§ 18. For the division of continuous three-dimensional space

THE MOLECULAR TACTICS OF

A CRYSTAL

_LORD KELVIN_

London

HENRY FROWDE

OXFORD UNIVERSITY PRESS WAREHOUSE

AMEN CORNER, E.C.

[Illustration]

New York

MACMILLAN & CO., 66 FIFTH AVENUE

THE

MOLECULAR TACTICS OF

A CRYSTAL

BY

LORD KELVIN, P.R.S.

PROFESSOR OF NATURAL PHILOSOPHY IN THE UNIVERSITY OF GLASGOW

AND FELLOW OF PETERHOUSE, CAMBRIDGE

_Being the Second ROBERT BOYLE LECTURE, delivered before

the Oxford University Junior Scientific Club

on Tuesday, May 16, 1893_

WITH TWENTY ILLUSTRATIONS

Oxford

AT THE CLARENDON PRESS

1894

Oxford

PRINTED AT THE CLARENDON PRESS

BY HORACE HART, PRINTER TO THE UNIVERSITY

ON THE MOLECULAR TACTICS OF A CRYSTAL

By LORD KELVIN, P.R.S.

§ 1. My subject this evening is not the physical properties of

crystals, not even their dynamics; it is merely the geometry of the

structure--the arrangement of the molecules in the constitution of a

crystal. Every crystal is a homogeneous assemblage of small bodies

or molecules. The converse proposition is scarcely true, unless in

a very extended sense of the term crystal (§ 20 below). I can best

explain a homogeneous assemblage of molecules by asking you to think

of a homogeneous assemblage of people. To be homogeneous every person

of the assemblage must be equal and similar to every other: they must

be seated in rows or standing in rows in a perfectly similar manner.

Each person, except those on the borders of the assemblage, must have

a neighbour on one side and an equi-distant neighbour on the other: a

neighbour on the left front and an equi-distant neighbour behind on the

right, a neighbour on the right front and an equi-distant neighbour

behind on the left. His two neighbours in front and his two neighbours

behind are members of two rows equal and similar to the rows consisting

of himself and his right-hand and left-hand neighbours, and their

neighbours’ neighbours indefinitely to right and left. In particular

cases the nearest of the front and rear neighbours may be right in

front and right in rear; but we must not confine our attention to the

rectangularly grouped assemblages thus constituted. Now let there be

equal and similar assemblages on floors above and below that which

we have been considering, and let there be any indefinitely great

number of floors at equal distances from one another above and below.

Think of any one person on any intermediate floor and of his nearest

neighbours on the floors above and below. These three persons must be

exactly in one line; this, in virtue of the homogeneousness of the

assemblages on the three floors, will secure that every person on the

intermediate floor is exactly in line with his nearest neighbours above

and below. The same condition of alignment must be fulfilled by every

three consecutive floors, and we thus have a homogeneous assemblage of

people in three dimensions of space. In particular cases every person’s

nearest neighbour in the floor above may be vertically over him, but

we must not confine our attention to assemblages thus rectangularly

grouped in vertical lines.

§ 2. Consider now any particular person _C_ (Fig. 1) on any

intermediate floor, _D_ and _D′_ his nearest neighbours, _E_ and _E′_

his next nearest neighbours all on his own floor. His next next nearest

neighbours on that floor will be in the positions _F_ and _F′_ in the

diagram. Thus we see that each person _C_ is surrounded by six persons,

_DD′_, _EE′_ and _FF′_, being his nearest, his next nearest, and his

next next nearest neighbours on his own floor. Excluding for simplicity

the special cases of rectangular grouping, we see that the angles of

the six equal and similar triangles _CDE_, _CEF_, &c., are all acute:

and because the six triangles are equal and similar we see that the

three pairs of mutually remote sides of the hexagon _DEFD′E′F′_ are

equal and parallel.

[Illustration: FIG. 1]

§ 3. Let now _A_, _A′_, _A″_, &c., denote places of persons of the

homogeneous assemblage on the floor immediately above, and _B_, _B′_,

_B″_, &c. on the floor immediately below, the floor of _C_. In the

diagram let _a_, _a′_, _a″_ be points in which the floor of _CDE_ is

cut by perpendiculars to it through _A_, _A′_, _A″_ of the floor above,

and _b_, _b′_, _b″_ by perpendiculars from _B_, _B′_, _B″_ of the floor

below. Of all the perpendiculars from the floors immediately above

and below, just two, one from each, cut the area of the parallelogram

_CDEF_: and they cut it in points similarly situated in respect to

the oppositely oriented triangles into which it is divided by either

of its diagonals. Hence if _a_ lies in the triangle _CDE_, the other

five triangles of the hexagon must be cut in the corresponding points,

as shown in the diagram. Thus, if we think only of the floor of _C_

and of the floor immediately above it, we have points _A_, _A′_, _A″_

vertically above _a_, _a′_, _a″_. Imagine now a triangular pyramid,

or tetrahedron, standing on the base _CDE_ and having _A_ for vertex:

we see that each of its sides _ACD_, _ADE_, _AEC_, is an acute angled

triangle, because, as we have already seen, _CDE_ is an acute angled

triangle, and because the shortest of the three distances, _CA_, _DA_,

_EA_, is (§ 2) greater than _CE_ (though it may be either greater than

or less than _DE_). Hence the tetrahedron _CDEA_ has all its angles

acute; not only the angles of its triangular faces, but the six angles

between the planes of its four faces. This important theorem regarding

homogeneous assemblages was given by Bravais, to whom we owe the whole

doctrine of homogeneous assemblages in its most perfect simplicity and

complete generality. Similarly we see that we have equal and similar

tetrahedrons on the bases _D′CF_, _E′F′C_; and three other tetrahedrons

below the floor of _C_, having the oppositely oriented triangles

_CD′E′_, &c. for their bases and _B_, _B′_, _B″_ for their vertices.

These three tetrahedrons are equal and heterochirally[1] similar to the

first three. The consideration of these acute angled tetrahedrons, is

of fundamental importance in respect to the engineering of an elastic

solid, or crystal, according to Boscovich. So also is the consideration

of the cluster of thirteen points _C_ and the six neighbours

_DEFD′E′F′_ in the plane of the diagram, and the three neighbours

_AA′A″_ on the floor above, and _BB′B″_ on the floor below.

§ 4. The case in which each of the four faces of each of the

tetrahedrons of § 3 is an equilateral triangle is particularly

interesting. An assemblage fulfilling this condition may conveniently

be called an ‘equilateral homogeneous assemblage,’ or, for brevity, an

‘equilateral assemblage.’ In an equilateral assemblage _C_’s twelve

neighbours are all equi-distant from it. I hold in my hand a cluster of

thirteen little black balls, made up by taking one of them and placing

the twelve others in contact with it (and therefore packed in the

closest possible order), and fixing them all together by fish-glue.

You see it looks, in size, colour, and shape, quite like a mulberry.

The accompanying diagram shows a stereoscopic view of a similar cluster

of balls painted white for the photograph.

[Illustration: FIG. 2.]

§ 5. By adding ball after ball to such a cluster of thirteen, and

always taking care to place each additional ball in some position in

which it is properly in line with others, so as to make the whole

assemblage homogeneous, we can exercise ourselves in a very interesting

manner in the building up of any possible form of crystal of the class

called ‘cubic’ by some writers and ‘octahedral’ by others. You see

before you several examples. I advise any of you who wish to study

crystallography to contract with a wood-turner, or a maker of beads for

furniture tassels or for rosaries, for a thousand wooden balls of about

half an inch diameter each. Holes through them will do no harm and may

even be useful; but make sure that the balls are as nearly equal to one

another, and each as nearly spherical, as possible.

[Illustration: FIG. 3.]

§ 6. You see here before you a large model which I have made to

illustrate a homogeneous assemblage of points, on a plan first given,

I believe, by Mr. William Barlow (_Nature_, December 20 and 27, 1883).

The roof of the model is a lattice-frame (Fig. 3) consisting of two

sets of eight parallel wooden bars crossing one another, and kept

together by pins through the middles of the crossings. As you see, I

can alter it to make parallelograms of all degrees of obliquity till

the bars touch, and again you see I can make them all squares.

§ 7. The joint pivots are (for cheapness of construction) of copper

wire, each bent to make a hook below the lattice frame. On these

sixty-four hooks are hung sixty-four fine cords, firmly stretched by

little lead weights. Each of these cords (Fig. 4) bears eight short

perforated wooden cylinders, which may be slipped up and down to any

desired position[2]. They are at present actually placed at distances

consecutively each equal to the distance from joint to joint of the

lattice frame.

[Illustration: FIG. 4.]

§ 8. The roof of the model is hung by four cords, nearly vertical, of

independently variable lengths, passing over hooks from fixed points

above, and kept stretched by weights, each equal to one quarter of

the weight of roof and pendants. You see now by altering the angles

of the lattice work and placing it horizontal or in any inclined

plane, as I am allowed to do readily by the manner in which it is

hung, I have three independent variables, by varying which I can show

you all varieties of homogeneous assemblages, in which three of the

neighbours of every point are at equal distances from it. You see

here, for example, we have the equilateral assemblage. I have adjusted

the lattice roof to the proper angle, and its plane to the proper

inclination to the vertical, to make a wholly equilateral assemblage

of the little cylinders of wood on the vertical cords, a case, as

we have seen, of special importance. If I vary also the distances

between the little pieces of wood on the cords; and the distances

between the joints of the lattice work (variations easily understood,

though not conveniently producible in one model without more of

mechanical construction than would be worth making), I have three

other independent variables. By properly varying these six independent

variables, three angles and three lengths, we may give any assigned

value to each edge of one of the fundamental tetrahedrons of § 3.

§ 9. Our assemblage of people would not be homogeneous unless its

members were all equal and similar and in precisely similar attitudes,

and were all looking the same way. You understand what a number of

people seated or standing on a floor or plain and looking the same way

means. But the expression ‘looking’ is not conveniently applicable to

things that have no eyes, and we want a more comprehensive mode of

expression. We have it in the words ‘orientation,’ ‘oriented,’ and

(verb) ‘to orient,’ suggested by an extension of the idea involved in

the word ‘orientation,’ first used to signify positions relatively

to east and west of ancient Greek and Egyptian temples and Christian

churches. But for the orientation of a house or temple we have only

one angle, and that angle is called ‘azimuth’ (the name given to an

angle in a horizontal plane). For orientation in three dimensions of

space we must extend our ideas and consider position with reference to

east and west and up and down. A man lying on his side with his head

to the north and looking east, would not be similarly oriented to a

man standing upright and looking east. To provide for the complete

specification of how a body is oriented in space we must have in the

body a plane of reference, and a line of reference in this plane,

belonging to the body and moving with it. We must also have a fixed

plane and a fixed line of reference in it, relatively to which the

orientation of the moveable body is to be specified; as, for example,

a horizontal plane and the east and west horizontal line in it. The

position of a body is completely specified when the angle between the

plane of reference belonging to it, and the fixed plane is given; and

when the angles between the line of intersection of the two planes and

the lines of reference in them are also given. Thus we see that three

angles are necessary and sufficient to specify the orientation of a

moveable body, and we see how the specification is conveniently given

in terms of three angles.

§ 10. To illustrate this take a book lying on the table before you with

its side next the title-page up, and its back to the north. I now lift

the east edge (the top of the book), keeping the bottom edge north and

south on the table till the book is inclined, let us say, 20° to the

table. Next, without altering this angle of 20°, between the side of

the book and the table, I turn the book round a vertical axis, through

45° till the bottom edge lies north-east and south-west. Lastly,

keeping the book in the plane to which it has been thus brought, I turn

it round in this plane through 35°. These three angles of 20°, 45°,

and 35°, specify, with reference to the horizontal plane of the table

and the east and west line in it, the orientation of the book in the

position to which you have seen me bring it, and in which I hold it

before you.

§ 11. In Figs. 5 and 6 you see two assemblages, each of twelve equal

and similar molecules in a plane. Fig. 5, in which the molecules are

all same-ways oriented, is one homogeneous assemblage of twenty-four

molecules. Fig. 6, in which in one set of rows the molecules are

alternately oriented two different ways, may either be regarded as

two homogeneous assemblages, each of twelve single molecules; or one

homogeneous assemblage of twelve pairs of those single molecules.

[Illustration: FIG. 5.]

§ 12. I must now call your attention to a purely geometrical

question[3] of vital interest with respect to homogeneous assemblages

in general, and particularly the homogeneous assemblage of molecules

constituting a crystal:--_what can we take as ‘the’ boundary or ‘a’

boundary enclosing each molecule with whatever portion of space around

it we are at liberty to choose for_ _it, and separating it from

neighbours and their portions of space given to them in homogeneous

fairness?_

[Illustration: FIG. 6.]

§ 13. If we had only mathematical points to consider we should be at

liberty to choose the simple obvious partitioning by three sets of

parallel planes. Even this may be done in an infinite number of ways,

thus:--Beginning with any point _P_ of the assemblage, choose any other

three points _A_, _B_, _C_, far or near, provided only that they are

not in one plane with _P_, and that there is no other point of the

assemblage in the lines _PA_, _PB_, _PC_, or within the volume of the

parallelepiped of which these lines are conterminous edges, or within

the areas of any of the faces of this parallelepiped. There will be

points of the assemblage at each of the corners of this parallelepiped

and at all the corners of the parallelepipeds equal and similar to

it which we find by drawing sets of equi-distant planes parallel to

its three pairs of faces. (A diagram is unnecessary.) Every point of

the assemblage is thus at the intersection of three planes, which is

also the point of meeting of eight neighbouring parallelepipeds. Shift

now any one of the points of the assemblage to a position within the

volume of any one of the eight parallelepipeds, and give equal parallel

motions to all the other points of the assemblage. Thus we have every

point in a parallelepipedal cell of its own, and all the points of the

assemblage are similarly placed in their cells, which are themselves

equal and similar.

§ 14. But now if, instead of a single point for each member of the

assemblage, we have a group of points, or a globe or cube or other

geometrical figure, or an individual of a homogeneous assemblage of

equal, similar, similarly dressed, and similarly oriented ladies,

sitting in rows, or a homogeneous assemblage of trees closely planted

in regular geometrical order on a plane with equal and similar

distributions of molecules, and parallel planes above and below,

we may find that the best conditioned plane-faced parallelepipedal

partitioning which we can choose would cut off portions properly

belonging to one molecule of the assemblage and give them to the cells

of neighbours. To find a cell enclosing all that belongs to each

individual, for example, every part of each lady’s dress, however

complexly it may be folded among portions of the equal and similar

dresses of neighbours; or, every twig, leaf, and rootlet of each one

of the homogeneous assemblage of trees; we must alter the boundary by

give-and-take across the plane faces of the primitive parallelepipedal

cells, so that each cell shall enclose all that belongs to one

molecule, and therefore (because of the homogeneousness of the

partitioning) nothing belonging to any other molecule. The geometrical

problem thus presented, wonderfully complex as it may be in cases

such as some of those which I have suggested, is easily performed for

any possible case if we begin with any particular parallelepipedal

partitioning determined for corresponding points of the assemblage

as explained in § 13, for any homogeneous assemblage of single

points. We may prescribe to ourselves that the corners are to remain

unchanged, but if so they must to begin with either in interfaces of

contact between the individual molecules, or in vacant space among

the molecules. If this condition is fulfilled for one corner it is

fulfilled for all, as the corners are essentially corresponding points

relatively to the assemblage.

§ 15. Begin now with any one of the twelve straight lines between

corners which constitute the twelve edges of the parallelepiped, and

alter it arbitrarily to any curved or crooked line between the same

pair of corners, subject only to the conditions (1) that it does not

penetrate the substance of any member of the assemblage, and (2) that

it is not cut by equal and similar parallel curves[4] between other

pairs of corners.

[Illustration: FIG. 7.]

Considering now the three fours of parallel edges of the

parallelepiped, let the straight lines of one set of four be altered to

equal and similar parallel curves in the manner which I have described;

and proceed by the same rule for the other two sets of four edges. We

thus have three fours of parallel curved edges instead of the three

fours of parallel straight edges of our primitive parallelepiped with

corners (each a point of intersection of three edges) unchanged.

Take now the quadrilateral of four curves substituted for the four

straight edges of one face of the parallelepiped. We may call this

quadrilateral a curvilineal parallelogram, because it is a circuit

composed of two pairs of equal parallel curves. Draw now a curved

surface (an infinitely thin sheet of perfectly extensible india-rubber

if you please to think of it so) bordered by the four edges of our

curvilineal parallelogram, and so shaped as not to cut any of the

substance of any molecule of the assemblage. Do the same thing with

an exactly similar and parallel sheet relatively to the opposite face

of the parallelepiped; and again the same for each of the two other

pairs of parallel faces. We thus have a curved-faced parallelepiped

enclosing the whole of one molecule and no part of any other; and by

similar procedure we find a similar boundary for every other molecule

of the assemblage. Each wall of each of these cells is common to two

neighbouring molecules, and there is no vacant space anywhere between

them or at corners. Fig. 7 illustrates this kind of partitioning by

showing a plane section parallel to one pair of plane faces of the

primitive parallelepiped, for an ideal case. The plane diagram is in

fact a realization of the two-dimensional problem of partitioning the

pine pattern of a Persian carpet by parallelograms about as nearly

rectilinear as we can make them. In the diagram faint straight lines

are drawn to show the primitive parallelogrammatic partitioning.

It will be seen that of all the crossings (marked with dots in the

diagram) every one is similarly situated to every other in respect to

the homogeneously repeated pattern figures: _A_, _B_, _C_, _D_ are four

of them at the corners of one cell.

§ 16. Confining our attention for a short time to the homogeneous

division of a plane, remark that the division into parallelograms

by two sets of crossing parallels is singular in this respect--each

cell is contiguous with three neighbours at every corner. Any

shifting, large or small, of the parallelograms by relative sliding

in one direction or another violates this condition, brings us to

a configuration like that of the faces of regularly hewn stones in

ordinary bonded masonry, and gives a partitioning which fulfils the

condition that at each corner each cell has only two neighbours. Each

cell is now virtually a hexagon, as will be seen by the letters _A_,

_B_, _C_, _D_, _E_, _F_ in the diagram Fig. 8. _A_ and _D_ are to be

reckoned as corners, each with an interior angle of 180°. In this

diagram the continuous heavy lines and the continuous faint lines

crossing them show a primitive parallelogrammatic partition by two sets

of continuous parallel intersecting lines. The interrupted crossing

lines (heavy) show, for the same homogeneous distribution of single

points or molecules, the virtually hexagonal partitioning which we get

by shifting the boundary from each portion of one of the light lines to

the heavy line next it between the same continuous parallels.

[Illustration: FIG. 8.]

Fig. 8 bis represents a further modification of the boundary by

which the 180° angles _A_, _D_, become angles of less than 180°. The

continuous parallel lines (light) and the short light portions of the

crossing lines show the configuration according to Fig. 8, from which

this diagram is derived.

§ 17. In these diagrams (Figs. 8 and 8 bis) the object enclosed

is small enough to be enclosable by a primitive parallelogrammatic

partitioning of two sets of continuous crossing parallel straight

lines, and by the partitioning of ‘bonded’ parallelograms both

represented in Fig. 8, and by the derived hexagonal partitioning

represented in Fig. 8 bis, with faint lines showing the primitive and

the secondary parallelograms. In Fig. 7 the objects enclosed were

too large to be enclosable by any rectilinear parallelogrammatic

or hexagonal partitioning. The two sets of parallel faint lines in

Fig. 7 show a primitive parallelogrammatic partitioning and the

corresponding pairs of parallel curves intersecting at the corners of

these parallelograms, of which _A_,_B_,_C_,_D_ is a specimen, show a

corresponding partitioning by curvilineal parallelograms. Fig. 9 shows

for the same homogeneous distribution of objects a better conditioned

partitioning, by hexagons in each of which one pair of parallel

edges is curved. The sets of intersecting parallel straight lines in

Fig. 9 show the same primitive parallelogrammatic partitioning as

in Fig. 7, and the same slightly shifted to suit points chosen for

well-conditionedness of hexagonal partitioning.

[Illustration: FIG. 8 bis.]

[Illustration: FIG. 9.]

§ 18. For the division of continuous three-dimensional space[5] into

equal, similar, and similarly oriented cells, quite a corresponding

transformation from partitioning by three sets of continuous mutually

intersecting parallel planes to any possible mode of homogeneous

partitioning, may be investigated by working out the three-dimensional

analogue of §§ 16-17. Thus we find that the most general possible

homogeneous partitioning of space with plane interfaces between the

cells gives us fourteen walls to each cell, of which six are three

pairs of equal and parallel parallelograms, and the other eight are

four pairs of equal and parallel hexagons, each hexagon being bounded

by three pairs of equal and parallel straight lines. This figure, being

bounded by fourteen plane faces, is called a tetrakaidekahedron. It

has thirty-six edges of intersection between faces; and twenty-four

corners, in each of which three faces intersect. A particular case

of it, which I call an orthic tetrakaidekahedron, being that in

which the six parallelograms are equal squares, the eight hexagonal

faces are equal equilateral and equiangular hexagons, and the lines

joining corresponding points in the seven pairs of parallel faces

are perpendicular to the planes of the faces, is represented by

a stereoscopic picture in Fig. 10. The thirty-six edges and the

twenty-four corners, which are easily counted in this diagram, occur

in the same relative order in the most general possible partitioning,

whether by plane-faced tetrakaidekahedrons or by the generalized

tetrakaidekahedron described in § 19.

§ 19. The most general homogeneous division of space is not

limited to plane-faced cells; but it still consists essentially of

tetrakaidekahedronal cells, each bounded by three pairs of equal and

parallel quadrilateral faces, and four pairs of equal and parallel

hexagonal faces, neither the quadrilaterals nor the hexagons being

necessarily plane. Each of the thirty-six edges may be straight

or crooked or curved; the pairs of opposite edges, whether of the

quadrilaterals or hexagons, need not be equal and parallel; neither

the four corners of each quadrilateral nor the six corners of each

hexagon need be in one plane. But every pair of corresponding edges of

every pair of parallel corresponding faces, whether quadrilateral or

hexagonal, must be equal and parallel. I have described an interesting

case of partitioning by tetrakaidekahedrons of curved faces with curved

edges in a paper[6] published about seven years ago. In this case each

of the quadrilateral faces is plane. Each hexagonal face is a slightly

curved surface having three rectilineal diagonals through its centre in

one plane.

[Illustration: FIG. 10.]

The six sectors of the face between these diagonals lie alternately

on opposite sides of their plane, and are bordered by six arcs

of plane curves lying on three pairs of parallel planes. This

tetrakaidekahedronal partitioning fulfils the condition that the

angles between three planes meeting in an edge are everywhere each

120°; a condition that cannot be fulfilled in any plane-faced

tetrakaidekahedron. Each hexagonal wall is an anticlastic surface of

equal opposite curvatures at every point, being the surfaces of minimum

area bordered by six curved edges. It is shown easily and beautifully,

and with a fair approach to accuracy, by choosing six little circular

arcs of wire, and soldering them together by their ends in proper

planes for the six edges of the hexagon; and dipping it in soap

solution and taking it out.

§ 20. Returning now to the tactics of a homogeneous assemblage, remark

that the qualities of the assemblage as a whole depend both upon the

character and orientation of each molecule, and on the character of

the homogeneous assemblage formed by corresponding points of the

molecules. After learning the simple mathematics of crystallography,

with its indicial system[7] for defining the faces and edges of a

crystal according to the Bravais rows and nets and tetrahedrons of

molecules in which we think only of a homogeneous assemblage of points,

we are apt to forget that the true crystalline molecule, whatever its

nature may be, has sides, and that generally two opposite sides of each

molecule may be expected to be very different in quality, and we are

almost surprised when mineralogists tell us that two parallel faces on

two sides of a crystal have very different qualities in many natural

crystals. We might almost as well be surprised to find that an army in

battle array, which is a kind of large-grained crystal, presents very

different appearance to any one looking at it from outside, according

as every man in the ranks with his rifle and bayonet faces to the front

or to the rear or to one flank or to the other.

§ 21. Consider, for example, the ideal case of a crystal consisting

of hard equal and similar tetrahedronal solids all same-ways oriented.

A thin plate of crystal cut parallel to any one set of the faces of

the constituent tetrahedrons would have very different properties on

its two sides; as the constituent molecules would all present points

outwards on one side and flat surfaces on the other. We might expect

that the two sides of such a plate of crystal would become oppositely

electrified when rubbed by one and the same rubber; and, remembering

that a piece of glass with part of its surface finely ground but not

polished and other parts polished becomes, when rubbed with white

silk, positively electrified over the polished parts and negatively

electrified over the non-polished parts, we might almost expect that

the side of our supposed crystalline plate towards which flat faces

of the constituent molecules are turned would become positively

electrified, and the opposite side, showing free molecular corners,

would become negatively electrified, when both are rubbed by a rubber

of intermediate electric quality. We might also from elementary

knowledge of the fact of piezo-electricity, that is to say, the

development of opposite electricities on the two sides of a crystal

by pressure, expect that our supposed crystalline plate, if pressed

perpendicularly on its two sides, would become positively electrified

on one of them and negatively on the other.

§ 22. Intimately connected with the subject of enclosing cells for

molecules of given shape, assembled homogeneously, is the homogeneous

packing together of equal and similar molecules of any given shape. In

every possible case of any infinitely great number of similar bodies

the solution is a homogeneous assemblage. But it may be a homogeneous

assemblage of single solids all oriented the same way, or it may be

a homogeneous assemblage of clusters of two or more of them placed

together in different orientations. For example, let the given bodies

be halves (oblique or not oblique) of any parallelepiped on the two

sides of a dividing plane through a pair of parallel edges. The two

halves are homochirally[8] similar; and, being equal, we may make a

homogeneous assemblage of them by orienting them all the same way

and placing them properly in rows. But the closest packing of this

assemblage would necessarily leave vacant spaces between the bodies:

and we get in reality the closest possible packing of the given bodies

by taking them in pairs oppositely oriented and placed together to form

parallelepipeds. These clusters may be packed together so as to leave

no unoccupied space.

Whatever the number of pieces in a cluster in the closest possible

packing of solids may be for any particular shape, we may consider each

cluster as itself a given single body, and thus reduce the problem to

the packing closely together of assemblages of individuals all sameways

oriented; and to this problem therefore it is convenient that we should

now confine our attention.

§ 23. To avoid complexities such as those which we find in the familiar

problem of homogeneous packing of forks or spoons or tea-cups or bowls,

of any ordinary shape, we shall suppose the given body to be of such

shape that no two of them similarly oriented can touch one another

in more than one point. Wholly convex bodies essentially fulfil this

condition; but it may also be fulfilled by bodies not wholly convex, as

is illustrated in Fig. 11.

[Illustration: Fig. 11.]

§ 24. To find close and closest packing of any number of our solids

_S_{1}_, _S_{2}_, _S_{3}_ ... of shape fulfilling the condition of § 23

proceed thus:--

(1) Bring _S_{2}_ to touch _S_{1}_ at any chosen point _p_ of its

surface (Fig. 12).

(2) Bring _S_{3}_ to touch _S_{1}_ and _S_{2}_, at _r_ and _q_

respectively.

(3) Bring _S_{4}_ (not shown in the diagram) to touch _S_{1}_, _S_{2}_,

and _S_{3}_.

(4) Place, any number of the bodies together in three rows continuing

the lines of _S_{1}S_{2}_, _S_{1}S_{3}_, _S_{1}S_{4}_, and in three

sets of equi-distant rows parallel to these. This makes a homogeneous

assemblage. In the assemblage so formed the molecules are necessarily

found to be in three sets of rows parallel respectively to the three

pairs _S_{2}S_{3}_, _S_{3}S_{4}_, _S_{4}S_{2}_. The whole space

occupied by an assemblage of _n_ of our solids thus arranged has

clearly _6n_ times the volume of a tetrahedron of corresponding points

of _S_{1}_, _S_{2}_, _S_{3}_, _S_{4}_. Hence the closest of the

close packings obtained by the operations (1) ... (4) is found if we

perform the operations (1), (2), and (3) as to make the volume of this

tetrahedron least possible.

[Illustration: FIG. 12]

§ 25. It is to be remarked that operations (1) and (2) leave for (3)

no liberty of choice for the place of _S_{4}_, except between two

determinate positions on opposite sides of the group _S_{1}_, _S_{2}_,

_S_{3}_. The volume of the tetrahedron will generally be different for

these two positions of _S_{4}_, and, even if the volume chance to be

equal in any case, we have differently shaped assemblages according as

we choose one or other of the two places for _S_{4}_.

This will be understood by looking at Fig. 12, showing _S_{1}_

and neighbours on each side of it in the rows of _S_{1}S_{2}_,

_S_{1}S_{3}_, and in a row parallel to that of _S_{2}S_{3}_. The plane

of the diagram is parallel to the planes of corresponding points of

these seven bodies, and the diagram is a projection of these bodies

by lines parallel to the intersections of the tangent planes through

_p_ and _r_. If the three tangent planes through _p_, _q_, and _r_,

intersected in parallel lines, _q_ would be seen like _p_ and _r_ as a

point of contact between the outlines of two of the bodies; but this is

only a particular case, and in general _q_ must, as indicated in the

diagram, be concealed by one or other of the two bodies of which it is

the point of contact. Now imagining, to fix our ideas and facilitate

brevity of expression, that the planes of corresponding points of the

seven bodies are horizontal, we see clearly that _S_{4}_ may be brought

into proper position to touch _S_{1}_, _S_{2}_, and _S_{3}_ either from

above or from below; and that there is one determinate place for it if

we bring it into position from above, and another determinate place for

it if we bring it from below.

§ 26. If we look from above at the solids of which Fig. 12 shows the

outline, we see essentially a hollow leading down to a perforation

between _S_{1}_, _S_{2}_, _S_{3}_, and if we look from below we see a

hollow leading upwards to the same perforation: this for brevity we

shall call the perforation _pqr_. The diagram shows around _S_{1}_

six hollows leading down to perforations, of which two are similar

to _pqr_, and the other three, of which _p′q′r′_ indicates one, are

similar one to another but are dissimilar to _pqr_. If we bring _S_{4}_

from above into position to touch _S_{1}_, _S_{2}_, and _S_{3}_, its

place thus found is in the hollow _pqr_, and the places of all the

solids in the layer above that of the diagram are necessarily in the

hollows similar to _pqr_. In this case the solids in the layer below

that of the diagram must lie in the hollows below the perforations

dissimilar to _pqr_, in order to make a single homogeneous assemblage.

In the other case, _S_{4}_ brought up from below finds its place on the

under side of the hollow _pqr_, and all solids of the lower layer find

similar places: while solids in the layer above that of the diagram

find their places in the hollows similar to _p´q´r´_. In the first

case there are no bodies of the upper layer in the hollows above the

perforations _similar_ to _p´q´r´_, and no bodies of the lower layer in

the hollows below the perforations _similar_ to _pqr_. In the second

case there are no bodies of the upper layer in the hollows above the

perforations _similar_ to _pqr_, and none of the under layer in the

hollows below the perforations _similar_ to _p´q´r´_.

§ 27. Going back now to operation (1) of § 23, remark that when the

point of contact _p_ is arbitrarily chosen on one of the two bodies

_S_{1}_, the point of contact on the other will be the point on it

corresponding to the point or one of the points of _S_{1}_, where its

tangent plane is parallel to the tangent plane at _p_. If _S_{1}_

is wholly convex it has only two points at which the tangent planes

are parallel to a given plane, and therefore the operation (1) is

determinate and unambiguous. But if there is any concavity there will

be four or some greater even number of tangent planes parallel to any

one of some planes, while there will be other planes to each of which

only one pair of tangent planes is parallel. Hence, operation (1),

though still determinate, will have a multiplicity of solutions, or

only a single solution, according to the choice made of the position of

_p_.

Henceforth however, to avoid needless complications of ideas, we shall

suppose our solids to be wholly convex; and of some such unsymmetrical

shape as those indicated in Fig. 12 of § 25, and shown by stereoscopic

photograph in Fig. 13 of § 36. With or without this convenient

limitation, operation (1) has two freedoms, as _p_ may be chosen

freely on the surface of _S_{1}_; and operation (2) has clearly just

one freedom after operation (1) has been performed. Thus, for a solid

of any given shape, we have three disposables, or, as commonly called

in mathematics, three ‘independent variables,’ all free for making a

homogeneous assemblage according to the rule of § 22.

§ 28. In the homogeneous assemblage defined in § 24, each solid,

_S_{1}_, is touched at twelve points, being the three points of

contact with _S_{2}_, _S_{3}_, _S_{4}_, and the three 3’s of points

on _S_{1}_ corresponding to the points on _S_{2}_, _S_{3}_, _S_{4}_,

at which these bodies are touched by the others of the quartet. This

statement is somewhat difficult to follow, and we see more clearly

the twelve points of contact by not confining our attention to the

quartet _S_{1}_, _S_{2}_, _S_{3}_, _S_{4}_ (convenient as this is

for some purposes), but completing the assemblage and considering

six neighbours around _S_{1}_ in one plane layer of the solids as

shown in Fig. 12, with their six points _prq″p′r′q″′_ of contact with

_S_{1}_; and the three neighbours of the two adjacent parallel layers

which touch it above and below. This cluster of thirteen, _S_{1}_

and twelve neighbours, is shown for the case of spherical bodies in

the stereoscopic photograph of § 4 above. We might of course, if we

pleased, have begun with the plane layer of which _S_{1}_, _S_{2}_,

_S_{4}_ are members, or with that of which _S_{1}_, _S_{3}_, _S_{4}_

are members, or with the plane layer parallel to the fourth side

_S_{2}_ _S_{3}_ _S_{4}_ of the tetrahedron: and thus we have four

different ways of grouping the twelve points of contact on _S_{1}_ into

one set of six and two sets of three.

§ 29. In this assemblage we have what I call ‘close order’ or ‘close

packing.’ For closest of close packings the volume of the tetrahedron

(§ 24) of corresponding points of _S_{1}_, _S_{2}_, _S_{3}_, and

_S_{4}_ must be a minimum, and the least of minimums if, as generally

will be the case, there are two more different configurations for

each of which the volume is a minimum. There will in general also be

configurations of minimax volume and of maximum volume, subject to

the condition that each body is touched by twelve similarly oriented

neighbours.

§ 30. Pause for a moment to consider the interesting kinematical

and dynamical problems presented by a close homogeneous assemblage

of smooth solid bodies of given convex shape, whether perfectly

frictionless or exerting resistance against mutual sliding according to

the ordinarily stated law of friction between dry hard solid bodies.

First imagine that they are all similarly oriented and each in contact

with twelve neighbours, except outlying individuals (which there must

be at the boundary if the assemblage is finite, and each of which is

touched by some number of neighbours less than twelve). The coherent

assemblage thus defined constitutes a kinematic frame or skeleton

for an elastic solid of very peculiar properties. Instead of the six

freedoms, or disposables, of strain presented by a natural solid it has

only three. Change of shape of the whole can only take place in virtue

of rotation of the constituent parts relatively to any one chosen row

of them, and the plane through it and another chosen row.

§ 31. Suppose first the solids to be not only perfectly smooth but

perfectly frictionless. Let the assemblage be subjected to equal

positive or negative pressure inwards all around its boundary. Every

position of minimum, minimax, or maximum volume will be a position of

equilibrium. If the pressure is positive the equilibrium will be stable

if, and unstable unless, the volume is a minimum. If the pressure

is negative the equilibrium will be stable if, and unstable unless,

the volume is a maximum. Configurations of minimax volume will be

essentially unstable.

§ 32. Consider now the assemblage of § 31 in a position of stable

equilibrium under the influence of a given constant uniform pressure

inwards all round its boundary. It will have rigidity in simple

proportion to the amount of this pressure. If now by the superposition

of non-uniform pressure at the boundary, for example equal and opposite

pressures on two sides of the assemblage, a finite change of shape is

produced: the whole assemblage essentially swells in bulk. This is the

‘dilatancy’ which Osborne Reynolds has described[9] in an exceedingly

interesting manner with reference to a sack of wheat or sand, or an

india-rubber bag tightly filled with sand or even small shot. Consider,

for example, a sack of wheat filled quite full and standing up open. It

is limp and flexible. Now shake it down well, fill it quite full, shake

again, so as to get as much into it as possible, and tie the mouth very

tightly close. The sack becomes almost as stiff as a log of wood of

the same shape. Open the mouth partially, and it becomes again limp,

especially in the upper parts of the bag. In Reynolds’ observations on

india-rubber bags of small shot his ‘dilatancy’ depends, essentially

and wholly, on breaches of some of the contacts which exist between the

molecules in their configuration of minimum volume: and it is possible

that in all his cases the dilatations which he observed are _chiefly_,

if not wholly, due to such breaches of contact.

But it is possible, it almost seems probable, that in bags or boxes

of sand or powder, of some kinds of smooth rounded bodies of any

shape, not spherical or ellipsoidal, subjected persistently to unequal

pressures in different directions, and well shaken, stable positions

of equilibrium are found with almost all the particles each touched by

twelve others.

Here is a curious subject of Natural History through all ages till

1885, when Reynolds brought it into the province of Natural Philosophy

by the following highly interesting statement:--‘A well-marked

phenomenon receives its explanation at once from the existence of

dilatancy in sand. When the falling tide leaves the sand firm, as the

foot falls on it the sand whitens and appears momentarily to dry round

the foot. When this happens the sand is full of water, the surface of

which is kept up to that of the sand by capillary attractions; the

pressure of the foot causing dilatation of the sand more water is

required, which has to be obtained either by depressing the level of

the surface against the capillary attractions, or by drawing water

through the interstices of the surrounding sand. This latter requires

time to accomplish, so that for the moment the capillary forces are

overcome; the surface of the water is lowered below that of the sand,

leaving the latter white or drier until a sufficient supply has been

obtained from below, when the surface rises and wets the sand again.

On raising the foot it is generally seen that the sand under the foot

and around becomes momentarily wet; this is because, on the distorting

forces being removed, the sand again contracts, and the excess of water

finds momentary relief at the surface.’

This proves that the sand under the foot, as well as the surface around

it, must be dry for a short time after the foot is pressed upon it,

though we cannot see it whitened, as the foot is not transparent. That

it is so has been verified by Mr. Alex. Galt, Experimental Instructor

in the Physical Laboratory of Glasgow University, by laying a small

square of plate-glass on wet sand on the sea-shore of Helensburgh, and

suddenly pressing on it by a stout stick with nearly all his weight.

He found the sand, both under the glass and around it in contact with

the air, all became white at the same moment. Of all the two hundred

thousand million men, women, and children who, from the beginning

of the world, have ever walked on wet sand, how many, prior to the

British Association Meeting at Aberdeen in 1885, if asked, ‘Is the sand

compressed under your foot?’ would have answered otherwise than ‘Yes!’?

(Contrast with this the case of walking over a bed of wet sea-weed!)

§ 33. In the case of globes packed together in closest order (and

therefore also in the case of ellipsoids, if all similarly oriented),

our condition of coherent contact between each molecule and twelve

neighbours implies absolute rigidity of form and constancy of bulk.

Hence our convex solid must be neither ellipsoidal nor spherical

in order that there may be the changes of form and changes of bulk

which we have been considering as dependent on three independent

variables specifying the orientation of each solid relatively to rows

of the assemblage. An interesting dynamical problem is presented by

supposing any mutual forces, such as might be produced by springs, to

act between the solid molecules, and investigating configurations of

equilibrium on the supposition of frictionless contacts. The solution

of it of course is that the potential energy of the springs must be a

minimum or a minimax or a maximum for equilibrium, and a minimum for

stable equilibrium. The solution will be a configuration of minimum or

minimax, or maximum, volume, only in the case of pressure equal in all

directions.

§ 34. A purely geometrical question, of no importance in respect to

the molecular tactics of a crystal but of considerable interest in

pure mathematics, is forced on our attention by our having seen (§ 27)

that a homogeneous assemblage of solids of given shape, each touched

by twelve neighbours, has three freedoms which may be conveniently

taken as the three angles specifying the orientation of each molecule

relatively to rows of the assemblage as explained in § 30.

The Molecular Tactics of a Crystal · 第 1 / 3 段