STANDARD MIXED CHLORIDE SAMPLES THE EFFECT OF BALL H I L L GRINDING AND HIXING ON THE ACTUAL A N A Y S E S AS COHPARED WITH CALCULATED VALUES
G. FREDERICK SMITH University of Illinois, Urbana, Illinois INTRODUCTION
T
HE preparation of student samples for practice analyses, in case large classes are involved, is a difficult problem. If a number of individual students are to be given the same samples for analysis, the sample should be made for a single semester's use; otherwise such a series of samples soon discontinue to be "unknowns." For a single semester's use in a class of fifty to one hundred students ten separate samples may be sufficient. A second alternative is to provide separate samples for each student, or pair of students at the most, which for a large class requires a much larger number of samples. In the latter case the same samples can be used continuously over a succession of semesters and still remain "unknowns." In the first case the samples are made and analyzed in small gross lots just sufficient for the semester's needs. In the second case they may be made in larger lots and numbers, to provide for continued use. In either case the total number of analyses on the part of the instructor and assistants makes their preparation an arduous task. Either a few analyses must be made each semester, or a large number a t less frequent intervals. The practice often followed is to prepare large quantities of a few samples and use them continuously from semester to semester until they have lost most of their value as "unknowns." To purchase student samples from various possible sources of supply
soon mounts into considerable expense where large classes are involved. The remedy for both the alternatives mentioned is obviously to provide a method for the synthesis of such samples as mixed chlorides of potassium and sodium. By a knowledge of the purity of the separate ingredients and the weight of each, the resulting analyses can he calculated. The remaining point to be determined is that the two components are thoroughly ground and mixed and that the resulting mixture is homogeneous in each case. The separate ingredients, potassium chloride and sodium chloride, can be purchased in pure form a t a moderate price. The question of the proper method for ensuring homogeneity, following the customary ball mill grinding and mixing, is the unknown factor requiring special study. It is the object of the present discussion to describe a suitable procedure for the preparation of such synthetic mixtures and to compare the actual results obtained with those predicted by synthesis. BALL MILL GRINDING AND MIXING OF THE MIXED CHLORIDES OF POTASSIUM AND SODIUM
If a dry mixture of 40-mesh sodium chloride and potassium chloride is ground in a dry ball mill for a period of one hour the mixture has been reduced to such a fine state of subdivision that i t tends to cake on
the walls of the ball mill jar. A quart size Abbe hall mill jar half full of agate balls and containing a pound of the mixed chlorides is conveniently used in this case. After two and one-half hours rotation most all of the sample mixture is caked against the side walls and bottom of the hall mill jar, but not sufficiently to harden the cake thus formed. After three and onehalf hours the whole of the sample is caked but may still be easily removed from the jar, and simple working with a large mortar and pestle quickly restores it to its proper free flowing and finely ground condition. The conditions resulting in the formation of the cake in the ball mill jar are not remedied by any known procedure. The phenomenon of caking is inherent with this mixture of reagents, as it is also with many other dry mixed components. Certain other mixtures such as portions of diierent ground feldspars do not cake in the hall mill, no matter what the period of grinding may be. The question then to be answered is whether or not the caking results after the sample has been reduced to such a degree of fineness as to guarantee homogeneity. If not the analysis of the resulting product will show non-uniformity. In case the attainment of uniformity precedes the caking phenomenon, the process of synthesizing such mixtures is much simplified. In the opposite case it would he necessary to grind each portion of potassium and sodium chlorides separately to pass a 100-mesh sieve and mix weighed quantities of such samples by other means. The former process, which is much more convenient, was found to be adequate.
Each horizontal row represents results from four separate analyses. Sample Number 2, Table 1, was prepared by grinding each of the separate ingredients to pass a 100-mesh sieve and then mixed by repeated passage through a coarse sieve to mix to homogeneity followed by the analyses as given. The sample, Number 3, was then placed in the hall mill jar without the use of grinding balls and rotated several hours to determine the caking tendency. I t was not apparent. The process of grinding and mixing in one operation, being more simple in practice, was applied in the subsequent preparation of samples. All three of the separate modifications of mixing shown in Table 1 show a satisfactory agreement in uniformity and in calculated values. PREPARATION OF A SERIES OF STUDENT SAMPLES BY THE BALL MILL GRINDING AND MIXING PROCEDURE
A series of ten diierent mixtures of pure potassium and sodium chlorides were weighed in approximately one-pound lots. These were ground for two hundred ten minutes in one-quart Abbe ball mill jars half full of half-inch granite balls. The caked samples were then removed, the balls separated and the caked samples reduced to a free flowing mixture by a brief treatment in a large porcelain mortar. They were then analyzed by Mohr's method and the calculated values compared with actual analysis. The results are shown in Table 2.
EXPERIMENTAL PROCEDURE I N PROVING HOMOGENEITY
A sample of known weight of pure sodium chloride (40-mesh) was placed in a one-quart size Abbe ball mill jar half full of agate balls. A sample of pure
COMP*.ISON
Somi&
No.
0-
TABLE 2 C*LC"L*IHDC",.OR3NB VALUES W l m , AN*LYE&D VALUES FOR A SB-s OF KC1 NaCl Mrxmms
+
KC1
m,
NnCl 4n
Chlorine Colcvlolcd 4n
Chlo~inr Found 7 '"
Differerrre D/.
TABLE 1 AOKe.M&NT
BnTWB&N
Mrxluaes or KC1 NoCl E.
KC! 8.
Colc.
- % Cl
1.
60.2114
40.0010
65.43
2.
101.0490
80.7073
54:&
3.
......
...... ...... ......
..... .....
..... .....
V*L"*S POQ
LXLC~ATBD AND D S T B ~ N B D
... ... ...
+ NaCl
Vorinlio" from Vorinlion i n Pound Dwlicales Cnlculnlion % Cl 7% CI % Cl 65.65 +O.W to -0.09 +0.22 55.59 + O . l l t o -0.05 +0.16 65.00 +O.O3to-0.01 +0.16 54.89 +0.03to -0.03 10.05 55.02 + 0 . 0 2 t o -0.02 +0.02 54.90 +O.O5to -0.05 +0.01
potassium chloride (40-mesh), also of known weight, was added. The jar was closed and rotated in a motor driven revolving rack for a period of two hundred ten minutes. The ground caked sample was removed from the jar and the agate balls separated out. The sample was transferred to a mortar and lightly ground with the pestle to an easily prepared free flowing mixture of 100-mesh fineness or less. Samples were then 'taken for analysis by the Mohr method. The results obtained are compared with the calculated chlorine value and the agreement between individual determinations indicated a satisfactory condition of homogeneity, as well as close approximation to the calculated values. The results are shown in Table l.
~
Average
-
-0.15
From an examination of Table 2 it will be observed that the average diierence between the calculated values and those found is within the range of analytical accuracy which would he expected. The results tend to be somewhat low which may have been caused by slightly impure starting products. The water content of NaCl and KC1 not removed under 400°C. is of the order involved.' The possible range in values from such mixtures is 47.56 per cent. C1 for pure KC1 and 60.65 per cent. C1 for pure sodium chloride. The methods outlined have probably been previously employed, but no records can be found of a systematic discussion of the results, or an estimation of the agreement between calculated and determined values cited. SMITH. STUBBLEFELD,AND MIDDLETON, Ind. Eng. C h . , Anal. Ed., 6, 314 (1934).
