boinon, M., Capella, L., Cohen-Adad, R., Compt. rend. Acad. Sci., 2 64, 1111 (1967).

[4] Pistorius, C. W. F. T. and Clark, J. B., Z. Physik. Chem. 68,

157 (1969). 45
3.4. 3 d Transition Metal Carbonates

Heat capacity measurements in the temperature

range 1.6-80 K [1, 2] revealed that carbonates of

manganese, iron, cobalt, and nickel show antiferromagnetic to paramagnetic transitions at 29.5,

30.6, 17 and 22.2 K, respectively. Measurements

in the temperature range 70-300 K did not show

any anomaly in these carbonates except in C0CO3 which shows an anomaly due to the sorbed water

[3]. Crystal structure for all these rhombohedral

carbonates are tabulated by Graf [4].

3d Transition metal carbonates

Substances and measurement technique

Observations Remarks Refer- ences

Manganese carbonate , MnC03 , calcite type, D6 — R3c, Z = 2 (rhomboheral cell, and Z — 6 (hexagonal cell), a = 4. 777 A and c =

at 298 K

15.67 A

Heat capacity (Temperature

range: 1.6-80 K). An antiferromagnetic-paramagnetic transi- tion at 29.5 K is shown by a heat capacity

anomaly. At liquid helium temperature the heat capacity obeys the law CM = aP,

where

Excitation of the second branch of the

spin wave spectrum is observed at temperature close to TN/10 (TN , 32.4

K). The results provide an experimental

confirmation of the spin wave theory.

[1,2]'

a= 18.0 ±0 • 7 X 10- 4 J mol" 1 K"4

(Temperature range: 70-300

K). No anomaly was observed. A continuous

increase of heat capacity with temperature was found. The total entropy,

consisting of the lattice and magnetic

parts was also determined.

The entropy of magnetic ordering constitutes 14.7 percent of the total entropy.

The earlier results of Anderson [5]

differ from those of Kostryukov and

Kalinkina [3] possibly due to the nature and quantity of impurities.

[6].

Magnetic measurements Magnetic susceptibility was found to in- crease abruptly below Tc , 31.5 K and

to vary considerably with the field.

The observed anomalies are interpreted

by postulating that below Tc , MnC03 goes over to an antiferromagnetic

state in which the moments of the sublattices do not fully compensate each

other.

[3]-

Iron carbonate, FeC03 , rhombohedral (calcite type), a = 4.6887 A, c= 15.373 A [4]

Heat capacity (Temperature range: 1.6-70 K).

Transformation at 30.6 K is associated with change from antiferromagnetic to para- magnetic state. Nuclear heat capacity has

not been observed for FeC03 showing : that Fe has zero magnetic moment.

In FeC03 the spins are parallel to the principal axis so that the magnetic heat capacity should be practically nonexistent at low

temperatures.

[1]-

(Temperature range: 70-300 K) No maximum is observed in this range. The total entropy of FeC03 comprises of i lattice and magnetic contributions. The

latter is 10.6 percent of the lattice entropy. The entropy of magnetic ordering

constitutes 13.9 percent of the total entropy.

[3].

46
3d Transition metal carbonates — Continued

Substances and measurement technique

Observations Remarks Refer- ences

Cobalt carbonate, C0CO3, rhombohedral (calcite type), R3c, Z = 6, a = 4.659 A and c= 14.957 A at 299 K.

Heat capacity (Temperature range: 1.6-70 K). Transformation at 17 K is associated with a change from antiferromagnetic to para- magnetic state. At liquid helium temperature, the magnetic heat capacity

obeys the law C.\t — aT3

, where a =13.5

X10-4 J

- mol1

K-4

.

The results agree with those given by magnetic measurements. Excitation of the second branch of the spin-wave spectrum

is observed at temperature close to 7 at/3.

[1].

(Temperature range: 70-300 K).... Maxima found at 270 K, is attributed to the sorbed water.

[3].

The total entropy is comprised of the lattice and magnetic contributions. The magnetic contribution for C0CO3 is 8.3 percent of the lattice entropy.

At 298.15 K, the entropy of magnetic

ordering contributes 13.0 percent of the total entropy.

Magnetic measurements Magnetic susceptibility increases abruptly

below Tc , 17.5 K and varies consider- ably with field.

It is postulated that below Tc , the substance

goes over to an antiferromagnetic state

in which the moment of the sublattices do not fully compensate each other.

[6].

Nickel carbonate , NiCC>3, rhombohedral (calcite type), D6 — R3c,Z = 6, for hexagonal unit cell,

3d a = 4.609 A and c= 14.737 A at 298 K.

Heat capacity

range: 1.6-70 K). (Temperature The transition at 22.2 K is associated with

a change from antiferromagnetic to paramagnetic state. At liquid helium

temperature, the magnetic heat capacity

obeys the law C^ — aT3

, where a =

15.3 X 10-4 J moh1 K-4.

The results agree well with those obtained

from magnetic measurements.

[ 1 ].

(Temperature range: 70-300 K)... No anomaly is obtained in this temperature range. The entropy of magnetic

ordering was found to constitute 10.6 percent of the total entropy.

[3],

Magnetic measurements. Between 60 and 290 K the Curie-Weiss rela- tion represents the temperature depend- ence of the susceptibility of nickel car- bonate (both green as well as yellow

modifications).

The proportionality of the magnetization

with the field disappears at 40 K and the material becomes ferromagnetic at 4 K.

[7].

References

[1] Kalinkina, I. N„ Sov. Phys. JETP 16, 1432 (1963).

[2] Borovik-Romanov, A. S. and Kalinkina, I. N., Sov. Phys.

JETP 14, 1205 (1962).

[3] Kostryukov, V. N. and Kalinkina, I. N., Russ. J. Phys. Chem.

38, 422 (1964).

[4] Graf, D. L., Am. Mineral. 46, 1283 (1961).

[5] Anderson, C. T., J. Am. Chem. Soc. 56, 849 (1934).

[6] Borovik-Romanov, A. S. and Orlova, M. P., Sov. Phys.

JETP 4, 531 (1957).

[7] Bizette, H. and Tsai, B., Compt. Rend. 241, 546 (1955). 47
3.5. Silver Carbonate, Ag2 C03

(monoclinic, C|-P2i, Z — 2, a = 4.836 A, 6 = 9.555

A, c = 3.235 A and 0 = 92.64° at 298 K)

Ag2C03

Measurement technique Observations Remarks References

X-ray diffraction with impure

samples.

With the ratio of dopant Y(III) and Gd(III)

to Ag, rc3ff).005 a new orthorhombic

crystal structure is reported with a= 13.94 A, 6 = 5.97 A, c = 5.30 A.

[1]-

Heat capacity (room temperature — 453 K). A rapid increase in the heat capacity was

observed above 423 K. The anomaly is possibly due to the dis- sociation of the sample.

[2].

Differential thermal analysis Two endotherms, first at 458 K and the second above 500 K were found. A

small exotherm was also detected.

The first is attributed to a reversible

transition and the second to the dissociation. The exotherm is attributed to the annealing

out of defects in Ag20.

[3-5].

Differential scanning calo- rimetry (with the sample

sealed in CO-2 atmosphere

to prevent decomposition).

Two reversible endotherms in the temperature range 440-475 K were found. The first also observed previously [3] has AHtr , 730 ±80 cal mol-1 and the second found only in this work has AHtr, 473 ±30 cal mol -1

[6].

EPR studies of impure

samples..

EPR studies on y-irradiated Y(III)-Doped

Ag2 C03 also indicate the presence of a new crystal structure. The same crystal structure is thermally attained in undoped Ag2C03 at approximatly 423 K

under an atmosphere of C02.

The results agree well with x-ray diffrac- tion studies.

[1].

References

[1J Ashford, N. A. and Snelson, A., J. Chem. Phys. 51, 532

(1969).

[2] Kobayashi, K., Science Repts. Tohoku Univ. 35, 283 (1952).

[3] Leyko, J. and Maciejewski, M., Bull. Acad. Pol. Sci. 12,

273 (1964).

[4] Calbertson, W. J. (Jr.), Rept. No. AMRL-TR-64-119,

Denver Res. Inst. 6570th Aerospace Med. Res. Labs.,

Wright-Patterson, AFB, Ohio, Dec. 1964.

[5] Rao, C. N. R., Yoganarasimhan, S. R., and Lewis, M. P., Can. J. Chem. 38, 2359 (1960).

[6] Wyderen, T., Aust. J. Chem. 20, 2751 (1967).

48
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BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO.

NBS-NSRDS-53

2. Gov’t Accession

No.

3. Recipient’s Accession No.

4. TITLE AND SUBTITLE

Crystal Structure Transformations in Inoraanic Nitrites,

Nitrates and Carbonates

5. Publication Date May 1975

6. Performing Organization Code

7. AUTHORfS)

C.N.R. Rao, B. Prakash and M. Natarajan

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

Same as No. 9

13. Type of Report & Period Covered

N/A

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 74-18389

16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

A critical survey of the data describing crystal structure transformations in inorganic

nitrites, nitrates and carbonates is compiled. Data on crystallographic, thermodynamic

spectroscopic, electrical, dielectric and other properties are given for each solid.

Experimental techniques used to obtain the data are given and comments on the data are included in the tables. The literature is surveyed up to June 1973. References have

been selected on the basis of their pertinence to the data cited.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons)

Carbonates; crystal structure transformation; nitrates; nitrites; phase transformation;

x-ray diffraction data

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