56
A VERIFICATION OF ANDRADE'S FORMULA
OF VISCOSITY
N.S. CHENG (86 75 #8)
Department of Physies, University of Cheiang
(Received December 23, 1940)
‘The well known formula of Andrade?
for the viscosity 7 of a liquid at its
freezing point is
T=4 volo. a
where m is the molecular mass, ¢ the
average intermolecular distance (center-
to-center), and ¥ the freqiency of mole:
cular vibration of the liquid. Denoting
‘molar volume by 7, Avogadro number
by N, freezing point by 7, gas constant
by R, molecular weight by Mf, and
molecular radius by a, we may put
=winyh
and, as given by Lindemann’ theory?
of fusion,
veer hy "hy",
where
co¥Z glhwth,
e
p being'a fraction defined by
dase -o) °
Equation (4) means that ag is the short.
est face-to-face distance between the
assumed spheres representing two neigh-
boring molecules when they are at their
mean positions.
In support to Andrade’s theory, we
have found a simple, though not very
rigorous, way of verifying formula (1
The motion of each molecule may be
treated as one in a discontinuous mediuun
composed of all the rest molecules, The
resistance offered by this medium to each
molecule moving through it with velocity
R=4nehlf, «)
where
pats Loteeso.2m “M4, (5
T being the mean free path of the mole-
Mf we set £ equal to ep, i.e.,
twico the amplitude of vibration in
Lind: mann’s theory of fusion, equation
(9) gives
cules,
. 6)
«ie
Adopting Groneisen’s value! 2.8 x 10!
for C, equation (2) yields p=0.124. By
(6) and (5), we have f=1.27 for any
Higuid freezing point. The
equation of motion for any chosen
at its
direction x isA VERIFICATION OF ANDRADE’S'FURMULA OF VISCOSITY
mos ax
ae ae
where X is the force causing motion
and
+X,
a=4nalf, ”
As in Langevin's theory of Brownian
movement, multiplying through by x
changes this equation into
2 9 at y
am ae a 4
aa)
Toa 7%
Taking the statistical average of this
‘equation over all the molecules, we have
FA preg
ae ce di
since Xz=0 and, by the principle of
‘energy equipartition, $m GA 4aT,
4% being the Boltzmann constant. The
solution to this equation is
ast)
“at
PAT (Ie
@
If ¢ is greater than 10 second, the
exponential term in the bracket is
negligible compared to unity for all
molecules except hydrogen. In this
‘case, neglect of this term gives
fen 22 fia,
os (Ee BE,
7
UL Cis the time between two successive
collisions, i.e., equal to 1/2v, then s/t
‘is the average component speed, 3, of
‘the molecules along the x-direction
Le.
Substituting this expression of a into
(2), we have
ay
which, by (3), becomes
Putting in the munerical values of f and
p previously given, we have
(8)
which is only 1.09 times that of An-
Grade’s expression (1).
For diatomic liquids, the molecular
shape is not spherical and therefore58
not expected to give
It however yields the
equation (8)
accurate values.
correct tendency of change for different *
‘molecules as shown in the following
table:
Freezing
Molecule FECES calculated observed
Ch WK 7.7ep. 10.3e.p.%
ire 2650) 016) = lise
le, 286 14S B.S
O° 4 4 ar
Hy 14 0.037 0.0138
We note that the discreparcy is largest
Lindelaann, Phys. Zits. 11, (1912) 608,
orzog, R:
and Kudat, HL, Zelts. . Phys,
N. Sc CHENG
in the case of hydrogen’ This is in
the present thoory due to the fact that
for hydrogen
schich is certainly not riegligible come
pared to unity so that the simple solution
here used isnot applicable,
The writer is indebted to professor
HOFF LU for his suggestion’ of the
pfoblem and his colstant advice and
encouragement.
‘Andrade. E. N. 8, C., Phil. Mag, 17, (104) 497, 615,
(169) 217,
Davies C.N., Proc. Roy. Soe, ST, (045) 259,
Gerunsisen,-Awn. der Phys., 99, (WI2) 257
Steacie and Johnson, J: Am. Chem. Soe. 97. (1925) 154.
Rulako and Schubaikow, PAYS. Z. Sowjetunion, 6, (W&M) 470,”
Verschatfelt ,}.E,, Comm Phys. Lab. Leiden, 180, b, (197) 16
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