CHAPTER I.

INTRODUCTION

The hydrated sulphates of copper have, in the past

attracted the attention of many research workers and have
added much to the existing knowledge of their properties.
Copper sulphate is reported to have mono, di, tri,
penta, hexa, hepta and ennea hydrates.
( 1915) the existence of
possible.

a hemihydrated

According to Janecke
sulphate is also

The individuality of the hemi, di, hexa, hepta and

annea hydrates is not well defined but the mono, tri and

penta hydrates are the only hydrates which appear to be stable

according to Bell and Taber (1908).

Of these three the penta

hydrate is the most stable hydrate salt.

It can ,be grown as

a single crystal from the solution without much difficulty in

the laboratory.

A brief description of the same and a short

account of the various types of studies made on it so far is

given below.
1.1
Name -

General descriQtion.
(i} Copper Sulphate Penta Hydrate
( ii' Blue Vitro!
(iii) Chalcanthi te
(iv) Vitriolum Cupri
(v) Vitriolum Veneris
(vi) Cuprian Vi trio!
(vii) Blue Stone
(viii) Kupfer Vitriol
(ix) Couperose Bleue
(x) Cuivre Sulfate

(xi) Vitrtole de Rnme etc.

Chemical formula
Colour

Ul tramari.ne-blue,

.,_

Occurance

The mineral Chalcanthite, CuS04 ,5H 20

has been found deposited from cupriferous mine waters either

'"

in crystals or in stalacti.tic formations and according to

H.Oehmichen it occurs a!O a workable ore at Copaquire(Chile).
where it has probably been formed by the oxydation of
Chalcopyrite,
On a large scale, Cupri.ferous hi-products are
treated with Sulphuric acid,

In general
cupriflrous pyrite~
.
~

is roasted so that copper is largely oxidized to sulphate,

The hot roasted ore is extracted with water and the liquid
concentrated for crystallization,
In the laboratory if a gram atom of copper be heated with two mols. of Sulphuric acid, evaporated to dryness.,
exhausted

,,,j_ th hot water, filtered from copper and cupric

sulphide, blue crystals of the penta hydrated Cupric Sulphate,

euso 4 .5H 20,

1.2
Density

separate

on cooling.

Physical Properties.
The values range from 2.1943 (Hassen Fratz(l798J

to 2.330 Rudorf (1879)

The best representative value is

2.27 in agreement with 2.274 of Kopp (1859) and 2.276 of

Bachmetjeff (1893).

The density of the samples taken for

present study was found to be

Melting point

-~

'2 26 <j"m c"I'YI

------

~~---------

Does not melt when heated.

.. Thorpe and Watts (1880) gave 1091

Specific Volume
Nicho (1883) gave

18~322

for the mol,vol, of the penta

hydrate when 05 mol. i.s dissolved in 100 mols. of water at

20C.

1.3

Crystallization Its crystals can be easily grown from solution by

evaporation method or by controlled cooHng method.

Effect of condition of crystallization on size and
purity of crystal viz, the effect of rate of agitation and
composition of the solution on the size and purity has been
investigated by Matuserich (1960) who found that increasing
the rate of agitation from 6 to 60 r.p.m. and the nickel
content from 30 to 125 grams/litre decreased the size of
crystals but As+++ 47 grams/litre decreased the size by
20 %.

Twinning of crystals This was found by Boeris (1907) to be rarely as

cruciform inter growths of two individuals with the edges
001
and

and

100

on one crystal respectively parallel to

001

on the other and the planes

010

100

in common,

Etch figures and dehydration figures conform to pinacoidal

symmetry

Blasius (1885),

Gaudefroy (1914)

Mixed Crystals Stortenbeker (1897) and Hollmann (1901) found that

with zinc and cupric sulphate penta hydrate triclinic dark
blue crystals are formed.
Retger (1894) studied the mixed crystals of cupric aAd
magnesium sulphates and found the solid phases to be triclinic

wil'i
~9543

% Cuso 4 .5H 20.

He also found tricl inic crystals with

Cadmium sulphate and ferric sulphate having 982q and 9488

parts CuS0 4 .5H 2o. The corros;on figure produced on the
crystal by exposure to atmosphere was studied by Blasius
( 1885)

1.4

Crystalloqrilphi.c Description ,

110

r3o

010

F.s

tl \G.l

Un\t Cell

Measurement on the crystals and

determ~.11ation

of unit

. ,/cell
--- dimension, space group, crystal symmetry etc. was first
.,~""'-

/carried out by Kupffer (1826),'

f corrected

The values were later on

by Von Groth (1908) on the basis of unpublished

measurements made by Barlcer and were given as :

a : b : c
o(

05721 : 1 : 05554

= 825', ..0 = 1078', y = 10241 1

Tutton ( 1911) made a fresh study of the same and the

following values given by him are usually accepted.
Crystal System

Triclinic

Clas~

Pinakoidal holohed~al

't

Habit

Prismatic

Axial angles

o<

fb

= 10726 1

8216

y = 10246 1

Rilti.o of

a :b:c

axe~

Forms observed

05715: 1: 05575

,
uo ,
ou ,

= 121

,
,
,

= 111

a = 100

b = 010

p =

p'= 1l0

a =

t'= 021

c = 001
p"= t20

v = 131

s'= 121
..J.

Ecch of these forms consists of a pair of parallel

faces or pinakoids.
Crystnl angles

ab = 100:010
bp = 010:110

794'
532'

pa = 110:100

264'

ap'= .tOO: 1l0

~17'

p" b = 120:010

2240 1

and 41 other values not qiven here due to want of space,

These five angles were measured for the crystals
grown in this laboratory.

1.'2.

Fig,ABond structure.
1.5

Crystal Structure A.s a result of X-ray d tffraction work the crystal

structure of Cuso 4 .5H 20 was originally proposed by Beevers

and Lipson (1934) as follows The svstem ;s a bi-molecular unit and has the

dimensions
10.7 A,

c0

5.97 A

The two copper atoms are not equivalent as regards their

'

position in the crystal lattice, they occupy differemt

special positions (a)

o,o,o (e) i?t?O.All the other atoms are

in the general positions (0.01, 0.29, 0.64 ).The structure

as a whole is an aggregate of the S04 and Cu(H20)4 groups:
with t e fift' water molecule adjacent to the two sulphate
oxygen atoms and tro of the other water molecules, four of
the water molecules being closely associated with the copper
atoms.
Inspite of their crys,tallographic differences each-o11'
the c:opper. atom isc surrounded by a nearly regular. octahedron
of oxygen atoms,four of which belong to the-water molecules,
the ot<>er

ions.

Fi,
-

.,., c.;j;p..

--

...

i....CjYonf"~tI

Of "'

13 ]),,,.,.,;.,..

____..

Though each copper ion is at the centre of an octahedron

formed by four water molecules" and two oxygens, the' octahedron
is only an approximation, the four water molecules being
much closer to the Cu ion than the oxygen ion.

.. -

Four of the water molecules are arranged in a plane about

copoer ion to which they are aooarently connected by valency
bonds.

The additional water molecule is connected tetrahe-

d.rally to two water molecules of the first type and to the

two oxygen atoms of the sulphate i.on by Hydrogen bonds.
Atoms

Positions

Cu

(1)

(a)

Cu

(2)

(c)

(1)

0.28

064

s
0

(1)

(1)

089

015

069

( 2)

(1)

0.24

Oo31

062

(3)

(1)

Oo86

Oo38

064

(4)

(1)

002

030

038

(1)

(1)

083

o.os

016

(2)

(1)

029

011

017

(3)

(1)

048

041

032

(4)

(1)

072

042

o.o1

(5)

(1)

043

012

065

Table 1.

Parameters of the atoms in CuS0 4 .5H20

1-~

Fig. (a)

"

A projection of the triclinic CuS0 4 5H2o

crystal along the C axis.

Atoms of the

so4

ions, with oxygen represented by

large circles are connected by the light lines.

The copper

atoms are the small heavy lined circles, the large heavily
ringed circles being those of water molecules wh5.ch are not
co-ordinated by the atoms of copper.
I~

Fig.~(b)

A Packing drawing of

euso4 .5H 2o

structure.

The line shaded oxygen atoms of the tetrahedral

so4

ions nearly hide the sulphur atom they enclose. The small

(dotted) copper atoms also barely show from within the group
of large (dotted)water molecules arranged about them.

No

dtsttncHon is made between the co-ordinated and unco-ordi.nated water molecules.

Bacon and Curry (1962) studied si.ngle crystals of
CuS04 .5H 20 by neutron diffraction method and found that the
H-0-H angle for all the water molecules are wi.thin a degree
or two of tetrahedral value HOd the hydrogen bonds have to be
bent by up to 26
1.6

in order to accomodate them.

Optical Properties
I<:ohlrausch ( 1877) and Pabe ( 1873) found the crystal

to have negative double refraction.

Gerney ( 1905) found the crystal to be tribolumini-

scent.

The following data is due to Lavenir (1891).

Orientations

n (Na)

169

76

15140

Biaxial negative

76

78

15368

2 v = 56 02 1 (meus)

57

18

15434

-v-<

A photoconducting materi.al has been prepared by using copper

sulphate by Ranby and Hobb (1958).
1.7

Thermal Properties
The-Coefficient of Thermal expansion as determined

by Bachmetjeft (1893) for the crystal is 000165 and

Specific heat between 16 - 47 C
Pape (1877) and

is

the

0285

Rontgen (1878} found that the heat

conductivity of the pentahydrate. salt possesses a conductivity ellipsoid with axial rati.os

939 : 860 : 1

.J. Thomsen ( 1.872) stud)!'d the heat of hydrati.on of

the sulphates nf cooper

~s

folloYs :

CuS0 4 solid + 5H 20 lith = 18.55 Cals.

Cuc:;o 4
II

+ 3H 20 liq. = 129' Cals.

II

+ H20 liq. = 6.47 Cals.

'
' The rate of formati.on of pentahydrate
in moist air was mea-

sured by Cross (1.881).

Paoe (1877) found that the crystals of the pentahydrate effloresce in dry air.
Lescoeur ( 1886) found the dissociation pressure
for efflorescence to be 6.0 m.m. at 20.

.
To obtain the monohydrate Grahm (1.835) heated the
pentahydrate in vacuum at 38.- Hodgkinson heated the pentahydrate for a week at 98 and Horn and Taylor ( 1904) heated
the same in a current of dry air at 100.

Nobukazu et.al.

(19~1)

prepared CuS04 .5H 20 by heating the CuS0 4 ,5H 20 in air

at 105 :i- 5C,

Etard (1887) obtained the trihydrate by heating the

pentahydrate with excess of H2S04 at 200 C.

According to Guareschi (1915) over Calcium chloride
at 21- 23 the oentahydrate loses two water molecules and
passes into trihydrate.

A.t 60 it forms the monohydrate. In

air the pentahydrate is not changed at 40 but loses tw~

Nater molecules at 45- 50 and another water molecule at
60 and the remaining water is lost at 206.
In a current of dry air at 41- 42 the pentahydrate
loses

1.5

H2o

in

the

first

five

hours

and

it

ll
loses0.5 H20 in another five hours. There is no further
loss at 50- 60 but at 72 another 2H 20 is given off.
According to Pierre (1846) the pentahydrate crystallised above 25 loses all its water molecules in dry air at
114 is wrong,
Actording to Lattschinoff (1888) when the pentahydrate is heated to 180 it loses 4,75 H2o and all passes off
when heated to 360,
Krafft (1907) reported that all the water is lost when
the pentahydrate is heated to 250,
According to Richards ( 1891) 0.042 % water is retained by the salt heated to 365 and complete dehydration is
possible at 400C,
Rinne (1899) found that about a tenth of water is
lost from the pentahydrate ~rhen heated to 99 and the colour
is st:i.ll dark blue.

At 105, 2/5th of the water is given off

and the colour is paler.

At 117, 4/5th of the water is

expelled and the residue is greenish white in colour.

At

258 all the water is driven off.

Grahm ( 1835) found that the last water molecule is
lost at 242 but according to Richards (1891) some water still
remains at still higher temperature for the anhydrous salt
dried at 255 loses about 017 % of its weight when. heated to
365 and a small amount 012% is held even at 400.
According to Horn and Taylor (1904).it is impossible
to prepare pure anhydrous salt or monohydrate salt by heating
the pentahydrate.

The product is brown and losses in weight

12
are variable even at 220.
In every case this purity of the salt is affected
by the secondary reaction between water and CuS0 4
agrees with Naumann's observatlons.

This

Dehydration of the pentahydrate in an air stream

with a given partial pressure of water was studied by
Sakovich and Komarov (1960).
water (

At low partial pressure of

12 m.m. of mercury) the dehydration occurs in one

step with the formation of a salt close to Cuso4 .5H 2o. At

partial pressure of
1760 m.m. the dehydration occurs in two
stages, the first leading to the formation of CuS04 .3H 20.
Cupric Sulphate does not melt when heated.
(1904) and Bussy (1824)

stated that the anhydrous salt loses

sulphuric anhydride and forms a basic sulphate.

still higher temperature
and residue of

Proust

so 3

or

so 2

If heated to

and oxygen is given off

.eue 2 is left.

Bradford (1902) stated that the decomposition

begins at 653 forming a yellow, insoluble basic sulphate and
at 720 it is completely decomposed to Cupric Oxide etc.
Rechards (1891) found that no acid is lost from the anhydrous
salt heated at 365.

When the temperature of the salt is

observed from time to time while it is being heated, arrests

in the heating curve occur at about 340 , 380 , 500 and 620.
These critical temperatures correspond with the points at
which the salt begins to decompose or forms the basic salts
8Cu0.3S0 3 and 2Cuo.so 3
According to Mourlot (1897) Cupric oxide begins to

form at ahout 700,

Ketov and Starkov ( 1961) stated that the thermogram
of CuS0 4 exhibited peaks (endothermic) at 819- 860 and
867- 934, The loss in weight due to evolution of 00 3
increases rapidly with temperature.

After the first endother-

mic effect at 819- 60 the loss in weight of the sample

corresponds to 50% of the weight of 00 3 initially present,
In a flowing current of air the degree of decomposition of

Cuso4

oxygen

content in the gas increased from zero to hundred

increased with temperature and decreased as the

percent.
The dissoci.ati.on equilibrium of the crystallohydrate s of copper sulphate was studied by Eugen Segal ( 1958) from
the thermodynamic point of view and a theoretical relation
obtained from the variation of vapour pressure with temperature for the pentahydrate.
The relation did not agree

wit~

the experimental

results of Lescoeur (1890),

Bogdan Sujak (1958) studied the thermostimulated
. ---

-------

co-exo electron emission simulated by released water of

--------- --------- --

crystallisation.

Actually they were studying the influence

on the counting rate of ionisat i.on chambers of the water

vapour released by hydrated salt such as

euso4 .5H 20 and found

that glow curves can be obtained which are due to release of

---------water molecules instead of thermoele.ctrons from the solid.
For example glow curve peaks were obtained at temperature
where the degree of dehydration of

euso4 .5H 2o, CuS04 .3H 20

and

1.8

Magnetic Properties Krisnan and Mukherjee ( 1931'>) detenntned the direc-

t i.ons of ma111imum and minimum magnetic su sceptibil tties and

studied the anisotropy of the same, Their result
'X.L- "X- 11 = 300 x 10-6 cgs, emu. per gm. mol. poi.nted to the
ex5. stence of a rhombJ.c component in the crystalline field,
De Haas and Gorter ( 1930) stud ted the magnetic
susceptibilities in the powder form.

From their data

Jordahl (1934) and Jones (1935) concluded that in the pentahydrate the crystalline field actions on cu++ should b~ predominantly cubic,

This result has been shown to be in confir-

mity wi.th the structure of the crystal suggested by Beevers

and,Lipson (1934).
Transition from antiferromagnetJ.c st>ate to weakly
ferromagnetic state in a magnetic field was studied by
Kreines ( 19611.
The magnetic moments of

6-~nhydrous

'

copper sulphate

were measured for various crystallographic directions in the

range 13 - 300 K
A.t all temperatures i.n the magnetic field upto
"'4 Koe, the magnetlc susceptibility of the crystal was
independent of the field intensity.
Kreines ( 1958) also studied the magnetic anisotroPY of a single crystal of copper sulphate in the antiferro-
magnetic state,

He measured l(..l. and

sulphate obtained from a solution of

Sulphate at 15 - 300 K
..

"t 11 for

crystal of copper

euso4 in Ammonium

1\s the tel!lperature decreased

XJ.. increased

ly <>t 35K and r)f;e to a ffil!'Xi.mum at. 34.5K

'"*

abrupt-

Then it decrea-

sed to 3/4 th l its maximum value ,and remained constant below

12 - 14K.

x. 11 decreased

almost to zero below 3nK The

transition at 34.5K was to an antiferromagnetic state of

second kind in the region 1.5 - 34K.

X.

=a

+ q ( T/Tc ) ~

The Lande 'g' factor and the real and imaginary

parts of the comt:ilex susceptibility were determined as functions of angles for the pentahydra:te by Berger ( 1960).
~-~--

Mathur ( 1960) measured the 1p;i.ncipl~ 1 magnetic

susceptibilities of the pentahydrate.
Pierre E scoffier and Jean Gauthier ( 1961) sti.tdied
the thermomagnetic behaviour.

They determined the constants

of ,the Curie Weiss Law in the temoerature range 78 - 300.

1.9

Electrical Properties The electrical conducti.vi.ty of aq. solution of

cupric sulohate has been studied by Whetham ( 1900,1903),

Me Gregor and Archibald (1898), Kohlrausch (1885, 1893),
Kahlenberg (1899~1901), etc.
Sack (1891) and Kohlrausch (1893) have calculated
the the temperature coefficient of conductivity of the
solution.

Bouzat ( 1903), Whetham ( 1900, 1903) etc. have

calculated the degree of ionization.

Arrhenius (1884-S9-92) calculated the heat of
ionization to be 156n cals. at 35.

..

Freeman (1882) has studied the production of a

current during the

evaporat~on

of a solution of cupric

IUlphate.

Bollard ( 1906), aJid Goo4viD &: Horsob ( 1919)

measured the conductivit,r ot solD. ot cupric sulphate with

different proportions et IUlJihll:r:Lo acid.

Tbe potential

difference of' copper in a solution or cup:r:Lc sulpbate bas

been meaiUred by Von Hepperger C1880), Luaaana ( 1892) etc.
The decomposition potential or a so1Utiou ot copper
sulphate bas been studied by Moser (1887), Truchot (1883)
etc.
The above survey of the studies of' the properties
of' copper sulpnate reveals that most of them are cbiefly
concerDed with the physical, chemical, thermal., st:Nctural
and magnetic properties only and little or no iovestigations
-~---------------~-

.::.,

have been made regarding tne electrical.

ProPrt~~~ ~n

solid state. Hence, keeping in vi.ew tbe

~imited

:t:l.l

khwledge of

electrical -behaviour in tne solid state tne preset investigation has been undertaken.
It was thought to be of interest to study tb.e
electrical conduction in tb.e solid state and its dependence
on temperature and directioNs of crystallographic axea.
For this purpose single

crys~als

were needed which were

grown from tb.e solutions in the laboratory.

cr,rstal.s tb.e effects of tne following factors were obsel"Ved.

and

( 1)

Bate of rotation of tb.e sample.

(2)

Temperature of er,ystallizatioD.

{3)

Addition of' certaiB impuri tie a.

(~)

PaesiDg intermittent D.C.Cilrrent tbrougb the

solution.When single crystals of sufficiently largEr size

were obtained their interfacial angles and density was measured.
In order t..; study t''e structural cl1anges with temperature the differential thermal anlysis was carried out.The
purpose of carrying out D.T.A . was also to co-relate the
temperature dependence of a. c. and d. c. electrical conductance with the structural changes.X-I!ay powder photographs
and rotation photographs were also taken after heating the
samples to the temperatures corresponding to the peaks in the
D. T.A. curves.
The variation in conductance with temperature was
first measuredl for the samples in the powder form then the
same was repeated for samples cut from single crystals a long;
various crystallographic directions.
The variation in the dielectric constant with temperature was studied by determining the capacity of a small condenser having tl1e crystal plate as dielectric at different
temperatures. The capacitance for the samples cut along various crystallographic directions at room temperature at different frequencies(from 100 kc/s to 20 mc/s) was also measured.
This supplied t 11e data for the study of dielectric behaviour
under a.c. fields of different frequencies.
To see w:1ether the salt shows ferroelectric behaviour
under any condition the polarization-vs- voltage curves were
obtained using the circuit of SaWYer and Tower on the

C.R.a.

---------R E F E RE NC

Arnold Reisman and Joan Kartak,1958 1 (Intern. Busyness

Machines, Newyork N.K . ) J .Am. Chem.Soc.,
80 1 6500-3(C:t', C.A, 52 1 1'7866h)
Arrhenius,S.,Recherches sur la conductibilite galvanique
des electrolytes,Stockholm 1884;Zeit. Phys.
Chem., 1889 1 96; 1892 1 9 1 339.
Bacon, G.E. and

Curry,N.E.,1~62 1 (At.Energy

Research Estd.

Engl.) Proc. Roy. Soc.,London 1 266 1 95-108.

Bachmetje:t':t' 1 P.I., 1893 1 Journ. Russ.PHys.Chem.Soc.,25,263;

...

25; 265;
Bell 1 J.M:tand Taber,T.of.C, 1 1'908 1 Journ. Phys. Chem.,12 1 .172 1
also 1906 1 12 1 172; 1908 1 12 1 17:!; 1907 1 11 1 637
.J,~ ~-

.::

,.

'

Berger 1 W. 1 1960 1 Naturwissen Scha:t'ter, 47 1 424-5.

Beevers ,c.A. and Lipson, H., 1934 1 Proc. Roy. Soc.A., 146A 1 570;
.
.
1935 1 148A 1 664; 11935 1 151A 1 347;
1935 1 Ph1l.Mag. 1 1'9 1 887;
1966 1 Phil.Mag.,Vol.3 1 1 1 79-83;
1935,Krist.,91,157.
Berthelot,M., 1823 1 Compt. Rend., 77, 24;
1877 1 Ibid.84 1 676;(7) 1 1B98,14 1 203.
Bliasius,E., 1885 1 Zeit.Crust.,10 1 221 and 10238.
Boer is, 1907 ,Att.Soc. Ital.Sc.Uat.lUUan, 44 1 73.
Bogdan Sujak 1 1958 1 Czechoslov. J. Phys. 1 8-616-17.
Bouzat, 1903 1 Compt. Rend., 136 1 1395.

Bradford R.H, (J902) , Trans. Amer. Tnst. Min. Enq, 33,50,

Bussy A.A.P.. ( 18?4), Ann. Chim. Phys. 26, 4J 1.
C.A.L. de Rruyn (1892) Rcc, Trav. Chim. pays Ra~. 11, 112;
Zeit Phys. Chern. 10, 788.
Cross C.F. (J88t) Chern. News, 44, 209;
(1879) Journ. Chern, Soc, 35, 799.
De Haas and Gorter, (1930), Leiden Comm. 210 d.
Etard A. (.1876) Cornot. Rend. 83, 899; (1878) ib. 87, 602;
(1887) t04, 1615;

(1892) 114, 112;

( 1894) Ann, Chim. Phys. 7 , 2, 503.

Eugen Segal ( 1958) Univ. C. I. Parhon, Bucuresti Romania.
Analele Univ. Univ. C.I.Parhon Bucuresti Ser
Slint nat. No.18.
Freeman S.H. (1882) Phil. Mag., (5) 69-78, 13, 398; Arner.
Journ. Science,

(2),

23, 428,

Grahm T. (1835), Phil, Mag. (3); 6, 419; Phil. Trans.123,253,

Guareschi I (1915) AttL .Accad. Torino, 50, 1125.
Gaudefroy ( 19141, BulJ. Soc, Min, 35, 129.
Gerney D.

(1905), Compt. Rend, 140, 1338,

Goodwin H.llt, and Horsch W.G. ( 1919) Met.Chem. Fng. 21, 181.
Hassenfratz (1798) Ann. Chim. Phys. 28, 3.
Hollmann R., ( 1901) Zei.t, Phys. Chern, 37, 193; ( 1902) 40,575;
( J905) 54, 98.
Hollard A. (1906) Bull Soc. Chirn., (3), 35, 1248.
Horn D.W, & Taylor E.D. (1904), Arner. Chern. Journ.32, 276;
( 1908) 39, 194; ( 1904), 32, 277.

ib.

Jordahl (1934), Phy. Rev. 45, 87.

Janes, (1935)

ib. ' 48, 78!

Janecke E. (1915), Zeit. Phys. Chern. 90, 265.

t.V
Ketov A.N. and Starkov N.P,, ( 1961) Zhur. Prtklad Khim.
34, 517-21. cf. C.A. 50, 3715 g.
Kahlenberg L. et, al, (1899}, Jo~rn. Amer. Chem,Soc. 21, 1.
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& Mukherjee A. (1936), Phys.Rev. Vo1.50,

No.8 Nov.

Kohlrausch F. ( 1879) \Vied, Ann. 6, 40; ib. 6, 145;

( 1885), 26, 196; ( 1893), 50, 406; ( 1877) Zeit,
Phys. 1, 100,
Krafft F. (1907), Ber.

40, 4770,

Kreines N.M. (1958), Zhur, Eksptl., Theoret. Fiz. 35.1391-7.

( !961) t
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