Sound Absorption in Liquids

in Relation to Their Physical Properties

Viscosity and Specific Heats
By S. Pa r t h a s a r a t h y and A. F. Chhapgar
With 4figures
Abstract
From a study of the physical properties of liquids such as viscosity, sound
absorption and the ratio of specific heats in relation to molecular constitution,
a few general rules regarding sound absorption have been derived. It has been
found that in all cases, the excess absorption decreases with increasing mole-
cular weight in the same manne,r as that of the ratio of specific heats. That
t,he ratio of specific heats is as important as viscosity in sound absorption at
high frequencies has been brought out clearly in the paper.
1. Introduction
It is well known that in liquid media the absorption of sound at ultrasonic
frequencies cannot be completely explained in terms of existing theories like
those of shear viscosity, second viscosity, relaxation etc. All the liquids
studied so far have been selected at random and bear no particular relation
to one another except by chance. It is also well known from previous work
on the velocity of ultrasonic waves in liquids that the velocity is related to
the molecular constitution which brings order out of the confusion of a mass
of data. This has been done1)2), both empirically and theoretically first by
Parthasarathy and later by Lagemann, Rao, Schaaffs, Bakhshi and
others. It was therefore considered interesting to study if similar relations may
hold between sound absorption as observed at high frequencies, above 3 Me.,
and molecular constitution as well as other physical properties. An exami-
nation of a few such physical properties, e. g. specific heats and light scattering
has been undertaken in this laboratory and paper~3) ~) ~) ~) are under publi-
2, S. Parthasarathy and N. N. Bakhshi , J. Sci. Ind. Res. 12A-10, 448 (1963).
3) Sound absorption in liquids i n relation to their specific heats by S. Parthasa-
rathy and D. S. Guruswamy, Ann. Physik (under publication).
4, Sound absorption in liquids in relation to light scattering data by S. Partha-
sarathy and A. P. Deshmukh, Ann. Physik (under publication).
j) Brillouin components in light scattering in relation to sound absorption by
S. Parthasarathy, D. S. Guruswamy and A. P. Deshmukh, Ann. Physik (under
publication).
6, Sound absorption in liquids in relation to their specicfic heats - Part 11 by
S. Parthasarathy and D. S. Guruswamy, Ann. Physik (under publication).
L. Bergmann, Der Ultraschall (1954).
298 Annalen der Physik. 6. Folge. Band 16. 1955
cation. These previous papers have suggested that for sound absorption vis-
cosity is not the only factor prominent in absorption but the ratio of specific
heats y enters in the formula and its influence is as great as that of viscosity.
In this paper wehave further examined sound absorption at high frequencies
in relation to viscosity and specific heats.
2. Data on Physical Properties
Data on absorption, viscosity and ratio of specific heats have therefore
been collected from available literature and critically examined. The data are
given in Table 1 where
liquids have been grouped
together according to their
molecular constitution. In
the following Table values
for viscosity have been taken
from International Critical
Tables while the observed
absorption of sound
are from the review paper of
Markham, Beyer and
Fig. 1. Aliphatic hydrocarbons Lindsay) except in the
case of esters where the
values of are from the paper by Parthasarathy, Ti pni s and
Panchol ys). The ratio of specific heats y are from our previous paper3).
The last column gives the ratios of observed to theoretical sound absorption.
Fig. 2. Alcohols Fig. 3. Esters
The data are also given in the form of graphs for a few typical cases in
figures 1 to 4. Each graph gives the relation (a) molecular weight and 7,
(b) molecular weight and y (c) molecular weight and observed sound absorp-
tion and (d) molecular weight and the ratio
( 4 V2 ) EXP.
(alv2),,.
~ - for a series.
) J. J. Markham, R. T. Beyer and R. B. Li ndsay, Rev. mod. Physics23-4,
353 (1951).
8) S. Parthasarathy, C. B. Ti pni s and M. Panchol y, Ultrasonic absorption in
liquids by an improved optical method and relation between absorption and specific
heats Z. Physik (under publication).
S. Parthasarathy and A. F. Chhapgar: Viscosity and Specific Heats
299
3. Observations
Briefly the relation between the different physical entities can be summari-
sed thus: (a) with increase in molecular weight, the viscosity always in-
creases for anyseries, as observed by earlier workers, notably Gar tenme is ter ;
(b) y decreases with molecular weight whatever the series ; ( c ) the observed
sound absorption decreases in the case of aromatic compounds, while it in-
creases for aliphatics ; and finally (d)
the excess sound absorption over the
classical value continues to diminish
as one ascends in the series. These
results are significant and will be
discussed further.
Considering the classical S t okes
theory of absorption, absorption is
directly proportional to viscosity.
Now it is well known that viscosity
and sound velocity v are related to
molecular weight for members of a
homologous series 9, and hence sound
absorption as given by Stokes theory will also be related to molecular
weight as determined by 5 . A plot of viscosity q against molecular
weight M shows that q increases with M. The observed absorption
however does not follow this relation. A plot of absorption against molecular
weight 1M shows that for a few series like alcohols the absorption does
increase with the molecular weight but that it is always higher than
expected from Stokes relation. For most other series however like aromatic
hydrocarbons, alkyl halides etc., the absorption decreases with increasing
molecular weight and the absorption is very much higher than that given by
Stokes relation. I n the case of fatty acids and esters, it is found that the
absorption is dependent on the frequency v of sound. This relation may be
expected in accordance with the relaxation theory put forward by Her z -
feldlO), Kneserl l ) and others; yet the agreement is not complete. Even so,
if a plot is made of the absorption at the same frequency against the molecular
weight the same relation is found to hold good as with other series, namely
the absorption decreases with molecular weight at each frequency and is higher
than that given by theory. I n general, it can be stated that for aliphatic
compounds, total abserved absorption increases with M (the exceptions to
this are esters, bromides, etc.) but the excess ratio decreases. For aromatic
compounds on the other hand total observed absorption decreases as M in-
creases and the excess ratio also decreases.
I n all the above cases it is found that it is always the first member of the
series which has an excessively high absorption and that the observed excess
absorption decreases with increasing molecular weight ; for very high values
of M, it approaches the theoretical value. I n other words, the excess absorp-
Fig. 4. Aromatic hydrocarbons
9, R. Gartcnmeister, Z . physik. Chem. 6, 624 (1890).
l o) K. F. Herzfeld and F. 0. Rice, Physic. Rev. 31, 691 (1928).
11) H. 0. Kneser, Ergcb. exakt. Naturwiss. 22, 121 (1949).
300 Annalen der Physik. 6 . Folge. Band 16. 1955
Table 1
Liquids
I Observed I Excess absorp-
Molecular Viscosity Ratio of 'Sound abSorP-
tion
(a/v*)Ex,.
weights 20" C specific tion
n-pentane . . . . . .
n-hexane . . . . . .
n-heptane
n-octane . . . . . . .
n-decane . . . . . .
n-undecane . . . . .
n-dodecane . . . . .
Methyl alcohol . . . .
Ethyl alcohol . . . .
n-butyl alcohol. . . .
n-nonanc . . . . . . .
n-propyl alcohol . . .
n-amyl alcohol . . . .
n-hexyl alcohol . . .
n-heptyl alcohol . . .
n-octyl alcohol . . . .
, M centipoise
I
Methyl acetate . . .
Propyl acetate . . . .
Ethyl acetate . . . .
Butyl acetate . . . .
Amy1 acetate. . . . .
heatsy 1(a/v2)Exp:1017 _ _ ~
I cm-1 sec2 (a/v2),h.
(i) Aliphatic Hydrocarbo
0.24 I 1.37
128,25
142,28
156,30
170,33
0,59
1,72
2,lO
2,80
4,65
4,37
32,04
46,07
60,09
74J 2
88,15
102,17
116,20
130,23
1,214
1,204
1,173
1,180
1,298
1,218
74,08 I
88,lO i
102,13
116,16
130,18
3Mc.SMc.7Mc.
- 296 219 156
1,436 1252 157 110
- 276 145 114
262 131 -
lT81 1241 145 106
3 Mc. 5 Mc. 7 Mc
44,5 32,2 22,9
30,3 18,9 13,2
26,5 14,O 11,O
26,2 13,l -
15,8 9,5 6,9
\ ,
0,37
0,44
0,58
0,73
0,81
Ethyl bromide . . . .
n-amyl bromide . . .
n-propyl bromide. . .
n-butyl bromide . . .
-
77
80
-
-
-
-
-
34
54
75
104
106
132
-
-
39
0,63 49
151,06 1 - c301 I - I
-
10
8
-
-
-
-
-
2,35
2,45
2,08
2,02
1,83
1,80
-
-
Benzene . . . . . . .
Toluene . . . . . . .
o-xylene . . . . . . .
p-xylene . . . . . . .
(viii)
Benzene . . . . . . .
Fluorobenzene
Chlorobenzene
Bromobenezene . . .
m-xylene. . . . . . .
. . . .
. . . .
' 78,11 900
92,13 I 8: : : ~ t::2: 1
106,16
' 0,81 -
106,16 0,60 1,319
106,16
1 0,64 I - 1 78 1
Aromatic Halogen Substitution Compounds
78,11 1 0,65 I 1,447 900 '
96,lO 0,68 ' - l -
112,56 1 0,80
157,02 I 1,17
167
40
25
-
6J
3,5
38
-
593
3,5
399
103
-
10,3
-
993
-
103
-
15,5
24
-
S. Parthasarathy and A. F. Ghhapgar: Viscosity and Specific Heats
301
tion becomes negligibly small or nil. This can be clearly shown by plotting
the excess absorption (expressed as a ratio of observed to theoretical absorp-
tions) against molecular weight. It is seen that the excess ratio diminishes
with increasing AT in all cases. Thus it can be stated in general that there
are two factors which influence absorption, both of them being some physical
properties of the liquid, (a) one which predominates at high molecular weights
and (b) the other which predominates at low molecular weights. The former
factor is evidently the shear viscosity of the medium and it can be expected
that for very high molecular weights, the observed absorption will reach the
limiting value given by theory. The question now to be answered is -
what is the other property of a liquid which fits in with all the above changes
of absorption as observed and whose trend is similar to them. That the ratio
of specific heats answers well this question appears to be clear.
4. Discussion
Most of the postulates put forward to explain the excess observed absorp-
tion do not succed entirely when applied to all the liquids. As was noted
above, viscosity by itself was not sufficient for the purpose. Therefore it was
proposed that there existed a ,,second viscosity" which was responsible for
the excess absorption at high frequencies. However sufficient experimental
evidence is not available to support this theory. It has been contended that
the streaming motion observed in a sound field is caused by this second vis-
cosity factor12), but it has been pointed out by others that this streaming
effect is due to other factors and not to second viscosity13). The theory of
thermal relaxation is very successful in explaining the excess absorption in
gases for which it was originally proposed. Rut it does not succeed in the case
of liquids except for a few cases like fatty acids and esters ; even for these
exceptions, the predicted dispersion of sound velocity is not found in spite
of careful observation, except for the case of acetic acid1'). The theory of struc-
tural relaxation 15) put forward for the case of water succeeds in the case of
this particular liquid but it is not applicable as a general rule to other cascs.
The absorption due to thermal conductivity as given by Kirchhoff 16) can
also be neglected in the case of all liquids, this factor being negligibly small.
Very recently another empirical relatian ha++ been put forward by one of us
(S. P.) and Gur~mwi trny~) relating the ratio of specific heats to the excess
absorption from data collected for over 40 liquids. The complete sound ab-
sorption can be expressed by
which has been found to be satisfactory not only in indicating and stating by
how much the excess absorption varies but also the variation of sound absorp-
12) L. N. Li ebermann, Physic. Rev. 76, 1415 (1949).
l 3 ) J . J . Markham, J. Acoust. Soc. Amer. 23, 144 (1951).
la) J. Lamb and J. M. M. Pi nkerton, Proc. Roy. Soc. A 199, 114 (1949).
15) L. Hall, Physic. Rev. 73, 775 (1948).
16) G. Kirchhoff, I'ogg. Ann. 134, 177 (1868).
302 Annaltn der Ph ysik. C. Fclse. Band 16. 1955
I
111
I V
tion as observed with temperature, pressure and at critical solution tem-
peratures. It may be mentioned that though specific heats and their ratio
occur in the Ki rchhoff factor of thermal conduction, the contribution of
this term itself to total sound absorption is negligible. It is the purpose of
this paper to show that y plays an important part in sound absorption. Un-
fortunately the values of y are not available for more series of liquids. For
cases where these values are known it is found that in a homologous series y
decreases with M, being highest for the lowest menber. This is very similar
to the variation of excess absorption with M and a plot of ~- against
M shows that this variation is in all cases similar to that of excess absorption.
This would seem to indicate that y can successfully explain the observed
absorption in liquids.
5. Classification of Liquids
From the above discussion it can be seen that y , an important property
of the liquid state, and q together can explain the observed absorption in
liquids, y being usually predominant at the low molecular weights and q at
at the higher end. A study of the various liquids shows that they can be
divided into four groups as follows, according as y or q is the predominant
factor.
This classification is similar to that proposed by Pi n kertonl7) who
classified them according to their absorptions and to their temperature varia-
tions. I n fact, it is seen that the same liquids form a group in both types of
classifications. In view of the fact that the excess absorption can now be
completely explained in terms of q and y, Pi nkerton's empirical classifi-
cation in terms of absorption takes on a physical significance in the classifica-
tion proposed above. We may indeed go further and state that since observed
absorption can be satisfactorily accounted for by q and y and therefore presents
no anomaly, the above classification, though useful, is no longer necessary
for grouping the liquids.
( dV2 ) E, , .
(@/V')T,,
Liquids showing anomalous absorption like
benzene, carbon disulphide etc.
Water, alcohols, etc.
1 No liquids known i n this class
1 High 1 High ~ Viscous liquids like glycerine, castor oil etc.
High Low
High 1 High
Low
-
Class Examples
As was stated above,it is unfortunate that the liquids which have been
studied so far for their sound absorbing properties have been mostly selected
at random. The foregoing discussion shows that a great deal of information
can be obtained if the liquids can bestudied in terms of their molecular con-
stitution. The liquids do not show any absorption in it random manner but
follow a regular order. There are very few data available for different homo-
l7) J. M. M. Pi nkerton, Proc. physic. Soo. 62B, 129 (1949).
X. Parthasarathy and A. P. Chhupgar: Viscosity and Specific Heats
303
logous series as regards y and z/vz and hence more data would fill in the gaps.
Experiments are on hand in this laboratory in this connection and results
will be published when completed.
6. Sound Absorption and Chemical Constitution
From the above observations and discussion, some general rules relating
sound absorption at high frequencies to chemical constitution may be derived.
This is possible since sound absorption shows definite regularity with molecular
constitution.
(1) Both y and 7 are operative in sound absorption.
( 2 ) High y or high 7 alone is enough to give high ultrasonic absorption.
(3) Liquids having both 7 and high are unknown.
(4) y is highest for the first member of a series (lowest C atom) and then
it decreases regularly.
( 5 ) In all cases, the excess sound absorption over the classical value also
follows the same trend as y, the noticeably excess absorption being found only
in the first few members of the series.
(6) I n aliphatic compounds, which have low y, ultrasonic absorption
increases with molecular weight but the excess absorption over the classical
decreases.
( 7) I n aromatic compounds however, both ultrbsonic and the excess
absorption decrease as molecular weight increases.
(8) The observed value of absorption for liquids of high molecular weight
approaches the limiting value given by Stokes s theory.
From these observations we may infer that what has been considered so
far as anomalous absorption does not exist, this anomaly being due to the
neglect of the part y plays in sound absorption at high frequencies. Sound
absorption is normal for any liquid if both y and 7 are considered as effective
in the process.
NewDel hi 12, National Physical Laboratory of India.
Bei der Redaktion eingegangen am 8.Marz 1955.