分子大小的新测定

U.S. copyright law (title 17 of U.S. code) governs the reproduction and redistribution of copyrighted material. e This new Dover edition, first published in 1956, is an unabridged .and unaltered republication of the translation first: published in 1926. It is published through special arrangément with Methuen and Co., Ltd., and the estate of Albert Einstein. Manufactured in the United' States of America. -INVESTIGATIONS O N THE THEORY .OF ,THE BROWNIAN MOVEMENT BY ALBERT EINSTEIN, PH.D. EDITED WITH NOTES BY R. F ü R T H TRANSLATED BY A. D. COWPER WITH 3 DIAGRAMS DOVER PUBLICATIONS, INC. l. MOLECULAR DIMENSIONS ' 37 III A NEW DETERMINATION OF MOLECULAR DIMENSIONS (From the Annalen der Physik (4), 19, 1906, pp. 289-306. Corrections, ibid., 34, 1911, pp. 591-5922.] (23) T HE kinetic theory of gases made possible the earliest determinations of the actual dimensions of the molecules, whilst physical phenomena observable in liquids have not, up to the present, served for the calculation of molecular dimensions. The explanation of this doubtless lies in the difficulties, hitherto unsurpassable, which discourage the development of a molecular kinetic theory of liquids that will extend tb details. It will be shown now in this paper that the size of the molecules of the solute in an undissociated dilute solution can be found from the viscosity of the solution and of the pure solvent, and from the rate of diffusion of the solute into the solvent, if the volume of a molecule of the solute is large 36 compared with the volume of a molecule of the solvent. For such a sofute molecule will behave approximately, with respect to its mobility in the solvent, and in respect to its influence on the viscosity of the latter, as a solid body suspended in the solvent, and it will be allowable to apply to the motion of the solvent in the immediate neighbourhood of a molecule the hydrodynamic equations, in which the liquid is considered homo- geneous, and, accordingly, its molecular structure is ignored. We will choose for the shape of the solid bodies, which shall represent the solute mole- cules, the sphericdi fom-* I. ON THE EFFECT ON THE MoTroN OF A 1,IQWID OF A VERY SMALL SPHERE SUSPENDED IN IT As the subject of our discussion, Iet us take an incompressible homogeneous liquid with viscosity K, whose velocity-components W , V , W will be given as functions of the Co-ordinates x, y, x, and sf the time. Taking an arbitrary point go, yo, x,, we wifl imagine that the functions u, V , W are de- veloped according to Taylor's theorem as func- tions of x - x,, y - yo, x - x,, and that a domain G is marked out around this point so small that within it only the linear terns in this expansion 38 THEORY OF BROWNIAN MOVEMENT have to be considered. The motion of the liquid contained in G can then be looked upon in the familiar manner as the result of the superposition of three motions, namely, I. A parallel displacement of all the particles' of the liquid without change of their relative position. 2. A rotation of the liquid without change of the relative position of the particles of the liquid. 3. A movement of dilatation in three directions at sight angles to one another (the prin- cipal axes sf ation^^ ion^^ We wif€ imagine now a. spherical rigid body in the domain G, whose centre lies at the point yo, x,, and whose ~~~e~~~~~~ are very small com- pared with those or" the domain G, We will further assume that the motion under c~nsidera- tion is so shw that the kinetic energy of the sphere is negligible as we11 as that of the liquid. It will be further assumed that the velocity com- ponents of an element of sudace the sphere show agreement with the corresponding velocity components of the particles of the liquid in the immediate neighbourhood, that is, that the contact- layer (thought of as continuous) also exhibits MOLECULAR DIMENSIONS 39 everywhere a viscosity-coefficient that is not vanishingly small. It is clear without further discussion that the sphere simply shares in the partid motions I and 2, without modifying the motion of the neigkibouring liquid, since the liquid moves as a rigid body in these partial motions ; and that we have ignored the effects of inertia. But the motion 3 will be modified by the pres- ence of the sphere, and our next problem will be to investigate the influence of the sphere on this motion of the liquid. We will further refer the motion 3 to a co-ordinate system whose axes are parallel to the principal axes of dilatation, and we x - x, = Q: x - z , = 5, then the motion can be expressed by the equations will put Y - YO = T', uQ == ' f f II) V0 = Bq, q.J a , in the case when the sphere is not present. A, B, C are constants which, on account of the incompressibility of the liquid, must fulfil the condition (2) A + B + C = 0 * (24) 40 THEORY OF BROWNIAN MOVEMENT Now, if the rigid sphere with radius P is intro- duced at the point x,, yo, q,, the motions of the liquid in its neighbourhood are modified. In the foliowing discussion we will, for the sake of con- venience, speak of €’ as “ finite ” ; whilst the values of 6, 9, 5, for which the motions of the liquid are no longer appreciably influenced by the sphere, we will speak of as “ infinitely great.” Firstly, it is clear from the symmetry of the motions of the liquid under consideration that there can be neither a translation nor a rotation of the sphere accompanying the motion in ques- tion, and we obtain the limiting conditions u = v = = w = o w h e n p = P where we have put p = JP 3- ?I2 4- P > 0. Here u, V , w are the velocity-components of the motion now under consideration (modified b~7 the sphere). If we put a4 = 4 3- u,, W = cg + wi, (3) = Br] 4- v1, ’ since the motion defined by equation (3) must be transformed into that defined by equations (I) in the “ infinite” region, the velocities ul, V,, wl will vanish in the latter region. MOLECULAR DIMENSIONS 41 The functions u, V , W must satisfy the hydro- dynamic equations with due reference to the viscosity, and ignoring inertia. Accordingly, the following equations will hold :- (*) where A stands for the operator 3 2 3% -+-+- 3e2 392 352 and 9 for the hydrostatic pressure. Since the equations (I) are solutions of the equations (4) and the latter are linear, according to (3) the quantities u,, V,, w1 must also satisfy the equations (4). I have determined u,, V,, q , and P, according to a method given in the lecture of Kirchhoff quoted in $ 4 (t), and find (*) G. Kirchhoff, “ Lectures on Mechanics,” Lect. 26. (t j ‘‘ From the equations (4) it follows that ap = o, If p is chosen in accordance with this condition, and a function V is determined which satisfies the equation A V = ;P, then the equations (4) are satisfied if we put and chose u’, V’, W‘, so that Au’ = o, Av’ = o, and AW’ = o, and 42 THEORY OF BROWNIAN MOVEMENT Now if we put and in agreement with this and the constants a, b, e can be chosen SO that when p P, = W = W = O. By superposition of three similar solutions we obtain the solution given in the equations ( 5 ) and W * where (5a) MOLECULAR DIMENSIONS 43 It is easy to see that the equations (5) are solu- tions of the equations (4). Then, since I 2 A t = o, A - = o, P A p = P and A($) = - ${A( ; ) } = o, we get But the last expression obtained is, according to the first of the equations (S) , identical with dpldE. In similar manner, we can show that the second 44 THEORY OF BROWNIAN MOVEMENT and third of the equations (4) are satisfied. We obtain further- But since, according to equation (sa), it' follows that the last of the equations (4) is satisfied. As for the boundary conditions, our equations for zd, V , W are transformed into the equations (I) only when p is indefinitely large. By inserting the value of D from the equajion (sa) in the second of the equations (5) we get We know that u vanishes when p = P. On the grounds of syrnmetry the same holds for V and W . We have now demonstrated that in the equations (5) a solution has been obtained to satisfy both MOLECULAR DIMENSIONS 45 the equations (4) and the boundary conditions of the problem. It can also be shown that the equations (5) are the only solutions of the equations (4) consistent with the boundary conditions of the problem. The proof will only be indicated here. Suppose that, in a finite space, the velocity-components of a liquid u, V, W satisfy the equations (4). Now, if another solution U, V , W of the equations (4) can exist, in which on the boundaries of the sphere in question U = zc, V = V , W = W, then (U - u, V - V , W - W ) will be a solution of the equa- tions (4), in which the velocity-components vanish at the boundaries of the space. Accordingly, no mechanical work, can be done on the liquid con- tained in the space in question. Since we have ignored the kinetic energy of the liquid, it follows that the work transformed into heat in the space in question is likewise equal to zero. Hence we infer that in the whole space we must have zc = u', ZI = V', W = W', if the space is bounded, at least in part, by stationary walls. By crossing the boundaries, this result can also be extended to the case when the space in question is infinite, as in the case considered above. We can show thus that the solution obtained above is the sole solution of the problem. 46 THEORY OF BROWNIAN MOVEMENT We will now place around the point x,, yo, x, a sphere of radius R, where R is indefinitely large compared with P, and will calculate the energy which is transformed into heat (per unit of time) in the liquid lying within the sphere. This energy W is equal to the mechanical work done on the liquid. If we call the components of the pressure exerted on the surface of the sphere of radius R, Xn, Yn, 2%) then where ,the integration is extended over the surface of the sphere of radius R. Here x, = - . (Xr 6 + x? + X<-) , 6 2% = - (zt 8 - + 23 + Zr), 86’. Y,=Z,=-k($+?) Y , = $ - z k - , 3v Z t = X g = - k ( z + g ) am 3% P P P Yn = - (y{ + y? + Y$), . P P 6 P P where W X t = p - ~ k - 311 MOLECULAR DIMENSIONS 47 The expressions for u, V , W are simplified when we note that for p -.- R the terms with the factor P6/p5 vanish. We have to put For P we obtain from the first of the equations (5) by corresponding onaissi~ms p = - 5kP 4- Bq2 + CC2 P5 + const. We obtain first A‘2 25kP3 t2(At2+Rrlt+CC2) x,= - 2kA+10kP3-- Pb P7 and from this With the aid of the expressions for Yn and Zn, obtained by cyclic exchange, we get, ignoring all 48 THEORY OF BROWNIAN MOVEMENT terms which involve the ratio .P /p raised to any power higher than the third, - 5kP-8(A2f2 + B2q2 + Cece) + 1 5 k # A f ~ + B q ~ + C S ~ ) 2 . ( ~ 3 ) P3 If W é integrate over the sphere and bear in mind that P* 5 ds = 4R%, 5 eds = 5 q2ds '= 5 = SmR4, 5 [4ds 5 $ds = 5 {*as = h R 6 , 5 q2{2ds = S t2E2dS = 5 t2q2dS = fTnRg, 5 (A[2+3q2+Cc2)2ds =