SURFACE TENSION

by the RING METHOD

APPLICABILITY OF THE. DU NOUY APPARATUS
RUDOLPH MACY
Edgewood Arsenal, Maryland

I t i s possible by the ring method to obtain surface-tension

employ a cnlibration curve i n which determinations d e
data uniform with those @en as "correct" in Intema- by the ring method are plotted againit correct values as
tional Critical Tables. Two methods available are: (1) giuen in International Critical Tables. The calibration
to apply correction factors according to the procedure procedure gives almost as good results as the exact method
recornended by Harkins and his associates, or (2) to of Harkins.

S URFACE-tension data obtained by t8e capil-

lary-height method are generally accepted as
correct. For example, the surface tensions
given in Internutional Critical Tables ( I ) by Harkins
and his associates have been, "for the greater part,"
corrected to agree with certain "standard" values for
water and benzene as determined by the capillary-
height method in air a t 760 mm.
On the other hand, one can hardly doubt that the
most rapid and simplest method for determining the
surface tension of liquids is one of the ring methods
made popular about fifteen years ago by the introduc-
tion of the du Nouy surface-tension apparatus (2, 3a,
3b, 4). It has been the experience of the writer that
the remarkable convenience of this instrument for
routine work and for such purposes as student instruc-
tion is largely nullified by the lack of proper informa-
tion as to its use and the consequent loss of time re-
quired for one to become acquainted with it.
It is the purpose of this article to show that the du
Nouy apparatus gives results uniform with the data in
International Critical Tables, if the readings made with
the instrument are corrected in accordance with the
information given in the papers by Harkins and co-
workers (5, 6), or if the instrument iscalibrated against
a few liquids, the data for which are given in Interm-
tional Critical Tables. It is hoped that the paper will
be of assistance to those who have put implicit faith in
the claims made by the bulletins describing the du
Nouy apparatus (3a, 3b), and to those whose work does
not allow an opportunity for making a thorough ex-
amination of the characteristics of the instrument.*
The apparatus discussed in this paper is the simple
model described in reference (3a). The liquid is slowly
* The Central Scientific Company has recently issued Bulletin
No. 101, "The Ring Method for Surface and Interfacial Tensions"
(no date), which contains an excellent bibliography and instruc-
tions for use of the Harkins correction factors (5.6).
raised by means of an adjusting screw until it touches
the platinum ring. By turning a knob and increasing
the torsion on the taut piano wire which supports the
ring, the ring is then slowly lifted until it suddenly
tears away from the liquid surface. The torsion on
the piano wire, expressed in dynes, is a measure of the
surface tension of the liquid. The relative surface
tensions for different liquids are read on a dial. On
the instrument used in this work the dial readings can
be made to about 0.3 of a scale division, but on a later
model (36) readings can be made much more accurately.
DIRECT DETERMINATION OF SURFACE TENSION
According to instructions in the bulletin (3a) issued
by the manufacturer, the instrument may he used for
direct surface-tension measurements. This is done by
forcing the ring hack to its zero position by adding
weights to it, after the tearing of the liquid surface
has taken place. The following experiment with ethyl
acetate at 26'C. illustrates this procedure, and also
shows how greatly the surface tension obtained differs
from the accepted value.
weightrequired to forcering back to zero = 0.223 g.
Surface tension * 0.223 = 27.3 dynes/cm.
2 x 4
In the calculation, the farce in dynes is divided by 8
because the ring has a mean perimeter of 4 cm., and
there are two surfaces, one on each side of the wire, com-
posing the ring. The accepted value for the surface
tension of ethyl acetate at this temperature is 23.5
-,..-I, .
r l . r n 0 ~/"rn
--L
increasing the torsion on the wire. The surface tension
of ethyl acetate, using this second procedure, was found
to be 25.7 dynes/cm. This procedure gives lower re-
sults, in better agreement, but not in good agreement
with accepted data. It is a tedious method, compared
with the original procedure of simply lifting the ring,
although i t is obviously more correct (4, 7 ) .
The surface tensions determined by both methods for
a number of liquids are shown in Table 1. In every
case, except for water, the values are much too high,
but the method of lowering the liquid gives the better
data. The results obtained by the two methods are
not quite parallel. For liquids with the usual surface
tension of-about 30 to 40 dynes/cm. the "pull-ring"
method gives data which are about 1.5 dynes/cm.
higher than the results obtained with the "lower-liquid"
method. For glycerol and water, however, the devia-
tion rises to 2.3 and 2.7 dynes, respectively.
METHOD OP STANDARDIZATION
In addition to the direct method of measurement of
surface tension described in the preceding section, the
instructions also recommend a standardization, so that
the dial reading on the surface-tension apparatus can
be converted directly to dynes/cm. This can be made
by putting the ring in any definite position, taking the
dial reading, and then placing weights on the ring and
noting how much weight is required to return the ring
to the zero position. For the instrument used in this
work, a weight of 0.3 g. was equivalent to a reading of
54 dial units,

It has been shown by Klopsteg (7, 8 ) that the proper

technic in handling the instrument is to keep the ring
Then 54 dial units - .,
O.3 8
.
= 36.8 ddynes/em

1 d i d unit' = 0.682 dyne/em.

in a constant level position, by lowering the liquid while
This value was used in converting the dial readings in
Table 1 to the surface-tension figures given in columns
4 and 5 of the table.

Did Surfarc lcnsion in dmrr/cm. Emor METHOD OP CRLIBRATION

rooding (0) V) (7) (7)
pull Lower Pull Lower I.C.T. Prom Col. A method of calibration which has been suggested
~.
17,,
(3a, 3b) is to obtain the dial reading a t which the ring
PC. Ring Liprid R h g Lipuid rolucr curve -Cot.
(6) pulls away from a water surface, and to use that value
Ether 24.0 29.0 27.0 19.8 18.4 16.5 -0.2 16.7 10.2 as a standard for other liquids. From Table 1 it will
kc-Bufyi alco-
hol 24.5 38.3 36.0 28.1 24.6 22.5 * 0 1 22.5 0 be seen that a reading 04107 dial units was obtained for
Acetone 25.0 39.8 37.0 27.2 25.2 23.1 -0.2 23.1 0 water a t 24'C. The accepted value for the surface
-,.---.,.-.-"~25.0
Ethylacetate
n
..
..
.
ho~
, "1""-
28.0 4 0 0 37.7 27.3 25.7 23.5 1;0.4 23.5
41.0 38.7 2 8 0 20.4 24.2 i0.4 24.2
0
tension of water a t this tem~eratureis 72.15 dvnedcm.
Benzene 25.6 47.0 44.5 32.1 30.4 28.2 * O O S 27.7 -0.5
From the ratio 107/72.15 we should be ahie t o cal-
~ t ehlo- h ~ ~ ~ ~ ~ culate the surface tensions of other liquids by simple
ride 22.0 54.2 51.8 37.0 35.3 31.9 -0.3 32.0 +0.1
Chloroben.ene 24.5 55.5 53.0 37.9 36.1 32.8 33.0 +0.4 proportion, after the dial reading has heen made a t the
A ~ I Yirothio-
I point when the ring is tom from the liquid surface.
cyanate 25.0 56.5 54.0 38.6 36.8 33.9 -0.3 33.9 0
methane 26.0 60.0 58.0 4K9 s9.5 35.8 -0.1 36.3 +0.5 From Table 1, however, it is obvious that W b r is the
Bromobenzene 24.0 60.7 58.5 41.5 39.9 36.0 -0.5 36.5 +0.5 worst &pato choose for cal&'ation purposes.
Bennaldehyde 25.0 64.3 61.7 43.8 42.1 39.5 -0.2 39.0 -0.5
~niiine 22.0 70.0 67.2 47.8 45.8 42.7 -0.4 42.4 -0.3 Water is the only liquid whose surface tension is
Nitrobenzene 27.0 70.0 67.7 47.8 46.2 43.1 -0.5 42.7 -0.4 measured directly with moderate accuracy by the du
Ethylene
22.0 77.2 74.2 52.6 50.6 47.6-10.5 47.2 -0.4 Nouy apparatus; the results for all other liquids are
Glycerol 22.0 100 96.7 68.2 65.9 63.3 *3.0 63.5 +0.; high. is shown graphically in ~i~~~~ 1, in
Wafer 24.0 111 107 76.7 73.0 7 2 . 1 5 ~ 0 0 572.1
- which the data point for water is indicated. If a
* The rearon for the use of the symbol (9)is explained at a later point io
the paper. straight line is drawn between the origin of the graph
and the point for water, this line will lie above the curve At any rate, a calibration curve similar to that in
which is shown and will give high surface-tension data. Figure 1 is necessary to convert readings on the surface-
A better way and perhaps the simplest way to cali- tension apparatus to surface-tension data in dynes/cm.
USE O F THE HARKlNS CORRECTION PACTOR

-Y
8
80
The fact that the ring method is not a reliable method
for the direct determination of surface tension has al-
2 60 ready been commented on extensively in the literature.
-
h
5
For example, MacDougall (9) states, "I do not think
that the simple theory of the experiment even with the
.- 40 procedure advocated by Klopsteg can lead to accurate
8
0
values of the surface tension." Johlin (10) mentions
that the value for benzene is high compared with the
value for water, nsing the same ring. Other papers of
$ z0
(0
interest are those cited in references (11, 12, 13, 14).
It remained for Harkins and his co-workers (5, 6),
20 40 60 80 100 however, to give the conclusive demonstration that the
Dial Reading measurements made as so far described in this article
FIGURE1.-RELATION BETWEEN DIAL READINGON THE are simply measurements of "the pull necessary to de-
SwPACE-TENSIONAPPARATUS, AND S-ACE-TENSION tach a ring from the surface of a liquid," and are not
DATAFKOM I N T E W I ~ NCRITICAL
AL TABLES measurements of surface tension. The expression
brate the du Nouy apparatus is to obtain a calibration
curve similar to that in Figure 1. This requires simply
the dial readings for a series of,common organic liquids
where M i s the weight of liquid raised above the free
as well as for water, and the plotting of these readings
surface of the liquid, and R is the radius of the ring
against the accepted values for the surface tension at
the corresponding temperature. Practically any of measured from the center of the ring to the center of the
wire, should not he equatedto y, the surface tension,
the common liquids of reasonable purity can be used
for the calibration. No attempt was made to purify but is better labeled by some other symbol, p..
The proper expression for the surface tension ( 7 ) is
the liquids recorded in Table 1, although C.P. or u.s.p.
then
products were employed in most cases.
The smoothed data for the construction of the curve
in Figure 1, as obtained for the instrument used by the
writer, are shown in Table 2. In column 7 of Table 1 where F is a factor which varies 6ith diierent rings and
are given the surface-tension data read from this curve. for different liquids. The factor for the size of ring is
It will be seen that they do not vary from the so-called given by the ratio R/r, where r is the radius of the wire.
"correct" values by more than 0.5 dyne/cm. This is The factor for the liquid is dependent on the ratio
good agreement when we consider that surface-tension Ra/V, where V is the volume of liquid raised above the
measurements by different methods Often vary to the free surface of the liquid [or V = M/(D<- d ) 1, D is den-
extent of as much as 3%. e
sity of the liquid, d is density of air saturated with
The calibration curve in Figure 1 was obtained by the vapor of the liquid. [For details the original paper,
"lower-liquid" method. If the dial readings obtained reference (6),should be consulted.]
by the "pull-ring" method are used instead, i t will be Harkins and his associates determined the values of
found that the curve does not go through the origin. F experimentally by measuring the true surface ten-
It is possible, however, to construct a calibration curve sions ( 7 ) of several liquids by -the capillary-height
using these measurements also. method, and comparing these results with the data for
pseudo surface tensions (p)obtained by the ring method.
TABLE 2 The correction factor is then F = y/p. A measnre-
ment made by the ring method, when multiplied by the
SUOOTaBD D A T A BOP CALCBEATrON CUPYE OF FlOUPB 1
proper value of F, should give the correct surface ten-
D i d Rcoding Svrfocr Tcnsia
(Lmering ihr Licuidl dmcr/cm. biod in dynes/cm.
Based
-- ~ -
~ on
-
~~ the values of F which thev obtained for
three pure liquids, and with sixteen carefully measured
rings, Harkins and his co-workers have published a
set of tables [ref. (6),page 17641 of correction factors
for the ring method.
In order to use the Harkins tables it is necessary
onlv to know the dimensions of the rina being used.
110 74.5 R/;, and the value of the expression R3/'t: ~ i t fo; a
the radius of the ring and of the wire of which it is made an R / r value of 0.6366/0.015 or 42.4, the value used in
are usually supplied by the manufacturer, so that R / r obtaining the correction factors for Table 3.
is readily calculated. The calculation of R 3 / V for Harkins measured his rings with an elaborate appara-
different liquids is obvious, and for ordinary purposes tus, not generally available, and found that the ring
the value of V in this calculation can be determined supplied with a du Nouy tensiometer had a wire radius
from the density of the liquid alone, disregarding the of 0.0157 cm., and an R/r value of 0.6366/0.0157 or
density of the air saturated with vapor. 40.55. The writer measured the ring, on the instm-
In Table 3 are shown the surface-tension data ( y ) ment used in this work, with a micrometer graduated
obtained hy applying these Harkins correction factors to 0.01 mm. and found the radius of the wire to he
to the measurements ( 9 ) obtained with the du Nouy 0.019 cm., and of the ring to be 0.627 cm. This yields
surface-tension apparatus. In this table, M is oh- an RJ7 ratio of 33.0, a value which gave poor results
tained from the dial reading by applying the standardi- when it was used to read the correction factors in the
zation value of 1 dial unit = 0.00555 g., and V = MID. Harkins tables.
The values of F were obtained from reference (6), p: By a trial-and-error procedure, various values of r
1764, corresponding to the R 3 / V figures in Table 3. were used to change the R / r ratio until correction fac-
The surface tension ( y ) is equal to pF. tors were found in the Harkins tables which would give
TABLE 3
s o a ~ A cTBNSIONS
s (I)OSTAINEDBY APPLY~NO COR=BCTION
HABEINS FACTOR
(F)TO TBB SURPACE-TENSION (9)MAD=BY TAB
MBASVRBMBNTS DU NOUY
MBTAOD
R/r = 42 R' * 0.258 7 = OF
Did I . C.T. uolucr, E~rar.
PC. read'# M D V RVV F 9 ? dyncs/mm. drxcr/cm.
Ether 24.0 27.0 0.150 0.710 0.211 1.22 0.895 18.4 16.5 16.5 - 0 . 2 0
iso-Butyl alcohol 24.5 36.0 0.200 0.798 0,250 1.03 0.908 24.6 22.4 22.5 * 0 1 - 0.1
Acetone 25.0 37.0 0.205 0.784 0.262 0.98 0.911 25.2 23.0 23.1 -0.2 - 0.1
Ethyl acetate 26.0 . 37.7 0,209 0.894 0.234 1.10 0.903 25.7 23.2 23.5 3 0 . 4 - 0.3
I-Butyl nlcohol 25.0 38.7 0.215 0.806 0.267 0.97 0.913 26.4 24.1 24.2 -0.4 - 0.1
Benzene 25.6 44.5 0.247 0.873 0.283 0.91 0.918 30.4 27.9 2812 -0.05 - 0.3
Ethylene d o r i d e 22.0 51.8 0.287 1.247 0.231 1.11 0.903 35.3 31.9' 31.9 - 0 . 3 0
Chlorobenzene 24.5 53.0 0.294 1102 0.267 0.97 0.913 36.1 32.9 32.6 + 0.2 f 0.3
Ally1 iaothioeyanate 25.0 54.0 0.300 1.015 0.296 0.87 0.921 36.8 . 33.9 33.9 * 0.3 0
Nitromethane 26.0 58.0 0.322 1.130- 0.285 0.91 0.918 39.5 36.2 35.8 * 0.1
36.0 * 0.5*
+-0.4
0.2
Bromobenzene 24.0 58.5 0.325 1.490 0.218 1.18 0.898 39.9 35.8
Benddehyde 25.0 7 0.343 1.040 0.330 0.78 0.930 42.1 39.2 39.5 0.2 - 0.3
Aniline 220 67.2 0.373 1.019 0.368 0.70 0.940 45.8 43.1 42.7 * 0.4 + 0.4
0.376 1.196 0.315 0.82 0.926 46.2 42.8 43.1 * 0.5 - 0.3

-
Nitrobenzene 27.0 67.7
Ethylene glycol 22.0 74.2 0.412 1.106 0.373 0.69 0.942 50.6 47.8 47.6 * 1.5 0
Glycerol 22.0 96.7 0.537 1.260 0.426 0.61 0.953 65.9 62.8 63.3 * 3 -0 2
Water 24.0 107.0 0.594 0.997 0.596 0.43 0.991 73.0 72.4 72.15 0.05 f 0.25
. ,
* Harkins (6) giver 35.75 at 25-C. ..
It is evident that the results obtained with the du good results when applied to the data in Table 3 for
Nouy apparatus are in good agreement with accepted such compounds as benzene and bromohenzene. The
surface-tension data, after the Harkins correction factor best R / r ratio found was 42, identical with the ratio
has been applied. according to the manufacturq's specification for the
Perhaps the most important question in regard to ring. This experience is interesqing, but just what it
applying the correction factor is the proper choice of means the writer is not prepared to say. At any
the R / r ratio. The ring supplied with the du Nouy rate, it is possible to arrive a t an R / r value which can
surface-tension apparatus is certified (4) to have a be used with the Harkins tables, even if one does not
diameter of 0.03 cm., accurate to 0.001 cm., and a mean know the exact constants for the ring used in the ring
perimeter of 4 cm. * 0.005 cm. This is equivalent to method.
LITERATURE CITED
(1) "International Critical Tables," Vol. IV, p. 446. McGraw- (8) KLOPSTEG. "Suface tension measurements by the ring
Hill
~-~
~ Book Co.. New York Citv.
~ ~ ~ method." itid... 63.599
, . .
(1926).
(2) DU NOUY, "~n'apparatusfor measuring surface tension." (9) MACDOUGALL, "Surface tension determined by the ring
J. Gen. Physiol., 1 , 521 (1919). method," itid., 62,290 (1925).
(3a) Bulletin No. 82, March 1, 1929. "du Nouy Surface Ten- (10) JOHLIN. "The ring method for surface tension measure-
sion Apparatus," Central Scientific Co., Chicago. ment."Qid., 64,93 (1926).
(3b) Bulletin No. 103. May 1. 1931. "The du Nouv Precision (11) DORSEY, "Ring methods for surface tension measurements."
ibid., 69, 187 (1929).
(12) NIETZAND LAMBERT, "Effect of some factors on the ring
..... .---
~~~~~-
-~ ~ ~

method for determining surface tension," J. Phys. Chem..

,(5) HARKINS,
YOUNG,AND CHBNO,
"The ring methddfor deter- 33,1460 (1929).
mination of surface tension," Science. 64,333 (1926).
(6) HARKINS AND JORDAN, "A method for the determination of
(13) TICHANOWSKY. "Zur Thenrie der Abreissmethode," Physik.
surface and interfacial tension from the maximum pull on Z.,26,522 (1925).
a ring," 3. A m . Chem. Sac., 52,1751 (1930). ( 1 4 ) Fsem AND FREUD, "A theory of the ring method for the
,(7) KLOPSTBG."A note on the ring method of determining determination of surface tension," J. Am. Chem. Sac.,
surface tension," Science, 60,319 (1924). 52, 1772 (1930).