THE: J O C ’ R S d L O F I S D L 7 S Z ’ R I . I L -4 S D E S G I S E E RI S G C H E V I S T R Y
Feb., 1917
T h e oil above t h e emuls:fie,d layer after t h e espiration of t h e test is carefully drawn off and shaken; then 2 0 cc. are mixed with 80 cc. of 58 O BaumC gasoline (from Pennsylvania Crude) in a graduated, flat-glass precipitating t u b e having t h e lower end drawn out. T h e oil-gasoline mixture is kept a t a temperature not over 80’ F. for one hour, or t h e water or watery liquid may be separated from t h e oil-gasoline mixture b y means of a centrifuge. T h e amount of water or watery liquid is read off and calculated t o percentage by \-olume arid subtracted from the oil above i.he e m u sified layer. Of course, this determination is only ry when the oil abol-e t h e emulsifed layer appears t o contain a n appreciable a m o u n t of water. IST C R PR E T . l T i O S O F K E SL-LT S
Dig. I1 illustrates t h e behavior of seven representative oi!s 7.yith l.!iis method. ns they appear after erpiration of the tests. EMULSION TEST ADPARATUS AND MUHOD FOR LUBRICATING OILS
16 j
The first sample of engine oil s h o m a t the end of the test a thick milky emulsion n-ith practically n o separation of mater, and t h e separated oil above t h e emulsified layer contains about 4 per cent of x t t e r . The second sample of engine oil shows considerable amount of separation of water and much smaller amount of emulsified layer; this layer is of :Llight foamy nature. I t should be particularly noticed in these two cases t h a t while I O O cc. of oil were used in t h e tests,. 1 0 2 cc. of separated turbid oil \x:ere found; deducting t h e amount of moisture or water found in the separated oil, 4 and 3 per cent. respecti7-ely. gives 96 and 9 ; per cent of deniulsiliilit>-. This is a clear illustration of t h e imporIance of gi\-ing a complete statement in the report of t h e beha\-ior of the oil nr oils in t h e emulsifying t e s t , as simply stating the percentage of demulsibility is clearly insufficient, and in cases of this kind Ti-odd be seriously inislcading. (Z.U.EN.I-SIGSAL OIL Co%irPnxs F R . ~ S K LPIEXK,K S Y L ~ A S I A
THE SAMPLING OF FERTILIZERS’
1 L-0 2 No 3 No 4 K-o 5 hTo.6 h-o 7 Fro 11-REPRESENTATIVE LEBRICATING OILS A T EXPIRATIOS or‘ EXULSIFYIKG TESTS
A-o
Table I gives detailed results of tests of these oils. T h e first turbine oil shows t h e oil entirely free from emulsifying property or elements. only retaining a very small percentage of moisture or water after t h e exTABLE~-EMUI,SIPICATIOX TESTSO F LUBRICATIKG C)ILS Sep- ConKind arated dition of Water of Oil Oil Cc. Water No. 1 Turbine 40 Clear
EmulSepMoisture Demulsified Kind of arated in Oil sibility Per Per Layer Emul- Oil Condition Cc. sion Cc. of Oil cent cent Xone , , . , 100 Slightly 0 . 2 99.8 turbid Slightly 12 Light 100 Turbid 1.0 9 9 . 0 turbid foamy Clear S o n e , .: , I05 Very turbid .i 0 95 . 0
2
Turbine
36
3
40
5
Crank Case Crank Case Engine
6
Engine
72
Clear
28
7
Spindle
20
3Iilky
140
4
4
Clear
150
.
50
h-one . .
,
Heavy Trace Practically ,, thick all emulsion Thick 102 Very turbid 4 . 0 milky Light 102 Turbid .1.0 foamy Thick Kone All emulsion . , milky
0.0 96.0
Yi.0 0.0
piration of t h e test. T h e second turbine oil shows quite a little of emulsified layer, b u t t h e condition of the emulsified layer is light and foamy, not compact or creamy. T h e amount of water or moisture retained in t h e oil is much higher t h a n in t h e first oil. Consider nest t h e two samples of crank-case oil: T h e first oil shows ready separation of water. which is clear and has no emulsified layer, b u t t h e oil after t h e test retains about j per cent of i n t e r . With other crank-case oil only very few cubic centimeters of water are separated at t h e expiration of t h e \:est. a n d a very large amount. of emulsified layer of a heavy thick nature is shown: in fact, t h e whole mixture is a he a v p e mu1s i on without s ep ar a t ion.
ny F. S. LODGE I n considering the question of sampling fertilizers. t h e first basic idea. t o be realized is t h a t we are not dealing with a homogeneous substance, b u t a mist u r e of a number of different ingredients, each of a different specific grayity, of a different texture, and of difierent sized particles. These factors ail contribute t o t h e tendency t o unmix or t o destroy the uniformity of t h e material and make the problem of obtaining average samples a most difficult one. T h e manufacturer is first concerned in getting a. proper sample of his raw materials, in order t h a t he may know how t o formulate his mixtures so as t o be assured t h a t his finished product will not only contain t h e amount of plant food specified, b u t t h a t a proper sampling and analysis of the goods will confirm his guarantees. T o accomplish this, when unloading bulk goods from a car, a small scoopful of t h e material is taken from each wheelbarrow or cart as i t passes some specified point, these samples being placed in a large can, t o be mixed and quartered d o r n when t h e entire sample has been collected. A scoop is used t o t a k e these samples, since it has been found t h a t there is considerable selective action when handfuls are taken, t h e finer particles sifting between t h e fingers. When cargoes or other large shipments are sampled, i t is usually necessary t o samplc each t e n t h load or some such fraction. I n sampling from bags, the manufacturer will usually draw samples from at least I O per cent of t h e bags, often from 2 0 per cent, and sometimes from all t h e bags. Some of t h e large companies have absolute instructions in force never t o sample less than I O per cent of t h e bags and i n smaller shipments t o sample all t h e bags. Most of them use t h e most approved t y p e of sampling tube. And this all in t h e face of t h e fact t h a t the so-called “raw materials” they are sampling are usually very uniform 1 Presented before t h e Fertilizer Division 53rd Meeting of American Chemical Society, S e w York City, September 25 t o 30, 1916.
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A 1. .4 N I ) EIYGINEEKI.V'G ( ' H E M I S T R Y
Vol. 9. No.
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a n d homogeneous i n composition a n d mechanical condition. I n t h e niodern fertilizer factory all sampling is supervised by t h e man in charge of chemical control. Ne is usually a graduate chemist, who has had special All mixed fert.ilizer training in sampling methods. shipments are controlled liy samples taken regiilnrly at t h e delivery point of t h e finished malcrial, hclorc
will t h e n fill with t h e same material from t h e t o p of t h e bag t h a t is i n t h e bottom of the tube, t h e plug preventing any of the material from t h e bottom of t h c bag from being collected. Three states are using this Bind. By far t h e most common t y p e is t h e so-called b u t t e r , l:ird or cheese tryer, which consists of a half round tube tapered slightly. This cannot remove a n average samplc, sincc t h e m a t e r i d nearest t h e point of withilrawal will tend t o scrape o u t material further down (lie t.uhe. Fourteen of t h e lventy-six states use !,his type, some of them with modifications. One iises i i n iron spoon, one a cup. one a sugar tryer i s merely ii slightly tapering t u b e a b o u t 2 in. r ;in,l S i n . long; one s t a t e uses a rjcc samu t (1 i n lung tapering from I in. in diami :I slot $ / s i n . X a 3 I s i n . a b o u t hall way. which is supposed t o allow t h e sample t o enter t h e tube. One st.ate nses a tube open at the bottom ani1 side b u t with i t flange turned Lo a c t as a scraper to f i l l the tuhc. W r t goods tend to clog this t y p e . I t would seem from t h e above t h a t only t h e two types ( I n d i a n a and butter trl-cr) were in general use, and an investigation was ulirlertaken t o determine t h e acciiracy of each. One large company after careful investigation found t h a t a complete fertilizer having a large a m o u n t of its ammonia derived from n i t r a t e of soda, upon being sampled from t h e bags, would almost invariably give onehalf of one per cent more ammonia with the Indiana t y p e of sampler t h a n with t h e butter-tryer type, t h e
can scarcely he called samplers, such a s c i i i ' c and spoons. T h e sampler which seems best t o meet ai! conditions is one designed at t h e Indiana slation, which consists of two telescoping slotted brass tubes terminating in a solid pointed end. This enables t h e sampler to be inserted full length into t h e hag before a n y material can enter t h e sample chamber. This is t h e n opened, t h e sample consisting of a complctc core allowcd i o fill in, whereupon t h e sampler is closed and t h e t u b e withdrawn, unquestionably removing a c o n of t h e entire bag. Five of t h e t w e n t p s i r states canvassed used t h i s type. Another t y p e is quile simiinr t o t h e Indiana sampler except t h a t t h e end of t h c tube is open. T h e objection t o this t y p e is that in hard material a plug is likely t o he formed when t h e lube is partially inserted, so t h a t when opened t h e t u b e is already partly full; t h e t o p p a r t of t h e sampler
were dragged o u t when t h e b u t t e r t r y e r was withdrawn. I n order t o test t h e accnrdcy of sampling b y means of t h e butter-tryer t y p e of sampler,, a box was built wiih burlap ends. This box was filled with layers of mat,erials crossways--first a layer of tankage, then one of acid phosphate, then one of bone meal, a n d finally one of nitrate of soda, t h e layers occupying approximately equal volumes, so arranged t h a t a sampler passing through t h e burlap woiild pass through t h e layers of material i n order as mentioned above. The sampling was done b y the Indiana sampler a n d by t h e butter-tryer type. Four samples were taken, one from each end with each sampler. T h e Indiana t u b e removed a sample with well defined layers corresponding to t h e layers in t h e box. T h e b u t t e r tryer when used from t h e tankage end
Feb.. 1917
T H E J O U R S A L O F I S D U S T R I A L A N D E S GI -V E E R I N G C H E M I S T R Y
of t h e box drew a sample which looked as if i t were composed largely of tankage, this material having dragged out some of t h e acid phosphate, bone meal, a n d nitrate farther along t h e t u b e a n d displaced i t ; b u t when used from t h e nitrate end of the box, little t a n k age was in evidence, whereas nitrate crystals were distributed along t h e entire length of t h e tube. T h e analysis of t h e samples taken b y t h e Indiana sampler showed 16.17 per cent N a K 0 3 when sampled from the tankage end and 19.71 per cent N a N 0 3 when sampled from t h e nitrate end. this difference being d u e t o t h e fact t h a t t h e tube, owing t o the closed end, was not quite long enough t o reach through the entire box, so t h a t slightly more nitrate was obtained when sampling from t h e nitrate end. However, with t h e butter tryer when sampling from the tankage end only 4.62 per cent of S a N 0 3 was obtained, while when t h e sample was t a k e n from t h e nitrate end 23.41 per cent N a N 0 3 was obtained. I n another experiment a box was made up of similar layers of tankage, acid phosphate, bone meal, and manure salts. When sampled from t h e tankage end, t h e analysis of t h e sample t a k e n b y t h e Indiana sampler showed: Ammonia 3.62 per cent, total P?05I j.6 j , a n d K 2 0 3.jg--mhich is close t o the calculated analysis; b u t t h e sample taken by t h e butter tryer g a r e : Ammonia 4.33’ per cent or 0.73 per cent more, total P z O j I j.13 per cent or 0 . j 2 per cent less, while t h e K20 was only 1.60 per cent or 1.99per cent less t h a n t h e other sample. T h e increase in ammonia a n d decrease in t h e other t w o ingredients would seem t o show conclusively t h a t t h e layer nearest t h e point of exit of the t u b e does drag out material collected toward t h e end of the t u b e and fill in t h e e m p t y space itself. This was also definitely shown in t h e case of t h e nitrate of soda samples mentioned above. We realize t h a t the conditions used t o test o u t this point are b y no means ones t h a t would be met with in actual practice, b u t i t is only b y going t o such extremes t h a t definite tendencies can be conclusively demonstrated. Under these conditions, especially after t h e vibration of long railroad hauls m a y have caused segregation a n d stratification, i t would seem t h a t t h e conditions of t h e law were not being fulfilled when t h e buttertryer t y p e of sampler is used, when the lam- specifies t h a t a core shall be taken through t h e sack or even when i t specifies t h a t an average sample shall be taken. Further analysis of s t a t e methods reported shows t h a t in most cases I O per cent of t h e bags in a shipment are sampled, although some s t a t e sample as lom as only 3 bags in a large shipment. Others will not sample shipments (of I t o n or less unless it is t h e only chance for a sample of t h a t brand. There are fen- criticisms t o offer on t h e percentage of t h e bags sample d . I n ten o u t of t h e nineteen states reporting, the sampling is directly under t h e S t a t e Chemist, while in t h e other nine it is under t h e Commissioner of Agriculture and the chemist only supervises t h e actual analysis. I n twelve o u t of t h e twenty-two states reporting. t h e
169
inspectors are either appointed or recommended for appointment b y t h e State Chemist, and are usually trained men and t h e positions usually permanent. I n t h e other t e n states t h e appointments are made by t h e Governor or Commissioner of Agriculture] often for political reasons, and t h e appointment is often for short periods, such as three months. I n conclusion I should like t o recommend t h a t t h e chairman of this division appoint a Committee of five members, two t o be State Chemists in charge of fertilizer control work, two t o be manufacturers” chemists, and one t o be a commercial chemist largely engaged in fertilizer work: this Committee t o formulate a standard method for t h e sampling of fertilizers. V h e n a satisfactory method has been agreed upon, t h e Committee is t o submit it t o t h e -4. 0. A. C. for their official consideration a n d action, looking toward its acceptance and incorporation among their official methods. L A B O R A T O ROY F .4RMOlIR & C O X P A X Y CAICACO
AN IMPROVED TABULAR ARRANGEMENT FOR CHEMICAL FACTORS By C L A R E N CV. E
EKROTH
Received J a n u a r y 1 1 , 1016
T h e writer for several years has been using a very convenient arrangement in his tables for gravimetric factors. This tabulation has been found t o be very satisfactory b y many of his co-workers, and upon their suggestion. a n d in t h e hope t h a t it will prove of help t o others who may have frequent occasions t o use factors, a brief description is given here. T h e arrangement is illustrated in Table 2 , and, for comparison, in Table I , t h e usual method of tabulation is given. T A B L E1 A
Weighed or Found
Required Weighed or B Required Found Calcium, Ca = 40.07 Ca . . . . . . . . . . . . CaClz Ca . . . . . . . . . . . . CaO CaO ... , . . . _. , C a Magnesium, hIg = 24.32 M g O . . . . . . . . . . Mg
.
B
A Factor
Logarithm
2.76989 1.39929 0.71460
0.44246 G.14591 1.85406
0.36103 0.71460 1.39929
1.55754 1.85406 0.14591
0,60317
T.78044
1.65590
0.21956
T A B L E2 Weighed or --t Required Found Calcium, C a = 40.07 0.26103 Ca ,. CaCh 0.,1460 Ca . CaO Magnesium, h l g = 24.32 0.60317 Mg ... MgO Weighed +Factor &Required t or Found
Factor
Logarithm
+ Factor --f Logarithm
i.55i54 7.85406 i.78044 Logarithm
..
...
.
2.76789 1.39929
0 44246 0.14591
1.65790
0.21956
By t h e proposed method, as shown in Table 2 , t h e necessity for reference t o t h e column headings is practically eliminated, as it is only necessary t o remember t h a t t h e factor for t h e substance “required’! is located by continuing in t h e same direction indicated b y a n arrow pointing away from t h e “weighed or found” a n d toward t h e “required.” This is shown in t h e column heads, t o p and bottom. Thus, if C a is “found” and CaO is “required,” t h e arrow will point t o t h e right-hand column (shown in heading a t t o p ) , where-
