June 15, 1941 ANALYTICAL EDITION 443

The amounts of sulfuric acid and buffer are adjusted so that
the solution is certain to be acid during oxidation with bromine
and the potassium acetate in the buffer will suffice to convert the
excess of sulfuric acid to acetic acid.
r cent potassium iodide solution is freshly prepared
ea?fti:t dissolving 1 gram of the salt in 3.7 cc. of iodine-free
water. The buffer is prepared by one-twelfth neutralization of
glacial acetic acid with a saturated solution of otassium car-
bonate that has been washed with iodine-free aiohol. Let us
suppose that the glacial acetic acid is 17.4 N , and the washed
potassium carbonate solution 10.8 N . To 10 cc. of glacial acetic
lo
acid one would add 17'4 or 1.34 cc. of the carbonate solu-
12 X 10.8
tion.
Summary
The reaction between minute concentrations of chromate or
dichromate and iodide is influenced b y many factors, notably
acidity, iodide concentration, catalysts such as iron, and ions
which form complexes with chromium, such as oxalate and
tartrate.
Conditions were found under which the reaction between
iodate and iodide goes t o completion long before liberation of
iodine b y chromate can be detected. This made it possible to
titrate iodate, and, after addition of acid and oxalate, t o
titrate chromate present in the same solution.
The procedure is of value in testing apparatus and methods
for determination of iodine in blood, and in preventing re-
turning end points when these are due to small amounts of
chromate.
Literature Cited
(1) dllott, E. N.,Dauphinee, J. A., and Hurtley, W. H., Biochem. J.,
26, 1665-71 (1932).
(2) Matthews, N. L., Curtis, G. M., and Brode, W. R., IND.ENG.
CHEM.,Anal. Ed., 10, 612-15 (1938).
(3) Shaffer,P. A., and Hartmann, A. F., J . Bid. Chem., 45. 365-90.
especially 366 (1921).
(4) Stevens, C. D., J. Lab. Clin. M e d . , 22, 1074-9 (1937).
(5) Trevorrow, V., and Fashena, G. J., J . BioZ. Chem., 110, 29-38
(1935); 114,351-5 (1936).

A Method of Measuring Contact Angles

J . J . BIKERRIAN
Glass Fibres, Ltd., Firhill, Glasgow, Iv. W., Scotland

the solid surface which may be due to corrosion of the surface by

W HEN a liquid drop lies on a horizontal solid plate, the
area of contact between liquid and solid depends on the
contact angle, 8, between air, liquid, and solid, and on the
shape and volume of the drop and t h e surface tension and
density of the Liquid. The relation between these factors and
the area of contact is generally too complicated to allow a
calculation of 6'from the size of the area. If, however, the
drop is very small and very nearly circular, the diameter, l a ,
of the basis of the drop is a function only of its volume, u , and
of e:
ba = 21 sin3@
u ,+ - 3 ~ 0 +~ 0COS^^) (1)
the liquid, deposition of the solutes present in the liquid, or set-
tling of particles suspended in it. If the marks are not clear enough,
this third effect may be artificially increased by dusting ignited
talc onto the drop surface; it slides down the slopes of the drop
and forms a white ring round its boundary.
If the volumes recommended above are used, A has values
between 0.05 and 0.5 cm. The diameter of the circular marks
can be determined using any method suitable for such lengths.
A microscope provided with eyepiece micrometer scale (for small
values of A) and a mechanical stage (for large values of A) is
most convenient. A total magnification of 20 diameters is suf-
ficient.
The precision of the value obtained for
AS
f is limited chiefly

This equation is arrived a t in the following manner. by the deviation of the mark from a n ideal circle. As no

The surface i;ension tends to give the drop the shape of a part
of a sphere (since a sphere has the smallest relative surface).
Gravitation on the other hand tends to flatten the drop. The
actual shape of the drop is determined by the simultaneous action TABLEI. RATIO, AOJlu, FOR VARIOUSVALUESOF CONTACT
of both these forces. The effect of the surface tension increases ANGLE@
when u decreases, since the ratio of surface to volume increases
as well; and the effect of gravitation decreases with v since the Change of >hange of
level differences in small drops are small. Therefore very small 9 4
- A:/V per e a:
- A:/D per
drops are pracxically spherical segments, and Equation 1 is the Des. U 10 Deg. U 10
geometrical relation between the diameter, A", of the base of the 30 18.54 0.62 92.5 3.575 0 094
segment, its volume, Y, and the angle, 8 , between the base and the 32.5 17.00 0.54 95 3.34 0 090
35 15.64 0.48 97.5 3.12 0 086
curved surface. 37.5 14.45 0.42 100 2.90 0 082
If the drops are larger than, say, 0.0001 ml., the diameter, A, 40 13.40 0.38 102.5 2.69 0 080
of the circle of contact is appreciably larger than the value, 10, 42.5 12.46 0.34 105 2.495 0 076
45 11.62 0.30 107.5 2.305 0 073
which it would have had in the absence of gravitation. The ratio 47.5 10.87 0.28 110 2.123 0 070
50
a3 has, therefore, to be measured for several values of u and then 52.5
10.18
9.55
0.25
0.23
112.5
115
1.948
1.781
0 067
0 064
55 8.97 0.21 117.5 1.622 0 061
extrapolated to Y = 0. A curve for the relation between A and 57.5 8.44 0.20 120 1.470 0 058
u is given by Wark (4). 60 7.94 0.19 122.5 1.326 0 055
I n order to make the extrapolation to u = 0 feasible, small 62.5 7.475 0.17 125 1.189 0 052
65 7.04 0.16 127.5 1.059 0 048
drops-e. g., 0.001, 0.002, 0.004, and 0.008 m1.-have to be 67.5 6.635 0.15 130 0.938 0 046
used. They are driven out from a microsyringe. The Agla 70 6.25 0.145 132.5 0.823 0 042
micrometer syringe of Burroughs Wellcome & Co. , London, 72.5
75
5.89
5.55
0.14
0.13
135
137.5
0.717
0.618
0 040
0 036
was found very convenient for determining the volume of such 77.5 5.22 0.12 140 0.527 0 033
small drops. It is supplied with a steel needle which is not 80 4.92 0.12 142.5 0.444 0 030
wetted by water and, therefore, delivers drops more readily than 82.5 4.62 0.11 145 0.369 0 027
85 4.34 0.107 147.5 0.302 0 024
B micropipet of glass. 87.5 4.075 0.102 150 0.242
The diameter, A, of the contact circle is measured after the 90 3.82 0.098
evaporation of a drop. After evaporation drops leave a mark on
444 INDUSTRIAL AND ENGINEERING CHEMISTRY
surface (under ordinary conditions) is rigorously uniform, the
diameter of the contact mark varies from point to point. If
the average diameter is wrong by 1 per cent the error of the
A3
ratio ; is 3 per cent.
A3
When the value of is measured or extrapolated, 8 may
be calculated using Table I, which gives the values of the
function *(2 - 324
COS e +
coss e)
for 49 values of 0. For non-
tabulated values of $ a linear interpolation is sufficient.
A3
Table I also shows that a 3 per cent error in f causes an
error of about 1 per cent (or less) in the value of 8. If the
solid surface is very good, like those of built-up multilayers
(g), can often be determined within *0.6 per cent and 8
therefore calculated within * 0.2".
In a recent paper Benedetti-Pichler and Rachele (1) esti-
mated the size of minute droplets of water on cellulose nitrate
by measuring the diameter of the circle of contact. They
found that the ratio was about 9; Table I shows then
A Wet-Combustion Micromethod for
Determination of Carbon and Hydrogen
Iodic Acid as an Oxidant for Wet Combustion
BERT E. CHRISTENSEN AND ROBERT WONG
Oregon State College, Corvallis, Ore.
C HRISTEKSEN and Facer (1) have recently published
a wetcombustion method using iodate as the oxidant
for the determination of carbon and hydrogen. Previous
experience has convinced the writers that the use of iodate in
this connection is best adapted to micro work. Since a
method which would handle small samples (2 to 5 mg.) is
highly desirable in many cases, the possibility of devising such
a procedure was studied.
In connection with these studies the method of Christensen
and Facer was modified. Changes in the procedures for de-
termining the evolved carbon dioxide and the method of
treating the unreduced iodate, and a number of other modifi-
cations resulted in a considerable saving of time.
Although these wet-combustion methods are simple, permit
intermittent operation, and employ the minimum of appara-
tus, their success depends upon the use of iodic acid as an oxi-
dant for the organic material. This reagent has given excellent
results for many organic compounds, yet some compounds
under the conditions specified for analysis cannot be quantita-
tively oxidized by iodic acid. It was the opinion of the
authors that much more information must be obtained regard-
ing the behavior of this reagent toward all kinds of organic
compounds (volatile, insoluble, etc.) before a wet-combustion
method involving iodic acid could be established. It was
possible that further study of the limitations of iodic acid as
an oxidant in wet combustions might afford a criterion for
predicting the behavior of a given compound when treated
with iodic acid. For these reasons the following investigation
was undertaken.
Vol. 13, No. 6
that the contact angle between air, water, and cellulose ni-
trate was about 55".
The method here described was used for drops of water on
built-up multilayers of soaps ( d ) , on lacquered tin plate (S),
and on glass plates.
U'hen compared with the usual method of a direct measure-
ment of 8 this method is indicated when determination of
volume and length is simpler than that of angle. It has also
another advantage. When the profde of a drop is observed,
the angle measured is that for one point only; the same drop
viewed from another side may have a different shape and form
a different contact angle. The area of contact between drop
and solid is a measure of an average of all the contact angles
present along the circumference of the drop, and the shape
of the mark shows how constant (or otherwise) is the contact
angle along this circumference.
Literature Cited
(1) Benedetti-Pichler, A. A., and Rachele, J. R., IND.ENQ.CHEM.,
Anal. Ed., 12, 233 (1940).
(2) Bikerman, J. J., Tram. Paraday SOC.,36, 412 (1940).
(3) Sumner, C . G., The Metal Box Go., Ltd.. London, W. 3., private
communications.
(4) Wark, I. W., J . Phys. Chem., 37, 623 (1933).
Reagents
Sulfuric acid, 96 per cent. It is important that the sulfuric
acid be made as free as possible from organic matter. This was
accomplished by addin 50 ml. of Superoxol dropwise t o 200 ml.
of hot concentrated sulfwic acid. This mixture was just brought
to boiling and the heating continued until the sulfuric acid at-
tained approximately its original volume.
Barium hydroxide, approximately 0.1 N , was prepared and
protected by a soda-lime tube.
Hydrochloric acid, approximately 0.05 N , was prepared and
standardized with potassium iodate.
Thymol blue indicator, 0.2 gram, was dissolved in 43 ml. of 0.01
N sodium hydroxide and diluted t o 500 ml. with distilled water.
Potassium iodidebarium chloride solution, approximately 0.5
N with respect to each reagent.
Potassium iodate, c. P. grade.
Potassium permanganate, approximately 0.1 N .
Acetone, acid-free.
Apparatus
The ap aratus is similar in design to one described in a previous
article (8r Two changes were made in the reaction vessel: The
bottom was enlarged to form a bulb and the cup on the side was
constructed from a male standard taper joint. The bulb made it
easier t o dissolve many substances, while the joint afforded a
better means of connectin the carbon dioxide-free air system to
the apparatus and provifed better protection a ainst organic
contamination. Since no carbon monoxide was formed during
iodate oxidation, the slow combustion unit was deleted from the
train. The modified apparatus is illustrated diagrammatically
in Figure 1. For the protection and accurate measurement of the
standard barium hydroxide solution the automatic pipet described
by West ( 4 ) was employed.