844

I N D USTRIA4LA N D ENGISEERING CHEMISTRY

pyrrole grouping is contained in small amounts in the majority of

proteins, and i t forms a very important component of chlorophyl,
the green coloring matter of plants which, as we shall see, is
very closely related, chemically, to hemoglobin. I t is not improbable, therefore, that inorganic iron salts added to an exclusive milk diet are not utilized for building up hemoglobin
simply for the reason that other component parts of the hemoglobin molecule as essential as iron itself are either lacking altogether in the milk diet or present therein in insufficient amount to
subserve the needs of the blood-forming tissues and those of the
other tissues as well.

The authors' work on milk powders and synthetic diets

containing butter fat and cod-liver oil indicates that this
statement must now be modified in the light of newer disroveries.
Conclusion
The following results of this investigation should be emphasized :
I-Reproduction results obtained with cod-liver oil depend upon the manner in which the oil is administered.

Vol. 19, No. 7

2-Reproduction is much better on synthetic diets containing cod-liver oil than on synthetic diets with filtered
butter fat. If the animals on the synthetic diet containing
butter fat have a low hemoglobin content (and such may
be the case) whereas those on cod-liver oil have a normal
erythrocyte count and hemoglobin content, then there is
present in cod-liver oil a specific vitamin which is required
for normal iron metabolism. This conclusion is based on
the supposition that the results of Hart, Steenbock, Elvehjem,
and Waddell are correct-namely, that their animals suffering from anemia received a sufficient quantity of vitamins
A, B, and C ; and that ultra-violet light did not remedy the
condition. This problem is now under investigation in this
laboratory and results d l be published when they are complete.
Acknowledgment
The writers desire to express their appreciation t o the
Fleischmann Company for kindly supplying the yeast.

Estimation of Methanol in Alcohol and Alcoholic

Beverages, Using the Immersion Refractometer'
By John F. Williams

u. s. INTERNAL R E V E N U EB U R E A UBRANCH
,
LABORlTORY, BUFFALO,
N.

Y.

This method is based upon the refractive indices of the alcohols, and the apparent total percentage of alcohol as ethyl
alcoholfrom the speczJic graoity, using a 20 per cent solution. It is simple,
rapid, accurate, and eliminates caZculations.
CMEROUS methods have been proposed and used reading oi 41 35, and specific gravity 0 97513 (20/4' C ) By the applicaof these figures t o the method given one will obtain a minus quantity
for t'he estimation of methanol in alcohol, depending tion
of 4 9 per cent of methanol
generally upon chemical reactions. Among these
Method
are the Riche and Bardy method,2 which converts the alcohols
into methyl and ethyl aniline dyes, comparing strips of wool
The method given here depends upon finding the numeridyed by these products; the method of Thorpe and Holmesj3 cal difference between the immersion refractometer reading,
which uses potassium bichromate and sulfuric acid t o oxidize R , and the exact percentage of total alcohol, P , calculated
the methanol into water and carbon dioxide, and the esti- as ethyl alcohol from the specific gravity, using a 20 per cent
mation of the latter; the method of Deniges-Simm~nds,~solution. Both the refractometer reading and the percentage
which depends upon the colorimetric est'imation of the form- of total alcohol are taken on a 20 per cent alcoholic solution
aldehyde oxidized from methanol; method based upon the of the original sample. That is, the original sample is
estimation of formic acid oxidized from methanol; and diluted to 20 per cent total alcohol by volume. This is
method depending upon combustion analysis.
done by taking the specific gravity, as usual, on the distillate
The method most universally used in this country is of the original sample, and assuming that all the alcohol
that given by Leach and Lythgoe in 1905) based upon the present is ethyl alcohol, diluting a measured amount, repredifference in the indices of refraction between the two alcohols. senting 20 volumes of absolute alcohol, to 100 cc. On this
The method is intended to be used with the Hehner Alcohol 20 per cent solution is then obtained the immersion refracTables 15.6"/15.6" C., but this fact was not' stated by the tometer reading, R, and also, from the specific gravity, the
authors in their original article,fl and the method was un- exact percentage, P , of total alcohol by volume, calculated
fortunately inserted, without revision, in the Methods of as ethyl alcohol. This last value may be slightly above
Analysis, Association of Official Agricultural Chemists, 20 per cent, depending upon the amount of methanol present,
1919 and 1924, which uses the Bureau of Standards Alcohol as explained later. The percentage of methanol is then read
Tables 2 O o , / 4 O C. This method will give an error of the off on a graph or table from the difference, R - P. A more
methanol value of 4 to 5 per cent in some cases, mainly detailed description is given under Procedure.
because of the difference in the two temperature standards.
The method is designed to eliminate the inaccuracy, as
well as the calculations necessary, in the method of Leach
Noh-This
f a c t may be shown abstractly b y assuming a pure ethyl
alcohol solution, 15 per cent by weight, which will have a true refractometer
and Lythgoe as printed in the h1ethods of Analysis, A. 0.
A. C. The new method also takes into account the fact
Printed b y permission of t h e Prohibi1 Received February 28, 1927.
that when ethyl alcohol and methanol are diluted the specific
tion Unit, U. S. Internal Revenue Bureau.
2 Compl. rend., 80, 1076 (1875).
gravities do not run parallel. The difference between the
3 J . Chem. SOC.(London), 85, 1 (1904).
specific gravities of the two are greater for dilute solutions
4 Simmonds, "Alcohol,"
p. 183 (1919).
than for strong solutions. When a 20 per cent by volume
6 2. Xahr. Genussm., 24, 7 (1912).
solution of pure methanol is calculated as ethyl alcohol,
6 J . A m . Chem. Soc., 27, 964 (1905).

I T D U S T R I A L 3 5 D E S G I S E E R I S G CHE-VISTRY

July, 1927

the apparent amount of ethyl alcohol is 21.5 per cent. When

met'hanol is 100 per cent, however, and then calculated from
the specific gravity as et,hyl alcohol, the apparent amount
of ethyl alcohol is 99.4 per cent.
Use is now also made of the accurate refractive indices
published b y Doroshevskii and Dvorzhanchik in 1909,'
the et'hyl alcohol indices of which hare been arranged by St'.
John* and calculated to 20" C. for the immersion refractonieter readings.
Good results are obtained even where 1per cent of methanol
in ethyl alcohol is present, but where the sample contains
less than that amount it is recommended that a set of colorimetric standards be made u p using the method outlined
by SVright9 (or the method of Georgia and Moraleslo may be
used). Traces of acetone or other substances have no
appreciable effect upon the accuracy of the method. The
method is rapid, for once the sample is reduced to 20 per cent
by volume of tot'al alcohol, results may be obtained in 30
minutes. It is accurate to within 0.5 per cent of methanol
in alcohol.
Procedure

The percentage of alcohol in the original sample is obtained

by the usual method from the specific gravity, and is recorded
in terms of total alcohol by volume calculated as ethyl
alcohol.
The proper solution is obtained by pipetting a sufficient
amount to give 20 volumes of
absolute alcohol into a 100cc. volumetric flask, and diluting with distilled water to
the mark. Both measuT*enients are made a t 20" C.

845
Table I

%::Fh:F$::f:
R-P

AIxOHOL

% by volume

23.85
23.65
23,45
23.25
23.05
22.80
22.60
22,40
22.20

yi ::
;;:::
21.20

:!:A;

20.60
20,40
20.15
19.95

19.15

$I!:
18.5,5
18.35
18.15
17.95
17.75

i17.10
:;!

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
21.0
22,0
23.0

;:::

26.0
27.0
28.0
29.0
30.0
31.0
32,0
33.0

Di:ggRR-P
16.90
16.70
16.50
16.30
16.10
15.90
15.70
15.50
15.30
15.10
14.90
14.70
14,50
14,30
14.05
13.85
13.65
13.45
13.25
13.05
12.85
12.65
12.45
12.25
12.05
11.85
11.65
11.45
31.25
11.00
10.80
10,60
10.40
10 20

'

%ALCOHOL
by volume
34.0
35.0
36.0
37.0
38.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
46.0
47.0
48.0
49.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
57 .O
58.0
59.0
60.0
61.0
62.0
63.0
64.0
65.0
66.0
67.0

";I,"'g.I~
~
~

D ~ ~ ~ ~ ' E R -

R--P

70ALCOHOL
b y volume

10.00
9.80
9.60
9.40
9.20
9.00
8.80
8.60
8.40
8.20
8.00
7.80
7.60
7.35

68.0
59.0

.In

6.95
6.75
6.55
6.35
6.15
5.95

5.z;

D.D.3

5.35
5.15
4.95
4.75
4.55
4.35
4.15
3.95
3.75
3.55

10.0

71.0
12.0
13.0
74.0
,5.0
76.0
77.0
z8.0
,9.0
80.0
81.0
82.0
83.0
84.0
85.0
86.0
87.0
88.0
89.0
90.0
91.0
02 0
93.0
94.0
95.0
96.0
07.0
98.0
99.0
100.0

The specific gravity determinations and refractometer

readings were made a t about bhe same time to prevent loss

Example:
Sample contains 61.7 per
cent alcohol by volume
20.0 + 64.7 X 100 = 30.9
30.9 cc. made up t o 100 cc.
with water = 20 per cent
alcohol

The Zeiss immersion refractometer scale reading at' 20.0"

C. is obtained on the prepared solution. This reading is called R. By use of a
pycnometer 20"/4" C. on the
same solution the exact percentage of alcohol by volume is obtained from the table for
ethyl alcohol." This percentage is called P.
Note-Depending
upon t h e a m o u n t of methanol present this figure
may be somewhat above 20.0 per cent. T h a t is, i t will be 20.0 per cent if
t h e sample is ethyl alcohol, a n d increase i f methanol is also present, until
t h e percentage will appear 21.5 per c e n t ethyl alcohol when only methanol
is present.

The difference ( R - P ) indicates on the graph or table the

percentage of methanol.
The graph was plotted from results obtained on standards
prepared by t,aking various mixtures of ethyl alcohol and
methanol to give 20 cc. of total absolute alcohol, calculated
from the specific gravity as ethyl alcohol, and diluting with
distilled water to 100 cc. a t 20" C. The curve was then
smoothed out somewhat to agree with the theoretical curve.
7

J. Russ. Phys.-Chem. SOC.,40, 908 (1909); C. A , , 3, 1358 (1909).

Assoc. Official Agr. Chem., Methods, Alcohol Tables, Zeiss Immersion

Refractometer.
9 THISJ O U R X A L , 19, 750 (1927).
10 Ibid., 18, 304 (1926).
1 1 Assoc. Official Agr. Chem., Methods, Specific Gravity Alcohol Tables,
20/40 C.
8

by evaporation of either portion. The standards were

exposed no longer than 10 minutes in the refractometer
beaker before taking readings. The specific gravities of
the standards were obtained by 50-cc. pycnometers and the
percentage of alcohol b y volume taken from the table for
ethyl alcohol. l

Pan American Conference Urges Metric

Standardization
A decisive victory for the metric movement in the Vnited
States was gained at the Pan American Standardization Conference, which recently closed its sessions in Washington, D . C.
By resolution it was declared that the decimal metric weights
and measures should be employed in trade between the United
States and the republics of Latin America. "Manufacturers
and exporters in the United States," i t was stated, "can extend
more readily their operations in Latin America by offering their
products in the same terms t h a t their competitors in Europe do."
The fact was emphasized that all of the twenty Latin American
republics use metric units, as do all the nations of continental
Europe and the majority of other peoples. This decision is
expected t o aid greatly the export trade of the United States
with Latin America.