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,;v
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International Scientific Series
VOLUME XCVIII.
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https://archive.org/details/b281 21 03x
KtPROlXlCTlONS OP AUTOCHROMP PHOTO-
I)1RK:T
Fig. 90
Fig. 97
Fig. 90. - Screen Picture in Polarised Light, with Nicols crossed, of a thick Plate
perpendicular to the Axis Off a naturally twinned Crystal of Quartz, the left
Quartz and the right half of alternately left and
half being of right-handed
to the Plate.
right-handed Quartz, the Planes of Demarcation being oblique
CRYSTALS
BY
A. E. H. TUTTON
D.Sc., M.A. (New College, Oxon.), F.E.S.
LONDON
KEGAN PAUL, TEENCH, TEUBNEE & CO. IA5
DRYDEN HOUSE, GERRARD STREET, W.
1911
WELLCOr. r INSTITUTE
Lltlr UW
Coll. welMOmec
Call
No.
PREFACE
The idea underlying this book has been to present
the phenomena of crystallography to the general
reading public in a manner which can be compre-
hended by In the main the sequence is that
all.
A. E. H. TUTTON.
January 1911 .
CONTENTS
PAGE
Preface v
CHAPTER
I. Introduction 1
Crystals ......
and its Influence on Early Studies of
10
X CONTENTS
CHAPTER PAGE
XL The Explanation Polymorphism and the
of
Relation between Enantiomorphism and
Optical Activity . . . . . 133
Index 295
CRYSTALS
(INCLUDING LIQUID CRYSTALS)
CHAPTER I
INTRODUCTION.
2 CRYSTALS
4 CRYSTALS
Fig. 2.
Monoclinic Acicular Crystals of Sulphur
produced by Solidification of Liquid.
'i.
PLATE II.
very large size and which may also be chemically
prepared by adding a dilute solution of sulphuric
acid to a very dilute solution of calcium chloride.
The radiating groups of needles shown in Fig. 10
(Plate II.) slowly crystallise out when a drop of the
mixed solution is placed on a micro-
scope slip and examined under the
microscope, using the one - inch
objective. These needles, so abso-
lutely different in appearance from
a crystal of selenite, are yet similar
monoclinic prisms, but in which the
prismatic form is enormously elon-
gated compared with the other
(terminating) form.
This difference of facial develop-
ment, rendering the crystals of one
Fig. 9. Crystal of and the same substance from dif-
Gypsum. ferent sources so very unlike each
other, was apparently responsible for the very tardy
discovery of the fundamental law of crystallography,
the constancy of the crystal angles of the same sub-
stance. Gessner, sometime between the years 1560
DIVERSITY OF HABIT 15
Fig. 12.
^
An instance of
a mineral with
tetrahedral molecules integrantes Haiiy gives in tour-
maline, and the primitive form of tourmaline he con-
sidered to be a rhombohedron, conformably to the
well-known rhombohedral cleavage of the mineral,
made up of six tetrahedra. Again, hexagonal
structures formed by three prismatic cleavage planes
inclined at 60 are considered by him as being
composed of molecules integrantes of the form of 60
triangular prisms, or molecules soustractives of the
shape of 120 rhombic prisms, each of the latter being
formed by two moUcules integrantes situated base to
base. This will be clear from Figs. 13 and 14, the
former representing the structure as made up of
THE WORK OF HAUY 29
volume of the \
triangular one, and \ / \ \
being of parallele- y 'y
pipedal section is \ / y
capable of produc- \ ./ ./
limite.
The essential between Haiiy's views
difference
and our present which will be explained in
ones,
Chapter IX., is that Haiiy takes cleavage absolutely
as his guide, and considers the particles, into which
the ultimate operation of cleavage divides a crystal,
as the solid structural units of the crystal, the unit
thus having the shape of at least the moUcule
integrante. Now every crystalline substance does
not develop cleavage, and others only develop
it along a single plane, or along a couple of planes
symmetry a.xes ;
for these three automatically involve
altogether the presence of no less than three tetra-
gonal, four trigonal, and six digonal axes of symmetry,
together with nine planes of symmetry, twenty-two
elements of symmetry being thus present in all.
The perfections of the cube, the simple lines of
which are illustrated in Fig. 20, as the expression of
the highest kind of symmetry, with angles all right
angles and sides and edges all equal, were so fully
001
ov
100
9 H O,
2
we have very clear developinent of the
tetrahedron, belonging to the lowest of the flve
classes (class 28) of the cubic system. The crystals
are almost all combinations of two complementary
tetrahedra, one of which is developed so very much
more than the other that the faces of the latter
only appear as minute replacements at the corners
of the predominating tetrahedron.
This is the last for the present of these fascinating
growths of crystals under the microscope, but
three more will be given subsequently, in Figs. 99
and 100 on Plate XXI., and Fig. 101 Plate
, ,
to
illustrate crystallisation from metastable and labile
solutions.
Fig. 34, Plate IX., represents another kind of
phenomenon, equally instructive. It shows a fleld
in a crystal of quartz, as seen under the same power
of the microscope, a one-inch objective with small
stop and an ordinary low power eyepiece. Just above
and to the left of the centre of the fleld is a cavity,
the shape of which is remarkable, for it is that of
a quartz crystal, a hexagonal prism terminated by
rhombohedral faces. The cavity is flUed with a.
saturated solution of salt, except for a bubble of water
vapour, and a beautiful little cube of sodium chloride
which has crystallised out from the solution. This
slide, therefore, gives us an example of a natural
cubic crystal, and also an indication of the shape
46 CRYSTALS
Fig. 38. The Cube and its Three
Fig. 39. Tetragonal
Prism and its
Ei jual Rectangular Axes.
three Rectangular
Axes.
Fig. 43.
Hexagonal Prism of
the First Order and its Four
Axes.
Fig. 40. Axial Planes of a
Pihombic Crystal.
Fig. 42. Axial Planes of a Triclinic Fig. 45. The Rhombohedron and
Crystal. its Three Equal Axes.
DESCRIPTION OF CRYSTALS 55
DESCRIPTION OE CRYSTALS 57
the intersection of
the sphere by
planes passing
through the centre.
Moreover, the
points would be
distributed along
these circles at
regularly recurring
angular positions,
corresponding to
the symmetry of
the crystal. If
the crystal belong-
fig. 47.-The Spherical Projection.
A
a iOO
a 100
A
Fig. 52.
Appearance of the Interfer- Fig. 53. Appearance a Minute or so
ence Figure half a Minute after later, the Axes approaching the
commencing the Experiment. Centre. Temperature of Crystal
Temperature of Crystal about about 85 C.
40" C.
Fig. 54.
The Two Optic Axes coin- Fig. 55.
The Axes re-separated in
cident in the Centre of the Figure, the Vertical Plane a Minute or
two or three Minutes from the two later. Temperature of
commencement. Temperature of Crystal about 125 C.
Crystal 106 C.
96 CRYSTALS
G
CHAPTER VIII
104 CRYSTALS
H
trobenzene, C 6 3 (N 02 ) 3 which possesses the axial
,
independently of isomorphism.
An interesting intermediate case between morpho-
MORPHOTROPY 105
White Light.
(Reproductions of Dialings by the author.)
To face p. 108.
MORPHOTROPY 109
anywhere in the
f
...
-1
molecule, so long as ft
the position chosen
'
i
-i 9<i>
occupying the 1
r
The
credit of this next stage of further progress
is due to Sohncke, whose long labours resulted
in the discrimination and description of sixty-five
Regular Point-Systems/' homogeneous assem-
blages of points symmetrically and identically
arranged about axes of symmetry, which are some-
times screw axes, that is, axes about which the points
are spirally distributed.Sohncke's point-systems
express the number of ways in which symmetrical
repetition can occur. Moreover, the points may
always be grouped in sets or clusters, the centres
of gravity of which form a Bravais space-lattice.
This latter fact is of great interest, for it means
that Sohncke's points may represent the chemical
atoms, and that the stereometric arrangement of
the atoms in the molecule is that which produces
the point-system and determines the crystal class,
while the whole cluster of atoms forming the molecule
furnishes, as above stated, the representative point
of the space-lattice.
This, however, is not the whole story, for the sixty-
five Sohnckian regular point-systems only account
for twenty-one of the thirty- two crystal classes,
the remaining eleven being those of lower than full
holohedral systematic symmetry, and which are
characterised by showing complementary right and
left-handed forms. In other words, the}^ exhibit
two varieties, on one of which faces of low
symmetry are developed on the right, while on
the other symmetrically complementary faces are
developed on the left-; that is, these httle faces modify
on the right and left respectively the solid angles
formed by those faces of the crystal which are
118 CRYSTALS
130 CRYSTALS
134 CRYSTALS
indices.
The explanation polymorphism thus proves,
of
which have now been laid
in the light of the results
before the reader, to be a remarkably simple one.
Special pains were taken in explaining those results
to show that the temperature had a great deal to do
with the conditions of equilibrium of the crystal
structure,for it determines the intermolecular
distances, that is, the amount of separation of the
molecules, and thus controls their possibility of
movement with respect to one another. Now the
behaviour of the chemical molecules on the advent
of crystallisation is undoubtedly largely influenced
by the stereometric arrangement of the atoms
136 CRYSTALS
142 CRYSTALS
CHOH
I
CHOH
COOH
Tartaric acid was isolated by Scheele in 1769,
and its discovery was described in the ver}^ first
memoir of that distinguished chemist. Another
very similar acid, as regards some of its more apparent
properties, was afterwards, in rS19, described by
John of Berlin, and investigated by Gay-Lussac
in 1826 the latter obtained it from the grape juice
;
1 Ann. de CTiim. et PJiys., 1848, 24, 28 and 38; also 1850, 28,56;
Coinptes Bendus, 1848, 26, 535; also 1849, 29, 297; also 1850, 31,
480; also 1853, 37, 162, and 1858, 46, 615.
POLYMORPHISM AND ENANTIOMORPHISM 143
rotate the plane of polarisation possesses an asym-
metric carbon atom, an atom of carbon which is
linked by its four valency attachments to four
different kinds of atoms or radicle groups ;
indeed,
the molecule of tartaric acid contains two such asym-
metric carbon atoms, namely, the two in the pair of
CHOH groups. For each of these carbon atoms is
linked by one attachment to the carbon atom of the
outer COOH group, by another to an atom of hydro-
gen, by a third to the oxygen of the group OH, and by
its fourth attachment to the carbon atom of the other
COONH,
CHOH
CHOH
COONa
COOH
^ Journ. Chem. Soc., 1891 , 59 , 233 . 2
Ibid., 1891 , 59 , 96 .
156 CRYSTALS
CALCIUM DEXTKO-GLYCERATE.
Crystal-system : monocHnic.
Class of Monoclinic System sphenoidal or mono-
clinic-hemimorphic
Habit prismatic.
Monoclinic axial angle : /5= 69 6'.
cm = 001 : Oil 10 31 47 32 19 32 3 32 2
r'n = 201 : 211 2 29 43 29 48 29 45 29 47
f ao = 100 : 111 7 53 59 54 10 54 3 53 54
1 om = 111 Oil : 7 18 20 18 35 18 26 18 29
1 ma = on TOO : 13 107 22108 24 107 41 107 37
*
an 100 : 211 11 62 32 63 44 63 6 63 10
ns = 2Tl : TTl 1 21 35 21 27
sa = TTl : 100 3 94 49 95 34 95 18 95 23
po 110: 111 9 43 51
44 44 44 35 44 38
oc = 111 001
: 9 32 56 33 15 33 7 33 7
cs = 001 TTl
: 7 41 32 43 2 42 10 42 17
<
sp == 111 : no 7 59 15
60 54 59 59 59 58
pc = TTO : 001 14 77 2 78 21 77 42 77 45
cp = ooT : no 16 101 39103 36 102 16 102 15
pm = 110:011
(
9 52 15 53 25 52 42 52 41
i mn = on
J
211 : 5 79 5 79 26 79 15 79 12
^np = 2Tl no : 5 47 41 48 23 48 4 48 7
= TTO : iTl 5 66 42
67 17 67 4 67 5
1
= ITT : 20T 6 40 36
41 29 41 5 40 56
pm = T10:011 3 75 5 76 21 75 37 75 45
160 CRYSTALS
L
CHAPTER XII
164 CRYSTALS
Fig. 67.
Experiment to show Rectangular Polarisation of the two Spectra
afforded by a 60-Prism of a Doubly Refracting Crystal cut to afford
two Indices of Refraction.
-Y
markedly different, both
facts indicating that the
terminal faces belong to
Fig. twO different butcomplc-
70. Tlie Rhomboliedron and its
mentary rhombohedral
forms, and that the system of symmetry is the
trigonal and not the hexagonal.
But there is much stronger evidence than this for
trigonal symmetry. For the little faces marked
s and X on Figs. 68 and 69 are characteristic of the
trapezohedral class of the trigonal system, and it
will be observed that on one crystal. Fig. 68, these
faces occupy and modify a left-hand corner or solid
angle on the crystal, while on the other crystal. Fig.
69, they occupy and replace a right-hand solid angle.
Now, if a plate be cut out of the former crystal per-
pendicularly to the axis of the hexagonal prism, that
SYMMETRY AND OPTICAL PROPERTIES 173
184 CRYSTALS
186 CRYSTALS
Uniaxial Interference
afforded by
Pig. 7'2.
Crystal Plate
Fij^ure
Calcite (Trigonal) in
'
cut perpendicularly to
Convergent Polarised
the Axis.
Tdght, with Crossed
Nicols.
Biaxial Interference
Figure afforded by
Fig. 73. Crystal Plate
cut perpendicularly to
Aragonite (Rhombic)
in Convergent Polar-
the Bisectrix of the
ised Light, with Nicols
Acute Optic Axial
crossed and parallel to
Angle.
the Vibration Direc-
tions of the Crystal.
To face p. 190.
iiiriMfl
EXPERIMENTS IN CONVERGENT LIGHT 191
Interference Figure
afforded by a Quartz
Plate, 1 Millimetre
Fig. 76.
thick, in strongly
Convergent Polarised
Light.
Interference Figure
afforded by a Quartz
Plate, 3 75 Millimetres
Fig. 77.
thick, in moderately
Conveigent Polarised
Light.
Interference Figure
(Airys Spirals) af-
forded by two super-
posed Quartz Plates,
375 Millimetres thick,
Fig. 78. one of Right-handed
Quartz and the other
of Left-handed
moderately
Quaitz, in
Convergent Polarised
Light.
Fig. 82.
Ten Diamonds exhibiting- Natural Faces, mounted for
the Lantern Polariscope, to show Polarisation Colours due to
Internal Strain.
Fig. 121.
Doubly Kefracting- Liquid Crystals of Cholesteryl Acetate,
projected on the Screen in the Act of Growth (see p. 281).
Fig. 83. A Disc h of 24 Mica Sectors under Crossed Nicols, showing- Effects
at a and c of Introduction of Left and Right-handed Quartz Plates.
Fig. 87. Natural Biquartz exhibiting the Black Band (Nicols crossed)
at the Oblique Junction of the Right-handed and Left-handed Parts.
Fig, 88. Artificial Biquartz, the two parts being obliquely joined
in order to produce the Black Band.
PLATE XVIII.
Fig. 89. Black Central Band and equidistant Spectrum Bands on each
side, afforded by Babinets Composite Plate of two Quartz Wedges,
one parallel and the other perpendicular to the Axis. (Direct
Photograph of Screen Picture as projected by Lantern Polariscope.
Fig. 94.
Section-plate of Amethyst, natural size, as seen directly in
Ordinary Light, showing Alternate Violet Sectors (see p. 223).
To face p. 218.
EXPERIMENTS IN PARALLEL LIGHT 219
222 CRYSTALS
Fig. 95.
Section-plate of large Amethyst Quartz Crystal, showing
relatively large Area of Sectorial Repeated Twinning of Right
and Left-handed Quartz (see p. 225).
Direct Photographs of Screen Pictures of Amethyst projected
BY THE Lantern Polariscope in Parallel Light.
To face p. 222 .
EXPERIMENTS IN PARALLEL LIGHT 223
\
NATURE OF CRYSTALLISATION 247
Fig. 106. Liquid Crystals of Am- Fig. 107. Ammonium Oleate under
monium Oleate under slight considerable pressure.
pressure.
iiii -ii|i , ;
1
^
-== - - === 1 1
^ 1
'
1
' 1
- -
ii
Fig, 108. Diagrammatic Representation of Arrangement of Molecules.
Fig. 111.
Cruciform, Boomerang, and Arrow-head Twins
of Ammonium Oleate.
Dicliroic Crystal
Fig. 104. Drops of Para-
azoxy-anisol.
'IG. 115. Tetragonal Astatic Magnet-system. Fig. 116. Cubic Astatic Magnet-system.
To face p. 262.
LIQUID CRYSTALS 263
!
LIQUID CRYSTALS 265
I vT.T
.r.;
v;
^'n^
'I -
LIQtriD CRYSTALS 271
Crystals.
Liquid
of
Projection
the
for
LIQIHD CRYSTALS 279
vital.
Especial interest has recently been attracted
on the part of chemists to the bearing of crystal-
lography on their science by a remarkable theory
which has been advanced by Pope and Barlow,
connecting the internal structure of crystals with
chemical valency, the power which the atom of a
chemical element possesses of combining with the
atoms of other elements, and which is generally
expressed by the number of atoms of a monad
element, such as hydrogen or chlorine, with which
it is capable of combining chemically. Thus the
electro-positive metal potassium is said to have monad
valency because it is capable of combining with one
atom of the electro-negative element chlorine to form
the salt potassium chloride, KCl; calcium possesses
dyad valency because it can unite with two atoms
of chlorine to form calcium chloride, CaCl2 alumin-
;
regions of in the
influence crystal structure.
Von Fedorow has developed his particular theory
in a very masterly manner, and with the aid of it
professes, and with very considerable success in
many cases, to determine the correct mode of setting
up a crystal for truly comparative descriptive
purposes, and has derived therefrom a remarkable
method of crystallochemical analysis.
Moreover, there is yet another view, that of
Sollas,^ that the packing of the molecules is a more
open one altogether, a view to which he has been
guided by consideration of the molecular volume.
Sollas has offered some remarkable explanations of
crystal structure, notably in the case of the di-
morphous forms of silver iodide. The abnormal con-
traction which occurs on heating this interesting
substance, and its sudden transformation at 146 from
the ordinary hexagonal into a cubic modiflcation as
discovered by Lehmann, appear capable of very clear
explanation on the basis of his theory. According
to this theory of SoUas the volumes of the spheres of
influence of the atoms of the different elements of
the same family group, such as those of the group
of alkali metals or those of the halogens, chlorine,
bromine, and iodine, vary progressively in a manner
which is dependent on the atomic volumes of the
elements, which have a real comparative significance
when the elements belong to the same family group.
It is probable that there is a considerable sub-
stratum of truth behind these various apparently
conflicting views, and what is now required is that
the germ of real fact shall be winnowed from the
1 Proc. Boy. Soc., 1898, 63, 270, 286, and 296 ; 1901, 67, 493.
CONCLUSION 293
INDEX
Airys spirals, 197 Barlow, discovery of remainder
Alpine snowfield, 49 of 230 point-systems, 118, 119,
Alum, ammonium 43 ;
iron, 140 ; and Popes theory, 285-
cesium,42; potash, 5, 16, 17, 77; 292
vicinal laces of potash, 248, 251 Bartolinus, Erasmus, 17
Amethyst quartz, 222-229 ; as Benzoic acid, screen experiment
example of pseudo-racemism, on crystallisation of, 229-231
231, 232 Bergmann and Gahns laws of
Ammonium chloride labile crys- cleavage, 18
tallisation, 248 ; iron alum, Berzelius and Mitscherlich,
43 ; NH4 group, and its isomor- atomic weights and isomor-
phism with alkalies, 82, 83, phism, 80, 82, 83, 85
131 oleate, liquid crystals of,
; Beudants researches on the
259-263 oleate, twins of, 262
;
vitriols, 75, 76
Amperes researches on am- Biaxial crystals, 60-prisms and
monia, 83 refractive indices of, 162, 163,
Anatase, crystal of, 37 184 ; optic axes of, 185 ; optic
Antimony oxide, dimorphism of, axial angle of, 191
87, 88 Biots researches on tartaric and
Apatite, crystal of, 37 racemic acids, 143
Aragonite, biaxial interference Biquartze>, natural and artificial,
figure of, 189, 190 181, 211, 214, 216, 217
Armstrong and Pope on sobrerol, Black band of quartz twins, 216-
153 218
Arsenic oxide, crystals of, 5, 88 Boisbaudran, Lecoq de, 238
Astatic systems of molecular Boyle, Robert, 17
magnets of Lehmann, 271, 272 Brauns, 254
Asymmetric carbon atom, 144, Bravais, 114; space-lattices, 114
145 Brookite, 91
Axes and axial planes of crystals,
51, 55, 56 C^SALPINTTS, 15
Axial ratios, 129 Caesium alum, 42
Calcite, crystals of, 10-13, 38
Babinets double- wedge quartz amount of double refraction
plate, 219 of, 174 ;
in rock sections, 177,
Bacteria, destruction of one en- 178 ; uniaxial inter erence
antiomorphous form by, 149 figure of, 189, 190 ; plate per-
Barium nitrate, 152 pendicular to axis of, 209
Barker, researches on perchlo- refractive indices of, 174 ; 60-
rates, 123 prism of, 165, 168
295
;
296 CRYSTALS
INDEX 297
298 CRYSTALS
Kipping and Pope, definition of 119, 134, 135 ; illustrated by
racemism and pseudo-racemism. quartz, 231
158, 154 Mitscherlich, experiment with
Kopp, 100 gypsum, 90-94 ; work of, 70-
Kundts powder, 149 97
Mixed crystals, 77, 86
Labile solutions, 241 Molecular compound, racemic
Laurent and Nickles organic acid a, 150
researches, 99 Molecular volume and distance
Lavoisier, 23 ratios, 129, 130
Law of rational indices, 24, 50, Molecule, individuality and
57, 59 directive force of, 139, 269
Le Bel and van tHoffs ex- Monochromatic illuminator, 192,
planation of optical activity, 193
151 Monoclinic system, 39 axes and
;
INDEX 299
tals of, 259,265 ; -benzoic acid, vergent light, 92, 186, 188, 189;
263 ;-cinnamic acid, 263 for parallel light, 201, 202
-phenetol, 258, 259 Progressive change of crystal
Parametral form, 56 angles in isomorphous series,
Pasteurs law, 155 ; research on 125 ; of double refraction, 126 ;
300 CRYSTALS
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