964

ANALYTICAL CHEMISTRY

together through the 3-way stopcock. If the copper block is a t

room temperature, the meniscus will fall in the right
leg- and rise
in the leftleg.
The copper block is then cooled by direct immersion in liquid
air until the meniscus in the right leg is back to a Dosition near the
upper tungsten contact. Theliquild air is remdved, a glass test
tube slipped over the copper block, and the test tube immersed in
liquid air. The position of the mercury in the manometer then
turns the heater current off and on, so as to maintain the meniscus
near the contact point. The rheostat in the heater circuit and the
depth of the liquid air around the test tube are adjusted so that
the off and on periods for the heater are approximately equal in
duration. Whe:
roperly adjusted the temperature remains
constant to *0.3
When it is desired to increase the temperature of the distil1in.g
tube to the next value, the height of the mercury in the left leg is
reset to the proper position with the mercury in the right leg still
a t the tungsten contact. Without further attention the tpmperature quickly rises to the desired value and then is automatically maintained constant at this point.

For use as both a method of temperature measurement and

temperature control the 120" type 3-way stopcock in the man.
ometer should probably be replaced with a T-type stopcock.
This type of stopcock has an advantage when measuring temperatures, as it permits adding mercury to both legs of the manometer
simultaneously until the meniscus in the right leg just touches thP
contact point. However, when the main application is the presetting of the control point a t some particular temperature and
the control of the temperature a t this point, the 120" type s t o p
cock is believed to be preferable. Although the location of the
stopcock above the bottom of the manometer makes somewhat
inconvenient the removal of all the mercury as required when
filling the thermometer with helium, it has the advantage of permitting relubrication of this stopcock without loss of the helium
from the reservoir.

DISCUSSION

(1) Buffington, R. M., and Latimer, TV. M., J . Am. Chem. SOC.,48,
2305 (1926).
(2) Savelli, J. J., Seyfried, W. D., and Filbert, B. M.,IND.ENQ
CHEM.,A N ~ LED.,
.
13, 868 (1941).
(3) Scott, R. B., J . Research .VatZ. BUT.
Standards, 25, 459 (1940).
(4) Shepherd, M., Ibid., 2, 1145 (1929); 26, 227 (1941).
(5) Southard, J. C., and Miluer, R. T., J . Am. Chem. SOC.,55, 4384
(1933).
(6) Ward, E. C., IND.ENG.CEIEM.,ANAL.ED.,10, 169 (1938).

'

This control unit has been found to be a very satisfactory means

of both adjusting and controlling the temperature required for

isothermal distillations a t low temperatures. The operation of

the thermometer is very simple and it requires a minimum of
attention from the operator. The apparatus should also be
applicable to the control of low temperatures as required in other
problems.

LITER4TURE CITED

RECEIVEDMaroh 1, 1948.

Quantitative Colorimetric Microdetermination of Methanol

with Chromotropic Acid Reagent
R. N. BOOS, Merck & Co., Znc., Rahway, N. J .
.4 rapid, accurate, and specific method for the quantitative determination of

methanol is described in which the methanol is oxidized to formaldehyde and

the latter measured colorimetrically with chromotropic acid. The method permits the determination of methanol with a relative error of <2'3&.

OBMALDEHYDE when heated with chromotropic acid

(1,8-dihydroxynaphthalene-3,6-disulfonicacid) in the presence of sulfuric acid gives rise to an intense violet-red color
( 1 , 2, 4). The formation of this color is the basis for the analytical method for methanol described below ( 7 ) . This method was
developed in connection with a problem requiring a rapid, accurate, and specific determination of methanol for which other
available methods, including the Zeisel method for alkoxy1
groups, were unsuitable. The specificity of the reaction is
indicated by the fact that the,following aldehydes do not react
with chromotropic acid to give a colored solution: acetaldehyde,
propionaldehyde, butyraldehyde, isobutyraldehyde, isovaleraldehyde. crotonaldehyde, chloral hydrate, glyoxal, benealdehyde, and phthalaldehyde. Glyceraldehyde gives a yellow
color (4).
REAGENTS

Methanol, reagent RIerck. Dilute phosphoric acid, 10 ml. of

60% acid diluted to 100 ml. Potassium permanganate, 57,
aqueous solution. Sodium bisulfite, reagent Merck, saturated
Rolution. Concentrated sulfuric acid.
Chromotropic acid, Eastman Kodak (P-1613), 2% aqueous
solution. Ten milliliters of the acid solution are prepared and
stored in a brown bottle. The solution darkens rapidly on standing unless preserved by cold storage.
PROCEDURE

The organic material is weighed into a distilling flask with 4 ml.

of water and distilled. Three milliliters of the distillate are col-

lected and diluted according to the expected methanol content

(the test solution). One milliliter of the test solution is transferred to a 10-ml. volumetric flask, to which are subsequently
added 3 drops of dilute phosphoric acid and 5 drops of potassium
permanganate solution (5). The solution is kept a t room temperature for 10 minutes with occasional swirling to ensure oxidation of the methanol to formaldehyde. Sodium bisulfite is then
added dropwise to the solution to reduce the excess permanganate.
The solution is cooled by swirling the flask in an ice bath while
4 ml. of cold concentrated sulfuric acid are added. If a buret is
used for the measurement of the sulfuric acid, the stopcock
should be lubricated with concentrated sulfuric acid only.
Four drops of chromotropic acid reagent are added to the solution and the 10-ml. volumetric flask is placed in a water bath at
60' C. for 15 minutes, during Tvhich time the flask should be
swirled occasionally. The flask is removed from the water bath
and cooled in an ice bath. Distilled water is added to bring the
level to within 2 mm. of the mark on the flask. The flask is
stoppered, shaken, and allovied to stand until the solution is at
room temperature, Sufficient distilled water is then added to
bring the level of the solution to the mark.
A blank is run on 1 ml. of distilled water each day, as chromotropic acid solution darkens with time. The solutions under test
and the blank are transferred to t t e cells of a Beckman spectrophotometer and compared a t 5800A. ( 5 ) . (Evelyn and Coleman
photometers have also been employed successfully.) The quantity of methanol in the test solution is then read from an optical
density-concentration curve which is determined as follows: A
series of aqueous methanol solutions containing from 20 to 100
micrograms of methanol per milliliter of solution is prepared and
treated according to the above procedure. The colored solution6
are stable for a t least 3 days.

V O L U M E 20, NO. 10, O C T O B E R 1 9 4 8

The following results are typical of the agreement obtained
between the Zeisel and the proposed colorimetric method when
methanol was the only alcohol present:
Zeisel,

70

5.5
4.8

Colorimetric,

70

5.0,5.2

5.0

The procedure here described may be employed to advantage

In the determination of methoxyl groups in methyl esters ( 6 ) .

As an example, a sample of dimethyl tartrate was saponified

with 4 ml. of 5 S sodium hydroxide. After 3 ml. of distillate had
been collected, the latter was diluted and its methanol content de-

965
termined by the procedure described. The results showed 2.0
moles of methanol as compared with a theoretical value of 2
moles.
LITERATURE CITED

(1) Boyd and Logan, J . B i d . Cham., 146, 279 (1942).

(2) Bricker and Johnson, ISD.ENG.CHEM.,
AN.4L. ED.,17,400 (1945
(3) Eegriwe, E., MGcrochim. Acta, 2, 329 (1937).
(4) Eegriwe, E., 2. anal. Chem., 110, 22 (1937).
(5) MacFayden, D. A , , J . BioZ. Chem., 158, 107 (1945).
(6) Snell and Snell, Colorimetric Methods of Analysis, Vol. 11, p
17, New York, D. Van Nostrand Co., 1937.
(7) U. S.Pharmacopoeia, 12th rev., p. 428. 1932.
RECEIVED
October 2 5 , 1947.

ELECTRON MICROSCOPE GONIOMETRY

A. F. KIRKPATKICK AND EVELYN G.4GNON D.4VIS
Stamford Research Laboratories, American Cyanamid Company, Stamford, Conn.
The frequent occurrence of unknown crystals in
electron microscopical samples presents the problem
of their identification. Their relatively small size
severely limits the ordinary methods of identification. The silhouette angles observed on the screen
or photographic plate are practically all the data
available to the electron microscopist. These
angles are functions of the interfacial angles of the
crystals and the orientation with respect to the
screen or plate. The interfacial angles, constants of

H h frequent occurrence of unknown crystals in electron

microscopical samples presents the problem of identification.
The microscopic size of the crystals or the nature of the sample
severell limits the ordinary methods of identification. Precipitated materials, pigments, and by-products, such as calcium
carbonate, which is used as the illustration in this paper, are an
example of the occurrence of microscopic sizes. Crystals associated v i t h other materials in such a manner that separation
is not possible, such as crystals attached to fibers or even to other
crystals, especially when common ions are present, illustrate
the limits due to the nature of the sample. The history of the
samples usually limits the number of possibilities and the problem
then can be reduced to confirmation of a suspected identity.
The authors were presented with the problem of identification of
crystals in electron micrographs n ith the suggestion that the
silhouette angles, practically all the data available to the electron microscopist, be considered as data for the confirmation of
identity. It was then realized that crystallographical concepts
could be applied to this problem.
ORIGIN AND NATURE OF PROBLEM

Electron micrographs of industrial sludges from the carbon

dioxide and sulfuric acid processes for the extraction of cyanamide from crude, commercial calcium cyanamide showed outlines of relatively small crystals (ca. 3 to 5, in breadth). The
nature of the sample suggested that the crysta!s might be calcite.
The confirmation of this hypothesis by a determination of some
physical property was desired. The identification of the crystals
as the calcite phase of calcium carbonate was confirmed by the
use of electron microscope goniometry.
Figure 1 is an electron micrograph of one of the crystals. Its
general appearance suggested that the crystal might be one of
calcite lying on a rhombohedral face.
Figure 3 is an orthographic projection of a calcite crystal showing only the unit rhombohedron, r { 1071 ]. The projection plane is
parallel to the face r,(lOil) and the crystal is lying on r6(iOlT).

a suspected compound as obtained from the literature, can be used to calculate the angles of an orthographic projection of the crystal, which is observed
with the electron microscope. A comparison of the
angles measured with those calculated may establish the identity of the crystal. It may be possible
to determine directly axial elements (axial ratios and
interaxial angles) and interfacial angles of unknown
crystals. This represents the determination of
physical constants with the electron microscope.

The solid lines represent the viaible edges, and the dotted lines
represent the edges not directly visible.
All faces in this form are identical; however, in the projection,
faces parallel to the projection plane show their true size, whereas
those a t an angle are reduced in size. -4ngle A is the angle between edges T2T6 and w 6 , and showvs the true value. Angle C i p
the angle between the projections of edges Tar6 and ~ 3 r d . The
plane formed by these edges in space is a t an angle to the projection plane: therefore, the angle between the edges as projected ie
different from the true value. The calculation of this angle, from
the axial elements and others such as B and C, is the problem for
the electron microscopiht. (In this paper interedge angles arc
considered as internal angles.)
Donnay and OBrien (4)showed how the apparent interedge
angles of crystals observed with the optical microscope could be
correlated with true interfacial angles and the axial element,.
They demonstrated how known methods of crystal drawing and B
knowledge of the spherical projection and its derivatives, the
stereographic and cyclographic projections, could be applied to
graphical calculations.
In electron microscopy, the silhouette angles of crystals are
practically the only determinative data available. In this paper
are presented the application of microscope goniometry to the
study of electron micrographs and the use of silhouette angles
for the determination of physical constants by means of the
electron microscope. The calculations follow the methods presented by Donnay and OBrien (4).
Calculation of Angles of Orthographic Projection. Figure 4 is
a stereographic projection of a calcite crystal showing only the
unit rhombohedron { loill. I t is derived from the interfacial
angle (OOOl):(lOil), which is 4436 (Dana, 2). This projection
was constructed with the use of the Wulff net (Donnay and
OBrien 4).
Point C is the projection of the polar axis of the fundamental
sphere of projection and of the c crystallographic axis. The three
points, UI, a2, and u3,are the positive poles of the three horizontal
axes of the hexagonal system. The three points, r l , T P , and
(double circles), are the stereographic projections of the face poles
which are above the equatorial plane of the fundamental sphere.