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On tlze Hall Effect in a Binary Electrolyte.
465
XL VI I. Tl1emy of the II all Effect in a Binar.IJ Electrolyte.
By F. G. DoNNAN, .M.A., Ph.D.*
I
N 1883 Roiti t investigated the subject of a possible Hall
. _effect in electrolytic solutions, but failed Jo obtain any
positive result. Uecently, however, the question has been
taken llp by Bngard :t, who has obtained very considerable
effects in aqueous solutions of zinc ami copper snlphates. On
the other hand, negati\e resuHs have been obtnined by Florio,
and as both Barrard and Florio maintain the correctness of
thei1 experimental work, a 1wlemic on the subject has arisen
between them. In this condition of affairs it seemed worth
while to examine what effect micrbt be expected theoretically.
:With this purpose in view I made the calculation contained
the following pages. Subsequently I discovered that a
Similar theory had been given by Van Everdingen,jun.jj; but
as I do not arrive at quite the same results, and ha \'e considered
the somewhat more generally, it seemed to me not to
be needless repetition to communicate this note.
Tho basis of the followinrr calculation may be stated briefly
as follows. The diagram slwws the directions of the primary
.current and the marrnetic field. The lines of flow of the
primary current are to be straight and the magnetic
Communicated by the Physical Society: read June 24th,
t Jown. de Pl1y.ique, 1883. . ... _ _
t Comptes Rendus, vol. cxxi1. pp. 71-19
1
and cxxm. pp. 1210-12,3
(1896).
Nuoro Oimento, r4] vol. iv. pp. 106-111 (189G).
II J.;Ietingen over het Verschijnsel van Hall en vau den
Weerstand in het Magnetisch Veld, p. 102 et seq. (Leiden, 1891).
466 Dr. F. G. Donnan on tiw
field everywhere uniform. The effect of the ponderomotive
forces on the moving ions in the magnetic field is to urge
both positive and negative ions in the positive direction of z.
The moving ions will thus acquire component velocities in
this direction, and these velocities being in general different
for each sort of ion, the result is the separation of positive
charges, whereby a potential-gradient is set up
m the duection of the z-axis which reduces the oriainally
velocities to equality. we thus obtain a flow of
matter in the positive z-direction. This produces in
1ts turn a reverse osmotic gradient or concentration-fall both
and undissociated salt. The stationary Rtate
Is finally aHamed when the net flux of ionic matter in the
direction of z is balanced by the flux of undissociated
salt In the opposite direction.
z
X
Let J = current-de?sity. of primary current,
c= col!-centratwn (m mols.) of positive plus negative
Ions,
P = corresponding osmotic pressure
C= concentrati?n (in mols.) of salt,
P= correspondmO' osmotic pressure
u, v= in "centim. per acquired under
umt one gram-mol. of positive and
_ w.mc matter respectively,
G- veloCity acqmred under unit force by one gram-
d7r mol. of undissociated salt
d.r: = potential-gradient of primacy current,
de
dz '"" potential-gradient of Hall-effect
'
q
"
1
1
I
Hall Effect in a Binary Elect1olyte. 461
e = quantity of electricity travelling per gram-equi-
valent. of ionic matter,
ro = valency of each ion,
H= magnetic field-strength,
t = temperature (absolute).
We shall suppose the laws p=cRt and P=CRt to hold for
the solution in question, although this is not essential. We
have furthermore
CrJ22C d7r
J=---y(u+v)dx' (i.)
Now an ion with a positive charge roe moving with a velocity
V in the posithe direction of axis of :c will he acted on by a
force in the positive z direction equal to roe VH; so that the
force in this direction on a positive gram-ion is given by
-ro
2
e
2
uH whence it has a component velocity in the same
d
. t' t' 2 -2 2Hd7r B . 'I .
1rec IOn amoun mg to -ro dx. y sum ar reasomng
the velocity of a negative gram-ion in the positive z direction
d7r
IS - ro
2
e
2
v
2
H dx.
Expressing quantities of matter in mols., we can now draw
up the following list, which takes into account all the fluxes
of matter occurring in the solution.
1. Quantity of positive ionic matter tra-
versing per unit time unit section
perpendicular to axis of z in positive
direction ofthis axis, due to pondero-
motive forces arising from the mag-
netic field.
Corresponding' quantity of negative
ionic matter.
Flux of positive ionic matter in same
direction due to potential-gradient
along z-axis.
Corresponding flux for negative ionic
matter.
5. Flux of positive ionic matter in same
direction due to oslllotic gradient.
6. Corresponding flux of negative ionic
matter.
7. Flu.'\: of undissociated salt in positive
z direction due to osmotic gradient.
CrJEC de
=+yv([z
Rt de
=-u2 dz'
Rtdc
=-v 2dz'
dC
=-GRt-
1

CZ
468 Dr. F. G. Donnan on tlte
The stationary condition then gives the equations:-
ro2e2c
2
Hdr. roec de uRt de +GRt dC -O
dx + T u dz + 2 dz dz - '
ro
2
e2e v2H dr. _ roec v de + vRt de + G Rt dC = O.
2 dx 2 dz 2 dz dz
(ii.)
(iii.)
dr. dC h . (' ) (" ' d
Elimination of- and - from t e equatiOns 1. , n.;, an
dx dz
(iii.) leads to the result
de_ 2 u-v HJ Rt u-v de (iv.)
dz - roee u + v - roec u + v ' dz '
It is to be observed that equation (iv.) holds for the v.ariable
as well as the stationary state, because although durmg the
Yariable state the left-hand members of equations (ii.) and
(iii.) are not zero, they are always equal to each other.
Accordingly for the initial phenomenon, before any appre-
ciable concentration-gradient occurs, we obtain, putting c=co
de
and dz =0,
de 2 u-v dr.
dz = roec
0
u +vHJ =roe(v-u)H dx' (v.)
or, integrating,
s.J
cdle dy dz= 2H dz ;
z roee
0
u+v
whence
2 U-t Hi
e=--- . (vi.)
roec
0
u+v d'
e=tota.l difference of potential measured in direction of
pos1hve z-ax1s, d = thickness measured in direction of mag-
field, and i =primary current-strength. So that we
obtam for the constant of the initial Hall-effect the nlue
2 u-v
const. = - --.
roec
0
u+v
In order to furthe: the stationary state, we shall
suppose !he required by the laws of
dissocwbon IS everywhere satisfied. 'l'his
tQ supposmg that the processes which adjust this equihbrmm
ve_rymuch more rapidly than any of the other changes
occurrmg m the system. In the uncertain state of knowledge
concerning the equilibrium-equation it may be written for the
I
I
Hall Effect in a Binar.IJ Electrolyte. 469
h
dO I ) de EI' . r dC
present C=cp(c); so tat dz =cp (e dz' umna mg dz
between this equation and (ii.) and between this equation
and (iii.), we obtain the equations
de {2Gcp'(e) +
1
}de, (vii.)
'dz = roee u + v roec u dz
de = _ _v_HJ + { 2Gcp' (el +
1
} de. . (viii.)
dz roee u+v roec v dz
WriiinO'
2
G'(e) + 1 = L,
2
G' (c) + 1 = l\I, we obtain from
.., u v
(vii.) and (viii.)
or
de=_!___ _1_ HJ, J
dz roer: L + .1\f u + v I

de roe dr. I
dz = L+l\1 (Lv-.1\Iu)H d.'C _j
(ix.)
For a completely dissociated electrolyte L = 1, l\1 = 1, and
we get instead of equations (ix.)
de =-l_u-vHJ=roe(v-u)Hdr.. (ix.a)

Comparing equations (v.) and (ix. ":e see that the
potentiul-gradient for a completely dissociated electrolyte IS
just one-half the initial gradient.
de!dr. V I I t . d
Let- -= D and denote by U, t 1e ve oc1 ws acqmre
dz dx '
under unit potential O'radicnt by a gram-mol. of positive and
negative ionic respecti,ely. Equation (ix. a) may
then be written
D=-k(V- U)H. (x.)
Van Everdingen arrived at the equation D= (V- U)H
for the stationary state in an electrolyte supposed to be .''ell
slightly dissociated; but be assumes in this case that wmc
concentration docs not vary throughout the. un
-assumption which is inconsistent with the equation.:; ( \'lL) and
{viii.); and t.herefore appears to me to he erroneous. .
Equation (x.) may now be applied to the_ data obtamed by
Bagard. He finds, for example, the
.Loc. cit. p. 207.
470 Dr. F. G. Donnan on tlze
CuS0
4
solution. Concentration =
1
Iu- grm. cquiv. per litre.
Temperature 21-26 C.
H. D.
D
il"
----------_-__ ------
385 C.G.S. units. 0018
0024
0034
46xl0-'
34xiO-'
35xlO-'
707
962
To test these results by means of the theory, it is only
to calculate the value of !(V- U), where it must
be noticed that V and U are the velocities of the gram-mols.
in centim. per second under a potential-gradient of one C.G.S.
electromagnetic unit of potential per centim. From Ostwald's
Lehrbuch, vol. ii. p. 770, the molecular conductivity of CuS04
solutions for the highest dilution at 18 C. is 217 in Siemens
units, and therefore 230 in mho's. As the calculation is only
very approximate, we may put consequently
230
(U + V)tso= 96540 X 2 X 108'
From the same source, p. 612, we get U 'l:T = 36, a value

may be regarded as fairly correct for temperatures
Ill the neighbourhood of :20 C. (accordina to Hittorf and
Bein, Zoe. cit.). Hence we obtain finally '"'
t(V- U)I
8
o= 16 X 10-13,
The value of t(V- U) for temperatures 21-26 C. will
probably be somewhat smaller. Of course the solution of
concentration.=--fs grm.-equiv. per litre is not by any _
completely dissociated; and by using the proper equahon,
namely,
D Lv-Mu
H =we L+M '
d h Lv-1\Iu v-u
smce v > u an t erefore > -- we should obtam a
L+l\1 2 '
higher value Nevertheless this would never account
for the difference between 39 x I0-5 as observed by Bagard
and 16 x 10-
13
as deduced theoreticaliy for the case of complete
dissociation.
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Hall Effect in a Bina1y Electrolyte. 471
So far as I can see, the theory here given is wholly in
favour of the negative results obtained by Roiti and Florio;
and it would therefore seem that Bagard has measured a phe-
nomenon not contemplated in the foregoing theory. Van Ever-
dingen in the paper refened to above supports Bagard; but
this is owing to his having accidentally omitted the factor
10-
8
in his numerical work.
The ionic concentration-fall can be readily calculated for a
c?mpletely dissociated electrolyte. From equations (iv.) and
(u. a) we get at once
Rtt!!!_ =HJ
dz '
or
whence
or
2
Rt =H(U + V)(z2-z
1
) 71"
2
-71"
1

me c
3
.x2-.r1
Thus, callina E the P.D. between two transverse electrodes
(of the same as the kation) due only to the differences
in concent.ration set up (a case which could be realized by
taking an electrolyte such as silver nitrate, for which U and
V are very nearly equal), it follows that
71"2-71"1
E=tH(U + V)(z2-zt) --.
.'1:2-.xl
Taking the case of copper sulphate, we get, as before,
u + v =00119.
Putting z
2
-z
1
= 1 centim., and 71"
2
-71"
1
= 1 (volt per centim.),
T2-T1
and H=20,000 C.G.S. units, we obtain
E=l2x 10-
8
volts.
Renee it would appear that in this, or in any other similar
experimental arranaement it would be not only to
an extremely strodg magnetic field, but also a very
high primary potential-gradient, i. e. of the orde.r of 10,00.0
volts per centim. This might perhaps be reahzed exper1-
472 Mr. J. Walker on tlte Admi8sible Width of
mentally by employing very dilute solutions and a large
accumulator-battery, such as that recently employed by Pro-
fessors Trowbridge and Richards*
20th 1898.
Note added J1Iay 27tlt.-Dr. Van Everdingen informs me
that he has discovered the slip in his calculation, and agrees
with. the remarks made above concerning the experiments of
Flono and Bagard.
I
f
Phil. )lag. February (1897). l
t Communicated bv the Author
t Ph}l. .Mag. [.'>J. xxviii. p. 80 (IS89). . .
I find tha.t thrs result of the widemng of the Elit has
already been grven by i\I. Ch. Fabrv in his thesis for the de!!Tee of Doctor
of Science, published at Marseilles in I89'l and recrret that I was not
aware of this interesting work until my pap7r was in type.