Colorimetric Determination of Silica in

Boiler Water
M. C. SCHWARTZ,~
Louisiana Steam Generating Corporation, Baton Rouge, La.

ards standardized in a similar fashion against

I
XFORMATION (3, 13) on the forma-
tion and methods of prevention of silica silica solutions. Figure 2 represents the data
of Table I.
boiler scale is becoming increasingly
more important in considering the design TABLEI. EFFECTOF VARYINGPH ON
of modern high-pressure steam plants. The COLORINTENSITY
APPARBNT slLIC.4
a n a l y t i c a l d e t e r m i n a t i o n of silica is HYDROCHLORIC ACID CONCENTRATION P H ~
naturally of fundamental importance in the M1. P. p . m.
consideration of such problems and is 0.25 (1 to 1) 35.0 1.85
0.5 (1 to 1) 35.9 1.39
capable of high accuracy (6), but the length 1.0 (1 to 1) 36.7 1.12
1.5 (1 to 1) 36.0 0.85
of time required to complete the analysis is 1.0 Concentrated acid 35.5 0.71
too long for certain types of investigations. 1 . 0 Concentrated acid +
0.5 ml. (1 to 1) 34.6 0.82
I n such instances one must resort to a 2.0 Concentrated acid 13.8 0.41
a Determined with quinhydrone-saturated calomel
more rapid method of analysis, such as electrode. The p H values although definitely re-
colorimetry. WAVE LENGTH MILLIMICRONS producible are not precise measurements of hydro-
FIGURE1. SPECTROPHO- gen-ion concentration because of 8ome reducing effect
Solutions containing dissolved silica react of quinhydrone on the silicomolybdate present in
TOVETRIC COMPARISOV OF solution.
with acid solutions of ammonium molyb-
STANDARDS
date to form colored silicomolybdates; EFFECTO F AMMONIUMM O L Y B D a T E CON-
soluble phosphates and iron salts likewise CENTRATION. Two m i l l i l i t e r s of c a l c i u m ,
form complex colored molybdates. The chloride solution were added to 100 ml. of
boiler water. After 1 hour the solution was
reactions (1, 3, 4,7-12, f4-16) are com- filtered, and enough of the filtrate was added
plicated and, although various complex to 1 ml. of a 1 to 1 solution of hydrochloric
molybdates have been isolated and pre- acid and the various amounts of molybdate
pared in a pure state, their existence in solution indicated in Table I1 to make up 50
ml. Figure 3 represents the data of Table 11.
solution is somewhat conjectural, owing to
the important effect of the hydrogen-ion TABLE 11. EFFECTOF VARYING AMMONIUM
concentration on the various equilibria MOLYBDATE COKCEKTRATION ON COLOR
FIGURE 2. EFFECT OF VARY- INTENSITY
existing. ING PH ON COLORIATEASITY
APP.4RENT SILICA
APPARATUS. Two colorimeters were MOLYBDATE SOLCTION CONCENTRATION
used, a 40-mm. Bausch and Lomb Du- lM1. % P . p . m.
0.5 10 13.3
boscq type and a 50-mm. Hellige Duboscq. 1.0 10 38.2
A Macbeth daylight lamp was used as the 2.0
2.0
10
25
39.7
38.6
source of i l l u m i n a t i o n . Hydrogen-ion 4.0 25 32.0
measurements were made using the hy- EFFECTOF TIME. Two milliliters of cal-
drogen-saturated calomel electrode and the cium chloride solution were added to 100 ml.
quinhydrone-saturated calomel electrode of boiler water. After 1hour the solution was
combinations. filtered, and enough of the filtrate was added
STANDARDS. Picric acid and potassium FIGURE to 2 ml. of 10 per cent ammonium molybdate
3. EFFECT OF AMMONIUMsolution and 1 ml. of 1 to 1 hydrochloric acid
chromate solutions have been used as MOLYBDATECONCENTRATION ON to make up 50 ml. Figure 4 represents the
permanent liquid standards. A spectro- COLORINTENSITY data of Table 111.
photometric comparison (prepared by A. C. TABLE111. EFFECTOF TIME ON COLOR
Hardy, Massachusetts Institute of Tech- INTENSITY
nology) of these liquids with a silicate solu- APPARENT SILICA
tion is shown in Figure 1. TIXE CONC~NTRATION
Min. P. p . m.
REAGENTS.C a l c i u m c h l o r i d e : 111 0 43.7
grams of c. P. anhydrous calcium chloride FIGURE 4. EFFECT OF TIMEON 10
25
43.7
43.7
per liter of solution (1 M ) . Ammonium COLORINTENSITY 45 43.0
molybdate: 10 and 25 per cent solutions 70 41.5
90 40.0
of (NH4)6M07024.4H20. Hydrochloric acid: concentrated
acid and 1 to 1 acid (by volume). Blank tests should be EFFECTOF INITIAL PH. Either sodium hydroxide or hydro-
made on these reagents for the presence of silica. chloric acid was added to 125 ml. of boiler water to produce the
desired initial pH. Two milliliters of calcium chloride solution
were added and the solution filtered after 1hour. Two milliliters
EXPERIMENTAL RESULTS of ammonium molvbdate and 1 ml. of 1 to 1 hydrochloric acid were
EFFECTOF VARYING P ~ T~~ , milliliters of calcium chloride added to 50 ml. Gf sample. In some instances the volume and
solution were added to 100 ml. of boiler water, After 1 hour the concentration of the acid added had to be varied to maintain a
solution was filtered, and enough of the filtrate was added to 2 colorimetric PH value of about 1.1. Somewhere between a PH
ml, of 10per cent ammonium molybdate solution and the various of 12.69 and 12.87 calcium hydroxide precipitates from the Soh-
amounts of acid indicated in Table I to make UP 50 ml. The tion. Figure 5 represents the data of Table IV.
colored solutions were compared with the appropriate silica stand- EFFECT O F BUFFER SOLUTION. The Wantities of buffer
solution indicated in Table VI were added to 100-ml. samples
1 Boiler Feedwater Fellow, Institute of Industrial Research, Louisiana of boiler water. The data of Table VI are represented in Fig-
State University. ure 6.
364
September 15,1934 INDUSTRIAL AND ENGINEERING CHEMISTRY 365
TABLEIV. EFFECTOF INITIAL PH OF BOILERWATERON ERROR calcium chloride solution were added and the solution was filtered
IN DETERMININQ SILICA after 1 or 2 hours. The pH was redetermined. Two milliliters
INITIAL
PH" SILICAFOUND E R R O R b FINALPHC of ammonium molybdate solution and 1 ml. of 1 to 1 hydro-
P.p . m. P. p. m. chloric acid were added to 50 ml. of solution and the silica and
1 8.62 59.1 +lS.l 0.98 pH determined. The data of Table VI11 are represented in
2
3
9.24
9.61
48.9
46.0
+ 7.9 1.01
f 5.0
Figure 7.
0.99
4
5
9.97
10.12
41.1
41.1
+
+ 0.1
0.1
1.10
1.09 TABLEVIII. COLORIMETRIC
DETERMINATION
OF SILICA IN
6
7
10.32
10.46
41.2
40.7
+ 0.2
- 0.3
1.10
1.10
BOILERWATER
8 10.68 40.7 - 0.3 1.10 (In presence of phosphate)
9 10.96 39.8 - 1.2 1.08 PHa O F PH
10 11.14 31.9 - 8.1 1.09
11.14 31.3 - 8.7 0.76 BUFFER INITIAL AFTER
SOLUTION P H ~ PPTN." SrLxcab ERRORC
FINAL
PH d
11 11.53 10.1 -30.9 1.15 P.p . m. P. p . m.
11.53 Too faint to be read 0.30
11.08 11.26 10.94 55.5 - 4.5 1.27
12 12.10
12.10
3.7
4.4
-37.3
-36.6
1.64
1.16 10.43
10.26
10.83
10.61
10.47
10.29
59.5
58.8
+
0.5
- 0.2
1.25
1.25
+++
12.10 4.2 -36.8 0.80
12.10 Too faint to be read 0.52 9.92 10.12 9.94 59.6 0.6 1.25
13 12.37 <3.7 >37.3 1.24 9.63 9.72 9.60 59.5 0.5 1.25
9.41 9.48 9.40 59.4 0.4 1.25
+++
12.37 Too faint to be read 0.82
14 12.69 Too faint to be read 1.00 9.17 9.23 9.10 61.8 2.8 1.25
15 12.87 .... 9.02
8.48
9.13
8.79
9.00
8.62
62.5 3.5 1.19
64.8 5.8 1.14
16 13.07
13.07
4:2
5.0
-36.8
-36.0
1:ss
0.66 8.04
7.61
8.46
8.19
8.28
8.04
68.0
71.9
+
9.0
+12.9
1.10
1.04
17 13.58 16.8 -24.2 1.25
18 13.85 11.1 -29.9 0.28 7.27 8.02 7.83 75.0 fl6.0 1.04
Determined with hydrogen-saturated calomel electrode. a Determined with hydrogen-saturated calomel electrode.
6 Average result of gravimetric analysis, 41.0p. p. m. b Dilution factor, 1.54.
C Determined with the quinhydrone-saturated calomel electrode, re re Average result of gravimetric analysis, 59.0 p. p. m.
sents the pH value of the solution after addition of ammonium molybcfat; d Determined with quinhydrone-saturated calomel electrode.
and hydrochloric acid.
EFFECTOF ALUMINUM. Solutions of boiler water were pre-
TABLEV. EFFECTOF PHOSPHATE PRECIPITATION ON INITIAL pared containing the proper amounts of aluminum and the initial
PH OF BOILERWATER pH was adjusted by adding hydrochloric acid. Two milliliters
EQUILIBRIUMP H ~ of calcium chloride solution were added. The sample was filtered
INITIALPHG (AFTBIR PHOSPHATE after 1 hour and the pH determined. The silica was deter-
PRECIPITATION)
9.61 7.36 mined colorimetrically and the pH was determined again.
9.97
10.12
7.38
7.69
The data of Table IX are represented in Figure 8.
10.32 7.84
10.46 7.92
TABLEIX. EFFECTOF SOLUBLE ALUMINUMON COLORIMETRIC
Determined with the hydrogen-saturated calomel electrode. DETERMINATION
OF SILICA
IN BOILER
WATER
PH AFTER
In order to determine the proper range of pH for phos- INITIAL PHOSPHATE ALUMINUM FINAL
pHa PRECIPITATION^ ADDEDb pHC SILICAd
phate precipitation more precisely, the fractional precipita- P. p. m. P. P. m.
tion of calcium phosphate and silicate was investigated with 10.23 9.09 0 1.03 62.2
10.25 8.85 6 1.03 45.0
the use of a series of buffer solutions (Table VII). 10.24 8.95 10 1.05 33.6
10.24 8.78 20 1.07 15.9
10.25 8.81 30 1.07 9.1
TaBLEVI. EFFECTOF ADDINQBORATE-SODIUM HYDROXIDE 10.25 8.87 50 1.08 approx. 3
BUFFER"SOLUTION(4) ON PH VALUESO F BOILER WATER a Determined with hydropen-saturated calomel electrode.
b Source of aluminum, aluminum chloride.
BUFFER PH BEFORE PH AFTER C Determined with the quinhydrone-saturated calomel electrode.
SOLUTION PHOSPHATE PHOSPHATE d Average result of gravimetric analysis, 64.2 p. p. m.
ADDED PRBICIPITATION
b PRECIPITATION
b
M1.
0 7.26 TABLEx. EFFECTOF I R O N O K COLORIWETRIC DETERMINATION
10 9.52 OF SILICAIN BOILERWATER
20 9.69
30 9.81 PH A F T l R
40 9.86 INITIAL PHO0PHATE IRON FINAL
50 9.89 PH" PRECIPITATIO~-$~ ADDEDb SILICA^ PHd
100 10.00 P. p . m. P. p . m.
a Borate solution, 12.404 grtms of HaBOs and 100 ml. of M NaOH per 10.24 9.72 0 61.3 1.04
liter. Sodium hydroxide solution 0.1 M . The buffer solution consists of 10.24 9.75 2 61.1 1.05
equal parts of borate and sodium hydroxide solution. 10.22 9.75 5 60.5 1.04
b Determined with hydrogen-saturated calomel electrode. 10.26 9.73 10 52.5 1.04
a Determined with hydrogen-saturated calomel electrode.
Fifty milliliters of buffer solution were added to 110 ml. of b Source of iron ferric chloride.
C Average resuli of gravimetnc analysis 63.0 p. p. m.
boiler water and the pH was determined. Two milliliters of d Determined with quinhydrone-saturatkd calomel electrode.

TABLEVII. BUFFERSOLUTIONS
COYPOSITION" EXPBICTBID
PH ACTUAL
pHb TBIMPZORATURBI RIFIRENCBI(4)
c.
75 ml. I
80 ml. I
++ 75 ml. I1
70 ml. I1
10.93 11.08
10.43
24
25
p. 208 ( 5 borate
p. 208
+ 5 NaOH)
82.5 ml. I + 67.5 ml. I1
e . . .

10.36; * 10.26 24 p. 208 ( 8.5 borate + 4.5 NaOH)

82.5 ml. I
90 ml. I
105 ml. I
+++ 67.5 ml. I1
60 ml. I1
10.36
9.87
10.22
9.92
25
25 p. 208 ( 6 borate ++ 43 NaOH)
NaOH)
120 ml. I
150 ml. I
+ 45 ml. I1
30 ml. I1
9.60
9.44
9.19
9.63
9.41
9.17
25
25
24
p. 208 ( 7 borate
p. 208 ( 8 borate
p. 208 10 borate)
+ 2 NaOH)
135 ml. I + 15 ml. I11
97.5 ml. I f 52.5 ml. I11
9.04
8.47
9.02
8.48
24
24
p. 209 9 borate
p. 209 6.5 borate
+ +1 HC1)
3.5 HCl)
37.6 ml. V
18 ml. V
++ 112.5 ml. IV
132 ml. IV
7.94 (IS")
7 46C 18')
8.04
7.61
24
23
(
p. 213 2.5 borate
p. 213 ( 1.2 borax +++9.4
7.5 HC1
8.8 €LIB&)
9 ml. V + 141 ml. IV 7:09 [18') 7.27 23 p. 213 ( 0.6 borax HaBOa)
BKffe:r solutions:
1, 12.?04-gra%e._of HsBOa and 100 ml. of M NaOH per liter.
11 0.1 M NaUH.
11i 0.1 M HCl.
IV ' 12 404 grams of H3BO3 per liter.
V 'I9.iOSgrams of NazB401.
b Buder solutions were not prepared rigorously. Value0 determined with the hydrogen-saturated aalomel electrode.
Interpolated values.
365 ANALYTICAL EDITION Vol. 6, No. 5
I1
t

INCOMPLETE PRECIPITATION
OF PHOSPHATES
$ I,”
8 0
‘Fi
0 1
ML BWFER SOLITON ADDED
-5
6. EFFECTOF BUFFERSOLU-
FIGURE
TION ON PH VALUES

PRECIPITATION
-30
-35
.A0

FIQURE
5. EFFECT PHON
OF INITIAL FIGURE7. DETERMINATION
OF SILICA FIQURE8. EFFECTOF SOLUBLE
ERRORIN DETERMINING
SILICA IN PRESENCEOF PHOSPHATE ALUMINUMON COLORIMETRIC DE-
TEFMINATION OF SILICA

EFFECTOF IRON.Solutions of boiler water were prepared
containing the proper amounts of iron and the initial pH was
adjusted by addin sodium hydroxide. Where 2 p. p. m. of iron
were added, a sligkt turbidity appeared, as well as precipitates
in the subsequent samples. However, the solutions were not
filtered. Two milliliters of calcium chloride solution were added.
The sample was filtered after 1 hour and the pH determined.
Silica was determined colorimetrically and the pH was re-
determined. The data of Table X are represented in Figure 9.
OF RESULTS
SUMMARY
The yellowish green color of the silicomolybdate complex
(approximate silica concentration 50 p. p. m.) develops its
maximum intensity (1) at a p H of approximately 1.1;
(2) a t a concentration of ammonium molybdate correspond-
ing to approximately 2 ml. of a 10 per cent solution; (3)
practically instantaneously if the molybdate and acid solu-
tions are added in quick succession; and remains so for ap-
proximately one-half hour, after which i t diminishes.
The precipitation of phosphates from boiler water by cal- publish this paper, and T. E. Crossan, superintendent of the
cium chloride results in a drop in the pIf of the solution.
The proper initial pH range of the boiler water for complete ment. Acknowledgment is also made of the assistance
removal of phosphates without precipitation of silica is 9.5 rendered by W. B. Gurney, L. Young, and J. C. Hill, all of the
to 10.5.
The use of a sodium hydroxide-borate buffer solution of
pH 10 maintains the proper p H for the removal of phosphates.
The presence of aluminum in the boiler water as an alumi-
nate reduces the determined silica concentration of the boiler
water, particularly near pH values of 10, by actual reaction in
the presence of calcium chloride.
Although very little iron can exist in solution in boiler water
of p H approximately 11, the effect of adding iron on the
colorimetric determination of silica has been determined as
resulting in an apparent decrease probably due to adsorption
of silica on ferric hydroxide.
PROCEDURE
As a result of the preceding work, the following reagents
and procedure were developed:
SODIUMHYDROXIDE-BORATE BUFFER S LUTION. Solution
A, 12.40 grams of boric acid plus 100 ml. of9sodium hydroxide
per liter. Solution B, 0.1 M sodium hydroxide. The buffer
solution is made by takin 6 parts of solution A and 4 parts of
solution B. The buffer issept in a hard-rubber bottle.
CALCIUM CHLORIDE SOLUTION.1 M calcium chloride.
AMMONIUMMOLYBDATE SOLUTION.Ten per cent solution of
(NH~)~Mo~O~~~~H~O.
HYDROCHLORIC ACID. Three volumes of concentrated acid to
2 volumes of distilled water.
Calcium chloride, ammonium molybdate, and hydrochloric
acid are kept in Pyrex glass bottles. Silica 62
blanks should be taken on the reagents.
PROCEDURE. To 110 ml. of boiler water 6o
add 50 ml. of buffer solution, 2 ml. of 58
calcium chloride solution, and stir vigor-
ously. A flocculent precipitate of calcium
phosphate forms which settles rapidly.
Allow the solution to stand for approxi-
mately 2 hours (in any event, a t least 1
hour) with occasional stirring, and then
filter. To 50 ml. of the filtrate add 2 ml. FxURE 9. ~ F F E a
of ammonium molybdate solution and 1 OF IRON ON COLORI-
ml. of 3 to 2 hydrochloric acid solution. Af- lKETRIC DETERMI-
ter allowing the solution to stand for 10 to NATION OF SILICA
15 minutes, compare the silica color in-
tensity with an appropriate potassium chromate or picric acid
silica standard. Subtract the buffer blank from the calculated
reading and multiply the result by the dilution factor (1.54).
ACKNOWLEDGMENTS
The author wishes to thank R. S. Nelson, president of the
Louisiana Steam Generating Corporation, for permission t o
corporation, for highly valued suggestions and encourage-
Louisiana Steam Generating Corporation.
LITERATURECITED
(1) Arnfeld, Dissertation, Berlin, pp. 1-60 (1899).
(2) Asch, W., a n d Asch, D., “Silicates in Chemistry a n d Com-
merce,” p. 16, D. Van Nostrand Co., N. Y.,1914.
(3) Christman. C. H., Holmes, J. A., and Thompson, H., IND.
23, 637-46 (1931).
M., “Determination of Hydrogen Ions,” p. 208,
& WiIkins, Baltimore, 1928.
(5) Copaux, H., BUZZ. soc. chim., 13, 324-32 (1913): C m p t . rend.,
156,71-5 (1913).
(6) Hillebrand, W. F.,U. 8. Geol. Survey, BUZZ. 700, 104 (1919).
(7) Krumholz, Paul, 2. anorg. allgem. Chem., 212, 91-6 (1933).
(8) Malaprade, L.,Ann. chim., (10) 11, 104-22 (1929).
(9) Melikov, P.,Compt. rend., 153, 1478-9 (1911).
(10) Miolati, A,, J . prakt. Chem., 77, 417 (1908).
(11) Rosenheim, A., Z. anorg. Chem., 34, 446 (1903).
(12) Rosenheim, A.,and Jaenicke, J., 2. anorg. allgem. C h m . , 101,
235-75 (1917).
(13) Stumper, R.,Wtlrme, 55, 272-8 (1932). See this article for
earlier references.
(14) Travers, A.,and Malaprade, L., Compt. rend., 183,292-4 (1926).
(15) Tschopp, Ernst, and Tschopp, Emilio, Helv. Chim. Acta, 15,
738-809 (1932).
(16) W u , Hsein, J . BioZ. Chem., 43,189-220 (1920).
LITERATURE
ON COLORIMETRIC
DETERMINATION
OF SILICA
Atkins, W. R . G., J . Marine BioZ. Assoc. United Kingdom, 14, 89
(1926); 15, 191 (1928).
Atkins, W. R . G., and Wilson, E. a,,Biochem. J.,20, 1223-8 (1926).
September 15,1934 I N D U S T R I A L A N D E N G I N E E R I N G C H E M IS T R Y 367

Bertrand, G., Bull. aoc. china. b i d , 6, 656-8 (1924).
Dienert, F., and Wandenbulcke, F., Compt. rend., 176, 1478 (1923);
Bull. soc. chim., 33, 1131 (1923).
Feigl, F., and Krumholz, P., Be?., 62B, 1138-42 (1929).
Fougler, J. H., J. Am. Chem. SOC.,49, 429-35 (1927).
Harman, R. W., J. Phya. Chem., 31, 616 (1927).
Isaacs, M. L., Bull. aoc. chim. biol., 6, 157 (1924).
Jollea, A., and Neurath, F. Z., 2. angew. Chem., 11, 315 (1898).
King, E. J., J. Bid. Chem., 80, 25 (1928); Contrib. Can. Bid. Fish-
em'es, 7, Nos. 8-11, Series D, Nos. 1-4, 121-5 (1931).
King, E. J., and Lucas, C. A., J. Am. Chem. SOC.,50, 2395-7 (1928).
Liebknecht, O., Gerb, L., and Bauer, E., J . angew. Chem., 44, 860-3
(1931).
Lincoln, A. T., and Barker, P., J. Am. Chem. SOC.,26, 975 (1904).
Lorenz, R., and Bergheim, E., 2. anorg. allgem. Chem., 136, 95-6
(1924).
Nemec, A,, Biochem. Z.,190, 42 (1927).
Oberhauser, F., and Schormuller, J., 2. anorg. Chem., 178, 381-8
(1929).
Salvadori, R., and Pellini, G., Gam. chim. ital., 30, 191 (1900).
Schreiner, O., J. Am. Chem. Soc., 25, 1056 (1903); 26, 808 (1904).
Thayer, L. A., IND. ENG.CHEM.,Anal. Ed., 2, 276-83 (1930).
Thompson, T. G., and Houlton, H. G., Ibid., 5, 417-18 (1933).
Veitch, F. P., J. Am. Chem. SOC.,25, 169 (1903).
Winkler, L. W., 2. angew. Chem., 27, 511 (1914).
Woodman, A. G., and Cayvan, L. L., J. Am. Chem. Soc., 2 3 , 9 6 (1901).
RFCEIVED May 16, 1934. Presented before the Division of Water, Sewage,
and Sanitation Chemistry at the 87th Meeting of the American Chemical
Society, St. Petersburg, Fla.. March 25 to 30, 1934. The present paper
includeu a portion of a program of boiler feedwater research being carried
out at the Louisiana Steam Generating Corporation under the general
direction of E. B. Powell, Stone and Webster Engineering Corporation, Bos-
ton, Mass., with the cooperation of the Institute of Industrial Reaearch,
Louisiana State University, and with the collaboration of S. T. Powell,
Baltimore, Md.

A Microscope Cold Stage with Temperature

Control
C. W. MASONAND T. G. ROCHOW,Cornel1 University, Ithaca, N. Y.

in place by vaseline. A hole for the reception of a low-

T
HE microscopist may be called upon to examine a speci-
men below room temperature in order that he may temperature thermometer extends into the central chamber.
observe temperatures, appearances, and optical prop- The whole stage is insulated by 5-mm. sheet cork, held in
erties of the specimen during freezing and thawing, trans- place by pins and rubber cement. Several layers of alumi-
formation, or chemical reaction. The apparatus to be de- num foil, cemented by rubber cement, pSotect the insulation
scribed consists of a cold stage and devices for controlling the from sweating. The cold stage is clamped on any microscope
temperature, and is designed for use at temperatures down to having a fairly roomy stand, preferably after removal of the
-25' C. and even lower. Accurate control of the tempera- rotating stage.
ture, to within 0.1' C., is considered important but means are CIRCULATORY SYSTEM. The complete system for circu-
also provided for quickly changing the temperature. lating cooled liquid through the stage is also shown in Figure
A simple cold stage has been described by Chamot and 1. Dried air passes into the air lift, L,where the liquid of
Mason ( I ) , and was used in 1928 in her study of the freezing the cooling system is forced up into the reservoir, R . From
of emulsions by Miss Newcomer (W), who cooled the stage there the liquid flows down into!the cooling coil, C, and then
with alcohol, flowing by gravity through a cooled copper either through the cold stage, S , or across the shunt, H , to
spiral. The present apparatus represents an improvement return to the air lift, completing the circuit.
in the design of the circulatory system so as to include an AIR LIFT. The air lift, L, is constructed 'as follows:
air lift for pumping the liquid around the system and a shunt One end of a piece of 6-mm. glass tubing is drawn and bent
for more accurate control of the temperature of the stage. into a curved nozzle with 2-mm. opening. Another piece of
tubing is drawn out, 10 mm.
APPARATUS
COLDSTAQE.T h e cold
m. from the end, into a neck about
25 mm. lone and 3.5 mm. in
diameter a t i t s narrowest part.
The bent nozzle is inserted into
s t a g e , p a r t S of F i g u r e I, the second tube at the lower
may be made by any com- end of its constriction. The
petent mechanic from a plate s t r a i g h t p a r t s of t h e two
members are s e p a r a t e d b y
of a l u m i n u m about 70 X pieces of cork and are bound
100 x 10 mm.; the upper together by copper wire. The
s u r f a c e of t h i s p l a t e i s assembly is placed in a large
c h a n n e l e d a n d a second test tube, 2.8 X 25 cm., which
is filled with the liquid to be
plate, 3 mm. thick, is fastened circulated and sealed with a
tightly upon it by means of rubber stopper with holes for
a lead foil g a s k e t , G, and the two tubes of the air lift and
closely spaced screws. The another hole for the return-
line.
c h a n n e l thus constitutes a The air, a d m i t t e d from a
tube for circulation of a cool- low-pressure air line, has its
ing agent t h r o u g h what is velocity further reduced by
substantially a block of alu- means of two stopcocks in a
side-arm U - t u b e , containing
minum. An opening, 19 mm. calcium chloride for drying the
in diameter, is provided for air so as to avoid diluting the
the specimen, and recessed circulating liquid w i t h con-
a t its edges to take windows densed water from the air. A
T-tube, T,with a stopcock in
of 25-mm. r o u n d c o v e r - the branch, is inserted between
glasses, the lower one sealed FIGURE1. DIAGRAM OF COLDS T A ~AND
E COOLINQ SYSTEM the U-tube and the a i r lift.