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Manufactured in the United'States WITH 3 DIAGRAMS of America. COWPER arrangément with Methuen and Co.and unaltered republication of the TRANSLATED BY translation first:published in 1926.. Ltd. PH. is an unabridged . l. . F ü R T H This new Dover edition. It is published through special A. first published in 1956.THE BROWNIAN MOVEMENT BY ALBERT EINSTEIN. D.OF . and the estate of Albert Einstein. -I NVESTIGATIONS O N THE THEORY .D.. DOVER PUBLICATIONS. EDITED WITH NOTES BY e R. INC.

ibid. V . x. and sf the kinetic theory of liquids that will extend t b details. as a solid body suspended III in the solvent.. the sphericdi fom-* T HE kinetic theory of gases made possible the earliest determinations of the actual dimensions of the molecules. and in respect to its influence on the viscosity of the latter.yo. and it will be allowable to apply to the motion of the solvent in the immediate A NEW DETERMINATION OF MOLECULAR neighbourhood of a molecule the hydrodynamic DIMENSIONS equations. accordingly. For such a sofute molecule will behave approximately. y. yo. hitherto unsurpassable.x. Iet us take an dimensions. MOLECULAR DIMENSIONS ' 37 compared with the volume of a molecule of the solvent. Taking an arbitrary point go. 1906. 1911. 289-306. W will be given which discourage the development of a molecular as functions of the Co-ordinates x.x . x. V . ON THE EFFECT ON THE MoTroN OF A 1. and. is ignored.x. within it only the linear terns in this expansion if the volume of a molecule of the solute is large 36 . in which the liquid is considered homo- (From the Annalen der Physik (4). which shall represent the solute mole- cules. 34.. W are de- of the molecules of the solute in an undissociated veloped according to Taylor's theorem as func- dilute solution can be found from the viscosity of tions of x . with respect to its mobility in the solvent. Corrections. and that a domain the solution and of the pure solvent.. geneous.IQWID OF A VERY SMALL SPHERE SUSPENDED IN IT phenomena observable in liquids have not.. up to the present. time. we It will be shown now in this paper that the size wifl imagine that the functions u. served for the calculation of molecular As the subject of our discussion. whilst physical I. K. 19. whose velocity-components W . its molecular structure pp. pp. y . The explanation of this doubtless incompressible homogeneous liquid with viscosity lies in the difficulties. We will choose for the shape of the 591-5922. and from G is marked out around this point so small that the rate of diffusion of the solute into the solvent.](23) solid bodies.

= 5. We will further refer the cipal axes sf ation^^ ion^^ motion 3 to a co-ordinate system whose axes are parallel to the principal axes of dilatation. these partial motions . A movement of dilatation in three directions to investigate the influence of the sphere on this at sight angles to one another (the prin. C are constants which. uQ== ' f f It will be further assumed that the velocity com.38 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 39 have to be considered. A rotation of the liquid without change of the effects of inertia. whose centre lies at the point x . incompressibility of the liquid. We will x-z. II) V0 = Bq. and we We wif€ imagine now a. sphere simply shares in the partid motions I and 2. the relative position of the particles of But the motion 3 will be modified by the pres- the liquid. x. spherical rigid body in will put the domain G. A parallel displacement of all the particles' without modifying the motion of the neigkibouring of the liquid without change of their liquid. and our next problem will be 3.YO= T'. show agreement with the corresponding velocity in the case when the sphere is not present. further assume that the motion under c~nsidera- then the motion can be expressed by the equations tion is so shw that the kinetic energy of the sphere is negligible as we11 as that of the liquid. motion of the liquid. and whose ~~~e~~~~~~ are very small com- Y . components of the particles of the liquid in the A. familiar manner as the result of the superposition It is clear without further discussion that the of three motions. and that we have ignored 2. The motion of the liquid everywhere a viscosity-coefficient that is not contained in G can then be looked upon in the vanishingly small. B. must fulfil the layer (thought of as continuous) also exhibits condition (2) A+B+C=0 * (24) . since the liquid moves as a rigid body in relative position.x. ponents of an element of sudace the sphere q. on account of the immediate neighbourhood. ence of the sphere. = Q: yo. that is. that the contact.J a .. pared with those or" the domain G. namely. I.

(*) venience. for which the motions of the liquid are no longer appreciably influenced by the where A stands for the operator sphere. q. there can be neither a translation nor a rotation Since the equations (I) are solutions of the of the sphere accompanying the motion in ques. the motions of the dynamic equations with due reference to the liquid in its neighbourhood are modified.. if the rigid sphere with radius P is intro. where we have put according to a method given in the lecture of p = JP 3. and P. 5. Kirchhoff quoted in $ 4 (t). the velocities ul. w1 must also satisfy the u=v==w=owhenp=P equations (4). 40 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 41 Now. motion now under consideration (modified b~7the (tj ‘‘ From the equations (4) it follows that ap = o. W = cg + wi. P > 0. W‘.P. w are the velocity-components of the (*) G.V. V’. V . V. and in the infinite” region. If we put function V is determined which satisfies the equation a4 = 4 3.. 9.. the foliowing discussion we will. it is clear from the symmetry of the 3e2 392 352 motions of the liquid under consideration that and 9 for the hydrostatic pressure. In the viscosity. yo. equations (4) and the latter are linear.u. Kirchhoff. AV = .. and find Here u. W must satisfy the hydro- duced at the point x.” -+-+- “ 32 3% Firstly. V. Av’ = o... I have determined u. 26. so that Au’ = o. then the equations (4) are satisfied if we put ’ since the motion defined by equation (3) must be transformed into that defined by equations (I) and chose u’. according tion. If p is chosen in accordance with this condition. (3) = Br] 4. and ignoring inertia. The functions u.v1. q .” Lect. for the sake of con. V . we will speak of as infinitely great. Accordingly.?I2 4. and will vanish in the latter region. “ Lectures on Mechanics. w l “ AW’ = o. . whilst the “ ” values of 6. speak of €’ as finite . following equations will hold :.. and a sphere).. and we obtain the limiting conditions to (3) the quantities u.

Then. identical with dpldE.42 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 43 where (5a) It is easy to see that the equations (5) are solu- tions of the equations (4). P Ap=P and and in agreement with this A($) = . ( 5 ) and W * In similar manner. we get and the constants a. By superposition of three similar But the last expression obtained is. since I 2 Now if we put A t = o.${A(. e can be chosen SO that when p P. = W = W = O.= o. b. A .)} = o. according to solutions we obtain the solution given in the equations the first of the equations (S). we can show that the second .

ZI = V'. W = W .V . in a finite space. V = V .44 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 45 and third of the equations (4) are satisfied. 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. no equations for z d. if the space is bounded.W ) will be a solution of the equa- it' follows that the last of the equations (4) is tions (4). as grounds of syrnmetry the same holds for V and W . W . W satisfy the equations (4). in the case considered above. can be done on the liquid con- equations (I) only when p is indefinitely large. another solution U. The proof will only be indicated here. if But since. On the the case when the space in question is infinite. V . Now. Hence we infer that in the whole space we must have zc = u'. at least in part.V . it follows (sa) in the second of the equations (5) we get that the work transformed into heat in the space in question is likewise equal to zero.u. this result can also be extended to We know that u vanishes when p = P. in which on the boundaries of the sphere in question U = z c. As for the boundary conditions. We can show thus We have now demonstrated that in the equations that the solution obtained above is the sole (5) a solution has been obtained to satisfy both solution of the problem. Accordingly. the problem. By crossing the boundaries. by stationary walls. W are transformed into the mechanical work. V . our at the boundaries of the space. according to equation (sa). . then ( U . W = W'. V . Suppose that. W of the equations (4) can exist. tained in the space in question. the velocity-components of a liquid u. in which the velocity-components vanish satisfied. We the equations (4) and the boundary conditions of obtain further. Since we have By inserting the value of D from the equajion ignored the kinetic energy of the liquid.

) . y? P + Y$). a The expressions for u. = $ . Xn.2%)then For P we obtain from the first of the equations (5) where .(y{ +.z k .Yn. 3v Z t = X g = . Y.(zt 8 + 2 3 + Zr). where R is indefinitely large note that for p -. which is transformed into heat (per unit of time) We have to put in the liquid lying within the sphere.5kP 4.R the terms with the factor compared with P.=Z.=-k($+?) Y .the integration is extended over the surface by corresponding onaissi~ms of the sphere of radius R. x.(XrP6 + x?P + X <P6. we get. and from this 86’.. - 6 P P where W Xt=p-~k. P A‘2 P7 2% = . If we call the components of the pressure exerted on the surface of the sphere of radius R. This energy W is equal to the mechanical work done on the liquid. W are simplified when we sphere of radius R. yo. Here p = . P5 x.k ( zam + g ) 3% 311 With the aid of the expressions for Y nand Zn.46 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 47 We will now place around the point x. obtained by cyclic exchange.= .=-2kA+10kP3--Pb 25kP3t2(At2+Rrlt+CC2) Yn = .V ... ignoring all .Bq2 + CC2 + const. We obtain first x. and will calculate the energy P6/p5 vanish..

the arbitrarily-chosen point x . 48 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 49 terms which involve the ratio . unit volume be . and consider again the most general volume V . a sphere 5 ds = 4R%. (23) spheres together is very small compared with the where we put domain G.. Q 2. and have investigated how this influenced the 5 [4ds 5 $ds = 5 {*as = h R 6 . in energy used up is therefore diminished by S2kG. We will now assume that 5 q2{2ds = S t2E2dS= 5 t2q2dS= fTnRg. motion of the liquid. If no spheres are present. that is very small compared with this domain. CALCULATION OF THE VISCOSITY-COEFFICIENT OP A LIQUID IN WHICH A LARGE NUMBER OF SMALL SPHERES ARE SUSPENDED IN IR- . that of the order of magnitude defined above.ence of the sphere.(~3) REGULAR DISTRIBUTION P* In the preceding discussion we have considered If Wé integrate over the sphere and bear in mind the case when there is suspended in a domain G. W. Let the number of spheres present in 52 = A2 + B2 + C2. an indefinitely large number of spheres are dis- 5 (A[2+3q2+Cc2)2ds= <ZrrR6(A2+B2+C2). by the equations (26) . y. 5 eds = 5 q2ds =' 5 = SmR4.TZ. motion of dilatation. (23) tributed in the domain G. of a homogeneous liquid. We will now start once more from the motion If the suspended sphere were not present (@ = o)..P/p raised to any power higher than the third. x in the domain G. the can express the velocity components z l. of similar radius and we obtain actually so small that the volume of all the + (7) W = $ ~ R 3 k 6 ~ &rP8k62 = za2k( V +:). by suitable choice of the Co-ordinate system we (74 W = 2S2kV.vo.5kP-8(A2f2+B2q2+ Cece)+ 1 5 kP3 #Af~+Bq~+CS~)2. without suspended then we should get for the energy used up in the spheres.where n is sensibly constant everywhere in tbe liquid. On account of the pres.

5 0 THEORY OF BROWNIAN . f q v 2 + [V2..yv. spheres has a result (neglecting indefinitely small consequently the additional velocity-components quantities of a . From the equation (7b) the viscosity-coefficient can be calculated of the heterogeneous mixture of liquid and suspended spheres (hereafter termed briefly '' mixture ") under discussion . w. V.. the energy per unit volume transformed into heat we get for the velocity-components u.xy. . and that gether are very small compared with @.+ (23) or (7b) W = 282k(I'+ f). .x. (23). in the domain G. taking into account the suspended spheres and neglecting terms of higher orders- W = zs2k ns2k@.V .. fv =x . where the summation is extended over ail spheres V. Further. but we must bear in mind that A .M. of the heat production per unit volume. (23) + where denotes the fraction of the volume occu- pied by the spheres. = A X . pu = &u2. yv.. W in the in the domain G has the value liquid. where A+B+C=o. Now a sphere suspended at the point -xv. will affect this motion in a manner evident from x.x.. and . = C$. we 'conclude from the equa- the average distance between neighbouring spheres tions (7) and (7a) that the presence of each of the is very great compared with their radius.we will call . yv x. = By.OVEMENT MOLECULAR DIMENSIONS 51 U. C are not the values of the principal dilatations in the motion of the liquid defined by the equations (8).. B. and we put W. Since we have assumed that sphere. =x . are the Co-ordinates of the centre of the the equation (6).. q v =y . higher order) (23) in an increase originating from all the suspended spheres to.

J K W = C2 +CW. lies at the origin of the Co-ordinate system. We will put. - 8*2 = S2(I 24). C* = C(r . W .. C ( 3% . C.V .. = . B*.-. spheres are now evenly distributed and introduce nate axes..*=o* ) If we exclude from our discussion the immediate neighbourhood of the single spheres. On the grounds of symmetry it follows that of a sphere K of very large radius R. We extend the summation throughout thk volume C*...G V 2 ) By analogy I 2 Yv2 Y. V = By +- CV.? ? B* = B(I . If we write the equations (8) in the an integral in place of the summation. . and therefore to the Co-ordi. + 5 PSxv(Axv2 Byv2$. p a . B.4). we obtain form + A X Ca. we get A* = (E) =A+X($') %==O Xa0 = A .+). If ture are parallel to the directions of the principal we assume further that the irregularly distributed dilatations A . where we put then neglecting indefinitely small quantities sf higher order.52 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 53 the principal dilatations of the mixture A*. whose centre the principal directions of dilatation of the mix. we can omit the second and third terms of the expressions for a.. pa "F + B"2 +. and obtain when x = y = z = o :- a.

O'OIS. then present in the solution per unit volume.= 0.61 C. 1.of solid sugar very small.98 C. 'k 'that of unit of time and volume the pure solvent.99 $.61. the result :. provided that this total volume is We must recollect here that I p. We can I . aqueous From the last three equations we obtain (neglecting sugar solution According to the observations i indefinitely small quantities of higher order) of Burkhard (Landolt and Börnstein Tables) + k* = k ( ~ 2 5 + ) . + We will calculate for a I per cent.00388. .C.5. sugar solution . then = I + 23+. k* -k . ON THE VOLUME OF A DISSOLVED SUBSTANCE ' in solution if the sugar solution is looked upon as OF MOLECULAR VOLUME LARGE IN COMPARISON a mixture of water and sugar in a dissolved form. Therefore S = 0. therefore C$ = If very small rigid spheres are suspended in a mately) 0-01grn.4 THEORY OF BROWNIAN. and can be and at 1795')- thought of as a rigid sphere of radius P. aqueous sugar Consider a dilute solution of a substance which solution (referred to water at the same tempera- does not dissociate in the solution. therefore.) for a We reach. (23) unit volume. the coefficient of internal friction is thereby solved in water has therefore the same effect on increased by a fraction which is equal to 2 3 times the viscosity as small suspended rigid spheres of the total volume of the spheres suspended in a total volume 0.00388 then apply the result obtained in Paragraph 2. WITH THAT OF THE SOLVENT The specific gravity of a I per cent.C. W* = 28*2k*. of sugar. has the volcme 0. (23) k*/k = 1. ' (23) Let us call the viscosity-coefficient of the mixture where 4 is the total volume of the molecules k*. ing the difference in the density of water at 4' pared with a molecule of the solvent . Suppose that ture) at 17.5"is 1. A gram of sugar dis- liquid.0245 (at zoo C. MOVEMENT MOLECULAR DIMENSIONS 55 We have found for the development of heat per If k* be the viscosity of the solution. We have then (neglect- a molecule of the dissolved substance is large corn. We shall find the same value for the specific volume S of the sugar present $ 3 .

If P is the osmotic pressure of the dissolved sub- cules present in solution limit the mobility of the stance.dP/dx. . therefore. (*) G. as a result of the fall in concentration will be molecule. the equation holds :-(*) times greater than would have resulted from the suspension of an equal mass of sugar. manner than by assuming that the sugar mole. of actual molecules' in a gram-molecule.is bound of the X-axis on the dissolved substance per unit on to the sugar-molecule.56 THEORY OF BROWNIAN MOVEMENT MOLECULL4R DIMENSIONS 57 While. '' Lectures on Mechanics. the sugar solution behaves." Lect. the effect on the viscosity is one and one-half That is. the osmotic SUBSTANCE IN SOLUTION IN A LIQUID pressure is given by the equation Consider such a solution as was dealt with in R Paragraph 3. N the number held bound by it respectively) behaves in hydro. volume of the solution = .98 . If a: force K acts on the molecule. as is determined by P and the viscosity k of the to its density. in any other diff usion-coefficient of an undissociated solution. It appears to me that this result can hardly be explained in We will use this relation for the calculation of the the light of the molecular theory. which is looked upon as the only force water immediately adjacent. the molecule will move with a velocity W which 26 (22). sideration.where 342 is the molecular weight of sugar unit of volume. that a dissolved sugar p grams in a unit volume and m is the molecular molecule (or the molecule together with the water weight of the dissolved substance. (23). $4. p = &PT# which we will imagine as a sphere of radius P. then the force exerted in the direction half (23)the volume of the sugar-molecule. then dynamic relations as a sphere of volume 0. sugar. like a mixture of water and solid solvent. ON THE DIFFUSION OF AN UNDISSOCIATED If the solution i s sufficiently dilute. therefore. and the force acting on a molecule and N the number of actual molecules in a gram. If there are We can say.C. whose volume is approximately one. so that a quantity producing motion in the dilute solution under con- of water.342/N (p/m)N is the number of (actual) molecules in a C. Kirchhoff.

49. the osmotic pressure in found in Ann. 1905. as a force acting on the individual molecules.58 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 59 where T is the absolute temperature and the case under discussion must be thought of as . However.-- I 3p . the value of the product of the number N ing systems of forces Px and . which correspond u=----RT I 3p to the differences in concentration of the solution. as can easily be established X-axis will be following thermodynamic methods. Thus the difficulty mentioned is overcome.. numerically equal to the In this calculation osmotic pressure is treated osmotic pressure. and a virtual force only.(*) which evidently does not correspond with the conceptions of the kinetic-molecular theory. the weight of substance passing per unit equal force acting on the single molecules in the of time across unit area in the direction of the opposite direction . two mutually eliminat- solvent. From the equations (I). . R = 8-31 IO'.Px p 3x' . 5. remains over as cause of motion.p. since. then -Px hydrodynamicdly-effective radius P of the mole. P 3% Accordingly. Phys. obtain therefore for the diffusion coefficient force acting on unit mass.Px applied to the of actual molecules in a gram-molecule and of the dissolved substance (per unit mass). D- (applied to the individual solute molecules) if .P x = o. 17. (*) A detailed statement of this train of thought will be according to the latter. therefore. establishes equilibrium with the osmotic pressure cule.5 2 by the force . . and only the force Px. 6nk N P 3x' can be established by the aid of a numerically Finally. we can calculate from the diffusion- coefficient and the coefficient of viscosity of the If we imagine. RT I 3p Equilibrium can be obtained with the osmotic WP=--*-- 6nk NF ax' We. (z).. d . this difficulty (3) we obtain for the velocity of movement of the vanishes if we reflect that (dynamic) equilibrium dissolved substance with the (virtual) osmotic forces.

10-8 cm. 19 August. 30 A $ d .RT . N = 3. '. sugar solution. DETERMINATION OF MOLECULAR DIMENSIONS . We get present in unit volume and m is its molecular N P = 2-08 .and of the tempera. if our theory is to correspond with the facts. The viscosity of water at 9'5" is radius of the molecule. It follows from the values found for NP3 and N P . we obtain Np3 --(x 3 m k* . 1905. If we bear in mind that 0*0135. 43 (23) According to the researches of Graham (calcu- lated out by Stephan). although they were N P -=-T obtained with IO per cent. solutions.60 THEORY OF BROWNIAN MOVEMENT MOLECULAR DIMENSIONS 61 We will carry out the calculation for an aqueous $ 5 . in These two equations put us in the position to order of magnitude.3 1oZ3. it follows from the data WITH THE HELP OF THE RELATIONS ALREADY given above for the viscosity of sugar solution at OBTAINED 20° c. (Received.384.5" is 0. we found in 8 4 P = 6.) ture. We found in Paragraph 3 N P a = 80 . .54 = 1 + zegn . . 1905. We will insert these data in our formula for the diffusion-coefficient.I). of the solvent. of the solute . and it is not n m to be expected that our formula will be precisely where p is the mass of the dissolved substance valid at so high a concentration. the diffusion-coefficient of where n is the number of solute molecules per unit sugar in water at 9. Firstly. with the values obtained by calculate each of the quantities P and N . Ion P that \ On the other hand. N must show itself to be independent of the nature Berne. 67rk D' The value found for N agrees satisfactorily.2 . of which other methods for this quantity. if the day is taken volume and P the hydrodynamically-effective as unit of time. (23) N p = .I . (23) k*k = 1 + 2. if we ignore the difference in P at 905" and zoo. I O Y weight.

and the number N of the actual molecules in a gram-molecule. . and the concentration 0-005 mol.2/day. Utilizing these data. 1906. January. p. From a table (p.49 . 81). IO-^ mm.5" C. corresponds to an increase of the viscosity of 0~00025. we find by interpolation that in dilute sugar solutions an increase in the sugar-content of I per cent. at 18. 1023. @3)2 (28) Berne. we find P = 0. . and N = 6-56.with the results of observations made by Hosking./litre the value 0-33 cm. Thovert found (Table. 372) for the diffusion-coefficient of sugar in water at 18-5"C.62 THEORY OF BROWNIAN MOVEMENT I In the new edition of Landolt and Börnstein's " Physical-Chemical Tables will be found very " useful data for the calculation of the size of the sugar molecule.