Proceedings of the chemical section of the Franklin Institute

6/ze~l;tca! 5ectto;,.

l ) e c , ,892.1

449

PROCEEDINGS OF THE

CHEMICAL

;

SECTION

:

OF TH~

F R A N K L I N INSTITUTE.

Proceedings of tke s/,~tcd meetittg~, held Tuesday, November 1.5, I89Z] HALL

OF THE

FRANKLIN

INSTITUTE)

PHILADELPHIA~ N o v e m b e r 15, I892. Dr. Win. H. Wahl, President, in the chair. Dr. Jayne presented a report on behalf of the special c o m m i t t e e appointed to arrange for a reception to be given to Professor Wiley. on t h e e v e n i n g of Erecember 6, I892. On motion, the report was accepted and the committee was given power to arrange the necessary details. Nominations for officers for the ensuing year were t h e n m a d e as follows : For President,

j" Prof, E d g a r F. Smith, ~. Dr. 1,Vm. H. Greene. Mr. H e n r y Bower, be elected), " ' { Dr. D. K. Tuttle. . . . . . . . Dr. W i n . C. Day, Dr. H. W . J a y n e , . . . . . . . Dr. W m . H. Wahl.

. . . . . . . . . . . . .

For Vice-?resi&nts (two to For Secretary, , . . . . . For Treasurer . . . . . . . . . . . . . . For 6bnservalor . . . . . .

Mr. H. Pemberton, Jr., on behalf of himself and Mr. G e o r g e P. Tucker, read a paper on " Deposits of Native Soda near Laramie, W y o m i n g . " Referred for publication. Dr. Win. H. W a h l read a paper, entitled " O b s e r v a t i o n s on FerroT u n g s t e n . " Both papers called forth considerable discussion. • The Section then adjourned. H. PEgnER'i'ON, JR., Seci'ektryl~ro/on.

450

(.'/zcmzca/ Section.

REPORT

ol,' Till,; P R O C E E D I N G S

[J. F. I.,

oJ,'

THE

NINTH

ANNUAL .~IEETING OF O F F I C I A L A G R I C U L T U R A L CHEMISTS~ IIEIA) AT W A S I [ I N G T O N , A U G U S T 25-27, I 8 9 2 , WITH SPECIAl, R E F E R E N C E TO T I l E METHODS A D O P T E D FOR THE CONTROI, OF THE F E R T I L I Z E R TRADF.. BY I)R. BRUNO TEI¢NF..

[[deact at t/~e Haled nl~'efing ~ /~e 6 ~ e m ~ Z See~ion, ~dff October zS, ¢892.] M R . P R E S I I ) F N T AND ~IE.~IBER!~ OF T I I E C H E M I C A L ~ E C T I O N :

Looking over the wide field of scientific societies, and more especially over the chemical o r g a n i z a t i o n s of our country, I know of none which has, in the s h o r t t i m e since its creation, done so m u c h practical good work for the benefit of the interested circles as the A s s o c i a t i o n of Official A g r i c u l t u r a l Chemists. Still, w h e n we come to criticise its work of t h e last few years, we cannot deny the fact t h a t the r e s u l t s g a i n e d are not in proportion to the work done A l t h o u g h e n c o u r a g i n g , the results are far from being final. A short historical sketch of the association will doubtless interest you, and serve as an i n t r o d t l c t i o n to t h e remarks which I propose to make in regard t o t h e r e s u l t s of the last m e e t i n g of the said association. W i t h the revival of business in the S o u t h e r n S t a t e s t h e consumption of fertilizing m a t e r i a l s for the c o t t o n p l a n t a tions soon assumed enormous proportions. The v a l u a t i o n of this material, based on c h e m i c a l a n a l y sis, was a source of g r e a t trouble both to seller a n d b u y e r , caused by the uneoneerted action of the c h e m i c a l l a b o r a tories. There were in use all possible m e t h o d s for t h e d e t e r m i nation of the different ingredients. This chaotic state of affairs has been c h a n g e d b y t h e concerted action of the analytical c h e m i s t s i n t e r e s t e d in s u c h work, and the g a i n of this very importa~nt poiJat i s t h e f r t t i t of fl~e earnest work of this association.

Dec.. 1892.]

C/lemica[ Section.

45x

The b e g i n n i n g of the organization dates from the following circular-letters : DEPARTMENT OF AGRICULTURE, ATLaNTa, Ga., May 2o, I88o. Di:,.xa S ~ a : - - T h e experience of the last fertilizer season has s u g g e s t e d to m y m i n d the importance of securing such uniformity of m e t h o d in determining, by chemical analysis, the percentage of v a l u a b l e ingredients in commercial fertilizers, as will give more uniform, and hence more satisfactory results. T h i s is especially desirable in determining, reverted phosphoric acid. W i t h a view to accomplishing so desirable an objeet, as well as others which m a y b e deemed proper, I have t h e honor to s u g g e s t the eailing of a convention of the several Commissioners of Agriculture, representatives from S t a t e Boards of Agriculture. State chemists and professors of c h e m i s t r y in S t a t e universities and State agricultural c o l leges, in those States using large a m o u n t s of commercial fertilizers, to m e e t at some convenient point early in the m o n t h of J u l y next. I w o u l d be glad to have y o u r views on the s u b j e c t ; and if f a v o r a b l e to the s u g g e s t i o n please nominate some gentlem a n who, b y general assent, m a y be informally authorized to fix t h e time and place of such convention, and issue the n e c e s s a r y notices. Y o u are also requested to give m e the n a m e s a n d post-offices of g e n t l e m e n in your State, holding e i t h e r of the above positions indicated, which do not appear in the l i s t below, that copies of this circular m a y be s e n t to them. A n early reply is desirable. V e r y respectfully, J. T. HENDERSON, G,mmissioner oJ' Agriculture. DEPARTMENT OF AGRICULTURE, ATLANTA, Ga., J u l y I, 188o. DEAR SIR :--I am gratified to announce that the recent circular-letter which I had the honor to issue, s u g g e s t i n g t h e c a l l i n g of a convention for the purpose of a d o p t i n g a

452

Chemical Section.

[J. F. 1.,

u n i f o r m s y s t e m for the analysis of commercial f e r t i l i z e r s , has m e t with f a v o r a b l e r e s p o n s e s from a large m a j o r i t y of the g e n t l e m e n to w h o m it was sent. A like m a j o r i t y h a s i m p o s e d upon me the d u t y of fixing the time and place of said convention, and i s s u i n g t h e n e c e s s a r y notices for the same. A f t e r c o r r e s p o n d e n c e with others, and d u e consideration of the i n t e r e s t s involved, I h a v e decided u p o n W e d n e s d a y , the 28th of July, as the time, and W a s h i n g t o n , D. C., as the place for the a s s e m b l i n g of the p r o p o s e d convention. Y o u are, accordingly, r e s p e c t f u l l y and e a r n e s t l y invited to be p r e s e n t and p a r t i c i p a t e in t h e convention. E v e r y r e a s o n a b l e facility for the d e l i b e r a t i o n s of the c o n v e n t i o n will be afforded b y Hon. W m . G. LeDuc, Commissioner of A g r i c u l t u r e , w h o is in h e a r t y s y m p a t h y with the o b j e c t s o u g h t to be accomplished. I h a v e a p p e n d e d h e r e t o a list of the n a m e s of g e n t l e m e n to w h o m this circular will be sent. T r u s t i n g that y o u will find it c o n v e n i e n t to a t t e n d and give the c o n v e n t i o n the benefit of y o u r experience, and r e q u e s t i n g t h a t y o u will at once inform m e b y l e t t e r w h e t h e r y o u will attend, I am, Respectfully, J. T. HENDERSON, Commissioner of Agriculture. T h e first c o n v e n t i o n m e t on the d a y set for and a d o p t e d m e t h o d s for the d e t e r m i n a t i o n of phosphoric acid, nitrogen and p o t a s h to be u s e d d u r i n g the e n s u i n g year. T h i s m e e t i n g was followed by m e e t i n g s in Cincinnati, Atlanta, and in I884 in Philadelphia. T h e c o n v e n t i o n in our city was the m o s t i m p o r t a n t one for the organization, b e c a u s e the association a d o p t e d (Sept e m b e r 9th) the n e w Constitution, and m a d e itself entirely i n d e p e n d e n t of its former connections as a subdivision of the Section of C h e m i s t r y of the A m e r i c a n Society for t h e A d v a n c e m e n t of Science, T h e first two p a r a g r a p h s of the Constitution are of general interest. (I) " T h i s association shall be k n o w n as the Association of Official A g r i c u l t u r a l Chemists in the U n i t e d States. I t s

Dec., 'g9:-]

C/mmica! Section.

453

object shall be to secure, as far as possible, uniformity in legislation with regard to the regulation of the sale of commercial fertilizers in the different States and uniformity a n d accuracy in the m e t h o d s and results of fertilizer analysis. (2) " nalytlcal chemists connected with D e p a r t m e n t s of Agriculture, State A g r i c u l t u r a l E x p e r i m e n t Stations a n d S t a t e Boards, exercising an official fertilizer control, shall alone be eligible to m e m b e r s h i p : and one such representative from e a c h of these institutions, w h e n properly accredited, shall be e n t i t l e d to a v o t e in the association. All analytical chemists and others interested in the objects of the association m a y attend its m e e t i n g s and take part in its discussions, b u t shall h a v e no vote in the assoclatl""on." T h e e x c l u s i o n of all chemists not to be classified as officials, f r o m full membership, varies from the custom of E n g l a n d a n d Germany. It is n o t m y i n t e n t i o n to question either the motive or the w i s d o m of this regulation, or of another rule denying the r i g h t to e n t e r a motion which has b e e n in force since 189i , as i t certainly g i v e s the excluded more liberty to eritielse t h a n if he were made responsible b y his vote for the action of t h e society. Since t h e Philadelphia m e e t i n g the society has macte its h e a d q u a r t e r s in W a s h i n g t o n , where, u n d e r the patronage of t h e D e p a r t m e n t of Agriculture, the annual meetings are held. T h e untiring efforts of the S e c r e t a r y of the society, Mr. H a r v e y "vV. Wiley, Chief Chemist of the D e p a r t m e n t of A g r i c u l t u r e , have secured to the association the support of t h e A d m i n i s t r a t i o n , and enabled the same to publish the r e s u l t s o f their annual work, as a 8u[lelin of the Depart. m e n t , d i v i s i o n of chemistry. T h e s e annual reports are edited by. the able pen of Prof e s s o r W i l e y and are an exceIlent guide for all connected w i t h t h e i n t e r e s t s of the society. T h e s c o p e of work of tile association has extended to a w i d e r field than was originally planned, including at p r e s e n t all s t a t i o n w o r k in t h e interest of the farming c o m m u n i t y . B e s i d e s the fertilizers analysis, we have had during t h e l a s t y e a r reports on analysis of fermented liquors, dairy

E/Ic;J/z~'al .~)'cltT,..

454 products, sugar.

foods

rich

and

l)~)(~r

[_J. F. I.,

in c g l r b < ) h } d r a t e s ,

and

on

Duringthe last hair years i ]l:tvc rc3ularlv:tttended the meetings o f t h e a . ~ s o c i a t l o n :ts :t i ] o n - n i c l n l ) c r , a n d t a k e n m u c h i n t e r e s t in t h e : t n a l v s i s (,f c , m ] n l c r c i g t ] f e r t i l i z e r s . I t w a s w i t h gFegt{ l)le:tEllt'(: l.]lgtt I a t l c n d c d from August 25I]] to :,Tth ,~i thi,q \'car.

the

meetings

I w i l l n o w r c l > o r t the: i~-,~{ d i n t g ~ r,.~fcrring for methods i n u s e t o t h e ~>itici:tl l ; . 1 k ' i e . N~, 31, i S g l :

the

I
t /re'Ill~tic O! I/,,'t [ tl,"l~'r~ .'~'/ag<:'5.

BY I)14, Gl';ill':ril,; I'. I'AVNI;, A i l a n t t, (.:a.

The work required by the association, of the reporter oI~ potash for I 8 9 2 , was an investigation as to whether the u>erd sodium chloride was e s s e n t i a l in the I.indo-Gladdlng ntethod of deterlnh~ing potanh. Four samples were prepared and were nunibered one, two, three a n d four. No. I was a high grade sulphate of potash. No. 2 was an acid phosl3hate with sulphate of potash ill the form o f kainit, No. 3 was an acid phosphate with sulphate of potash iIt the form o f kainit, and containing live per cent. of double stilt)hate of a l u m i n a a n d ammonia. No. 4 was identical with No, 3 with the substitution of five per cent. o f soluble sodium silicate in place of the double salt of ahunina a n d a m m o n i a . T h e ingredients of each sample were lirst finely powdered a n d t h o r o u g h l y mixed, then sifted through a very line sieve, then again intimately m i x e d and portions taken from forty different parts of the pile were well r e - m i x e d and used for filling the bottles. Only the best XX superfine long taper c o r k s were used, and were selected long enough to project well from the m o u t h o f the vial to secure easy opening and air-tight re-corking. The c o r k s were a l l well sealed withparaffine. With each package a circular was sent r e q u e s t ing that the determinations be made as soon as convenient after r e c e i v i n g samples to eliminate as far as possible any differences likely to o c c u r f r o m changes in the amount of moisture after bottling. Each chemist was also requested to carry out the method as o r d i n a r i l y managed in his laboratory, working each sample with and without s o d i u m chloride, side by side. and as nearly as possible under exactly the s a m e conditions. Twenty-two chemists took part in the work and their results were a s tollows: [See table inserted here.]

~mir. h;,'a~a/c, at,ft., Vo/. CXA'Y?V.

DETERMINATION

01," I ' ( Y I ' A S I I

I),,ccm/)er, 289~.

I;3,' T H E

(Term,)

t.INI)O-(;1,AI)DING

MI:.'I'HO1

WITH

AND

WH'I-IOUT

SODIUM

CHLORIDE.

Sample N o . 2.

Sample ~0.1. .*N'AM~:; OF ANAI.VS'I'F. AND I,Ot'ATIt}N. ( )FFI(.tAI, [,AIIOI{ATC)t~II.S.

Sample iNo. 3.

Sample N o . 4.

"iWithout NaCI.

With ' W i t h o u t With NaCI. NaC[. ] NaCI,

With NaCI.

Without NaCI.

With NaCI.

without NaCI.

i

Norman Robinson, State Chemigt, Tallahassee, Fla., . . . . . . . . . . . . . . . . . . . . . . . F. S . S h i v e r , A s s i s t a n t of S t a t e C h e m i s t , F o r t H i l l , S. C. (a), . . . . . . . . . . . . . . . . . . . F . S, S h i v e r , A s s i s t a n t of State C h e m i s t F o r t H i l l , S C . I'bl, P . L. H u t c h i n s o n , A s s i s t a u t o f S t a t e C h e m i s t , A t a n t a . Ga.', . . . . . . . . . . . . . . . . . . .

48"83 ,19.05 49'00 49"05

T h e . s . L . B ] a l o c k , E x p e r h n e n t S t a t i o n , N. C. (c), . . . . . . . . . . . . . . . . . . . . . . . . . l.ouis A. Voorhees, Experiment Station, New Brtmswick, N.j., . . . . . . . . . . . . . . . . L o u i s A . V o o r h e e s , E x p e r i m e n t S t a t i o n , N e w B r u n s w i c k , N. J . , . . . . . . . . . . . . . . . . . C• a s S . C a.t h c a t , A, g r c . tt ra Co lege , N e w F, r u n s• w l c k •N . 1~., . . . . . . . . . . . . . . . . . . k . t I . I i a r r m g t o n , E x p e r i m e n t S t a t i o n , C h a m p a i g n Ill . . . . . . . . . . . . . . . . . . . . . . T I os L. \ g a t s o ~, g x p e r i m e t S t a t on, B l a c k s b u r g , V a . A s , d s t a n t C h e m i s t , . .. . . . . . . . . R . C . K e d z l e , A g r i c u l t u r a ! C o l l e g e P. O., M i c h . , . . . . . . . . . . . . . . . . . . . . . . . . l,'~udolph de Roode., E x p e r i m e n t S t a t i o n , M o r g a n t o w n , W . Va., . . . . . . . . . . . . . . . . . . F-udolpi~ de .Roode, E x p e r i m e n t S t a t i o n , M o r g a n t o w n , W . V a , . . . . . . . . . . . . . . . . . . C . B. C o l l i n g w o o d , E x p e r i m e n t S t a t i o n , T u c s o n , A r i z . . . . . . . . . . . . . . . . . . . . Henry E. Curtis, Experiment Station, Lexington, Ky., . . . . . . . . . . . . . . . . . . .... W . S . S w e e t - e L E x p e r i m e n t S t a t i o n . St a t e C o l l e g e P. O . , Pa., . . . . . . . . . . . . . . . . . . W . S. S w e e t s e r , E x p e r i m e n t S t a t i o n . S t a t e C o l l e g e P. O . , Pa., H . F,. M c D o n n e l l . S t a t e C h e m i a t , C o l l e g e P a r k P. O . , M d . , . . . . . . . . . . . . . . . . . . . . W . D . B i g e l o w , U. S. D e p a r t m e n t of A g r i c u l t u r e , W a s h i n g t o n , D . C . . . . . . . . . . . . . . . .

48'96 48'9 o 49"13 40-27 49'3 t 49"~9 49 ~9 48.75 48"96 49"04 48"62 49'oo 49"~6 49'3o 48'47 ~18"56 . .

48"76 49'~o 48'91 49"19 49'29 49'34 49'00 48'95 48'69 48'96 49"o4 48"38 48'9x 49 '18 49'29 48"69 48 3 ~ , . . il

48"994 --

48,96x ~! "°33 I

49"88 49"67 49"89

48"70 49"~3

I

~ '58 1 '45 * "45

1'59

1"47

1'46

V40

l "44 --

1"40 I '4o

I "39

I"4o ~ "32

t 5o ~'5o

t'48 1"52

1 "57, 147

t',~8 1'36 I'56 x'48

t'4t I"44 --

~ "63

I

"63

~"48

l"4o t "4~ --l "46,

I "59 ~ '49 *'5 t 1 '5~ t '77 ~'55 I "55 ~'52 1"57 * "5~ ~'45 * %9

x'58 1 '46 x'5~ x'64

1-51 V35 1 "38 I 43 *'77

1"4g I"36 1 "42 1"45 r'66

t'46 1"36 1'36 1"35 1'6~

I '58 1 "53

I "4t x'54

x "~l:, x-~l

*'41 J %7

I "55 • '53 I '47 1"46 1"57 ~'57 t'6~ ~'58

I '4 ~ ~'48 --t'43 1'58 l'St t'58 1'57

r "42 1'46

1"37 x'39

I"39 I '37

r'a0 x 53 I"51 *'55 *'37

139 145 1"45 I'48 1'47

1"37 *'43 r'ao ~'45 t "4z

~'554 -,

, '538 "o16

t'484

~'456

I'439

1"4~7

1"87 ' i"6o l "6~ ---1 "66 -*'35 !

1"9 t 1'46 x'52

48~B -49'43

49"8o 49"~7 48'71 48-~l 48"69 48"54 48"99 49'47

Average, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Difference, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

49'550

48"948

,'62o '

Total average . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Difthrence, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

49"93

49"~5 49'~ --

Average, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , ...... Difference, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.

1 "(~I

--

• '46

"65 ~'49 .....

i "~8

~ "ao :t'34 --

~ "47 * "45 I "37 ~'37 1 "33 x'5t 1 "36 ~'65

--

--

'0~8

--

'o22

UNOFFICIAL LABORATORIES. Fhepard Laboratory, Charleston, S.C., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E h v y n W a l l e r S c h o o l of M i n e s , C o l u m b i a Col l e ge , N e w York C~ty . . . . . . . . . . . . . . E l w y n \ \ r a i l e r S c h o o l of M i n e s , C o l u m b i a Col l e ge , N e w Y o r k C i t y , Elveyn W a l l e r S ¢ l m o l o f M i n e s , C o t n b t C o eye, N e w Y o r k C i t y . . . . . . . . . . . . . . E h v y n \ V a l l e r S c h o o l of M in es C o l u m b i a C o l l e g e N e w Y o r k C t y ' H . T . V,, te, Aa~ s t a n t o f E h v y n W a l l e r S c h o o l of M i . . . . . C o l u m l ) i a C o l l e g e , "New {fork' City," [ [ 1;. C. } I i n m a n , A s s i s t a n t of E l w y n W a l l e r S c h o o l of M i n e s , C o l u m b i a C o l l e g e , N e w Y o r k C i t y , . F . S. H y d e , S t u d e n t o f S c h o o l of 7,.lines~ C o h m t b l a C o l l e g e , N e w Y o r k C i t y , . . . . . . . . . .

--

-

__

'6o~

48"957 '136

--

I "566 : --i

Htghest . . . . . . . . . . . . . . . . . Lowest . . . . . . . . . . . . . . . . . Differenc

i

. . . . . . . . . . . . . .

1"75

x'74

*'66

1"55

x "6~ "56

1 "53 :t'5~

z '59

I "59 *'53

I'58 i'5 x x'4 a

*'58 *'67

~'58 1"4o

c58 ] '41

*'5~ l "40

*'566

1'634

*'544 .o9o

1'560 --

1'518 .o4a

1 "543 --

1"474 )] "od9

l "458

I'438 "o2o

--

"o54

1'545 "O21

49"89 48'62

1'87 I 35

* 77 *35

v67 1"32

1"27

o'5~

o-4a

035

Dec., 1892.]

CTzemica/ Sectio~t.

45 5

T h e m e t h o d of Lindo-Gladding for potash d e t e r m i n a t i o n is a very s a t i s f a c t o r y one. T h e addition of NaC1 is absolutely unnecessary, and will n o w be stricken out of the official methods. T h e great differences in potash which often arise b e t w e e n g u a r a n t e e of b r a n d and anaylsis are not to be a t t r i b u t e d to the method, b u t in m o s t of the cases to the u n e q u a l mixing of the products. I have s h o w n in a p a p e r read before the association at the A u g u s t m e e t i n g of I89I, th~/fc/iJz No. 3I, pp. I5O, 152, the e x t r e m e di fficulty of m a k i n g mechanical mixtures sufficiently uniform to cover chemical guarantees, when for example e i g h t y pounds or even loo p o u n d s of high grade muriate of p o t a s h at a g u a r a n t e e of fifty per cent. potash, the bearer of t h e potash in a ton of mixture. 2"he same experience has been made by others, and the reports on potash give a vivid picture of this evil, which seems to g r o w as we go further South. T h e report on d e t e r m i n a t i o n of nitrogen was made by Mr. V a n Slyke, of Seneca, N. Y. T h e report appears in the a c c o m p a n y i n g table. [See p. 7.] T h e work on d e t e r m i n a t i o n of nitrogen has, from the beginning, given the m o s t satisfactory results. ~Phe introduction of t h e Kjeldahl m e t h o d s several year~ ago has g i v e n occasion for the careful testing of this m e t h o d in its original and modified form. tn 1887, Prof. M. A. ScovelI, of Louisville, Ky., introdueei a modification to m a k e t h e K j e l d a h l method likewise applic able to nitrates b y the u s e of salicylic acid (Bulletin No. 16 I887, PP. 51-54) w h i c h at the m e e t i n g of I888 was adopted a: official. T h e m e t h o d s a d o p t e d as official methods : (I) T h e a b s o l u t e (2) T h e K j e l d a h l of nitrate. (3) T h e K j e l d a h l able to all

or cupric oxide method. method, not applicable in presenc, method, modified b y Scovell, applic fertilizers containing nitrates.

456

pJ. v. 1., e~.-=- o

.'d

±

Z

•

~

.

~

.

~

, ~

~

© 0 "tl ~;I11JOd lllOq]!h~ poH~o~j Mu.uun 0

© © .,¢

~. ,

"ol~u -~u~:tu.t~d ql!/,x

~

~E~"

P°q~l~

~

~ ~

~u!uun O

t~ - u ~ m . t o d ~noq~!m

-o~gtl © © P~.~'~-"~m~l

- u'~ cu,~ d :mo q'l[a,. poq:l~IAi ~ u ! u u n , r)

-~:~u~uu~ d

qltax

•~ u ~ poq:lolA /

lq~pl~.[~

'~

~ * ~

.~

~'~ I I I ~'~

m.~.~. ~''~"~

"~'*-

"d ~ ~ " ~

-**~**

',-~

~4'.,s-'o

Dec., 1892.]

C,Zzemical Section.

457

(4) T h e Ruffle m e t h o d , applicable for all fertilizers c o n t a i n i n g nitrates. (5) T h e soda-lime m e t h o d s , not applicable for n i t r a t e s are all equally reliable in the h a n d s of a careful analyst. T h e K j e l d a h l m e t h o d is w i t h o u t a n y d o u b t an excellent m e t h o d and especially a d a p t e d for s t a t i o n work, w h e r e the work can be s u i t a b l v a r r a n g e d to divide labor with a large q u a n t i t y of samples of like character. I find t h a t m o s t the s t a t i o n c h e m i s t s work with this m e t h o d , while on the o t h e r h a n d the trade c h e m i s t s and m o s t the c h e m i s t s of m a n u f a c t u r e r s are u s i n g the soda-lime or Ruffle m e t h o d , because, if one has to h a n d l e only a single s a m p l e at a time, one saves time in d o i n g so. Differences in low g r a d e goods (two to three per cent. a m m o n i a ) s h o u l d not be h i g h e r t h a n o'I per cent., and in h i g h g r a d e never reach o'5 per cent. My experience d u r i n g the last fifteen years has been t h a t I never h a d m a t e r i a l difference on this point with reliable t r a d e or s t a t i o n chemists, b u t not so w i t h c h e m i s t s who i n s t e a d of n o r m a l acid use diluted m u r i a t i c acid to absorb the a m m o n i a and s i m p l y e v a p o r a t e and weigh as m u r i a t e of a m m o n i a . W i t h such I never could agree. It is h a r d to believe t h a t at the present d a y such m e a n s should be applied by analytical chemists, b u t it has been the ease until very recently, and is so doubtless yet in single instances. On the whole the d e t e r m i n a t i o n of n i t r o g e n by the s t a t i o n c h e m i s t s in the control of the work of fertilizers has g i v e n g e n e r a l satisfaction. T h e most i m p o r t a n t p a r t of a fertilizer m a t e r i a l is without question phosphoric acid in its different forms, as w a t e r soluble, reverted or citrate of a m m o n i a soluble, and insoluble, as well as total. T h e d e t e r m i n a t i o n of phosphoric acid is of such importance for the fertilizer trade t h a t since the first m e e t i n g of the association s t r e n u o u s efforts have been m a d e to give c o n c o r d a n t results.

458

CTzcmicaI Section.

[ J. F. I.,

H o w far t he association has been s u c c e s s f u l is best show n b y a r e c a p i t u l a t i o a of t he work done. I h a v e gone back f o r five years, and now give you on a c c o m p a n y i n g tables t h e d if f er en t r e p o r t s in c o n d e n s e d form.

x888. August i6, t 7 and tS,

Three Samples .5~nt Out. (A)

South Carohna acid phosphate.

(17) Engli'd~ acid phosphate. ( C ) Navassa acid phosphate laboratories h a v e sent results.

Moisture.

Soluble

l,~ever ted.

lnsohdfle.

18"x4 18"22 ~o'96 7"25 JS'lo

5'58 5'83 6'o1 6'0o 6"to 6't 5

4"45 4'37 4"0,) 4"x i 4'65 5'36

~'6o ~-'4o 2"4x "2"38 2'35 2"~ 7

12"63 I2'6o 12"54 :t:~'49 I3"Jo 13"68

1o"o3 Io'2o lO'i 3 lo'it ~o'75 1t'8t

J5"o3 ~7"o7 -x6"I5 t5"65 12"85

9'38 9'48 9"31 9"34 9'35 9'26

at'i 7 2"24 2"23 2'4x e'9o 2'~t

"43 "43

x x "98

"35 "85 '5o

iS'tO I2'57

:ti'55 xx'72 ix'54 xx'75 ~'~5 x2"o7

6'4z 6"3 x

9'63 9"53 m'81 8'57 8'60 8"78

5't7 6'o6 4"78 6"88 6'io 6'68

4'73 4,i't 3"7 x 4 'o6 4"25 4"32

I9"53 19'7o i9'3o x9"5x :~9'25 xo'78

x4"8o I5'59 x5'59 I5'45 15'00 i5'96

--

7"3I 5"4° 7"45

'2o

Total.

I2'I 5 Ix'74 12'10

Available.

Averages of Available Phosphoric Acid.

Mean, xo'45 Highest, x1'5x Lowest, 1o"o 3 Difference, z'4g

Mean, x~'3x Highest, 12'25 Lowest, ~ i ' 5 4 Difference, o ' 7 i

Mean, x5'3 t Highest, x5'59 Lowest, x4"8o Differet~eej 0 ' 7 9

Dec., 1892..]

459

67zemtcal Sectwn.

x889.

Five Samples Sent Oul. No. No.

z. 2.

Ground South Carolina Grour~d tankage.

N o . 3.

Ammoniated

N o . 4.

Dissolved

South

No.

Dissolved

Navassa

5.

super

phosphate.

phosphate.

Carolina

phosphate.

I?hosphate.

AVERAGES.

Numhe~ of Dctermin~tlOUS.

Average.

Highest.

Lowest.

Difference.

. S a m p l e A'o, z. Mob;tore, . . . . . . . . . . . ~'hosph oric acid, . . . . . . .

l7 3~

"95 28'o 7

~ 37 28'78

"76 27"47

'61 ,'3 x

S a m p l e -No. e. Moisture . . . . . . . . . Phosphoric acid, . . . . . . .

17 31

6'79 14"3 t

7'64 14"9 x

6'03 x3 -b2

x'6x x '~9

24 3:~

~9 6 5 8"57 2'27 960 2"2o xI'49

12"oo 6"00

7"65 2"57

3~ 3a 3z

x5'4o 7"x~ t "3 x 8'42 t'65 1o'o7

24 3~ 32 3~

9"6~ xo'88 a-93 x38I

xl"X4 xx'51 5"~x ~4"~

9"o3, 8'67 x'~x x~'37

3z

15"76

x6"2o

x5"x8

S a ~ t ~ l g JVO. 3" Moisture, Soluble Rev. Available

. . . . . . . . . . . ~ phosphoric acid, . . . ,c

" "' . . . . " "

Insoluble Total

Sample No. 4 Molstttr~, Soluble Rev. Available

~c

.

". . . ." " '~ , . . , ! .

.

.

3~

'8:~

1t'47 t'o8 "9o "~6

T9 z r'3 o 9"63

i

. . . . . . . . . . . i phosphoric acid, . . ~ i " " . , " " i

.

Total

"

'~

S a m p l e N o . 5, Moisture, . . . . . . . . . . Soluble phosphoric acid, Rev. " " Available '. . . . Insoluble '~ " Total . . . .

" " "i

. . .... " ' " "

I .......................... i ' 24 9'63 "i 3z T52 3~ 7"5 ° 3a 'S", " ,! 32 3"40 :i 3a ,8"5I

~

~'84 4'oo x '9~ ~'53 X'02

' ........ x5"8o ~o'°4 9'08 x5:9o

386

19"19

8"09 6"co

4"48 I

7"71

4"o4 4"5

x4"52 "93 x-x 5

U/wmica/ .Scc[zon.

460

[J. F. I.,

$9o.

T h r e e A'czmpl¢'s 3,?ug (.)u/. No.~.

Guano.

N O . '2. No. 3

Acid phospliatc. amnloniated super phosphate, AV ERAGFS.

N t l l l l i l e r /f l)eternlii/~{ i.[ oi1%

Average

Itlghest.

Lowe~t.

l)lfference

5 " a m p l e 2yD. I Molsturc . . . . . . . . . . . Total pho;phoric acid, . . .

g

I3"9i

16'o2

12"o 5

3"97

15

2~'4 {

~'2 "qo

2 I "i';I

I 'cx)

S a m ble N o .,. Moisture~ . . . . . . . . . . Soluble phosphoric acid, Rcv. Available " Insoluble " Total "

IO I4 Ia 15 15 15

~6"35

10"97 '2"15 13'I 5 :'81 14"96

17"¢J2 I£'2I '2"'84 13'64 2"16 15'48

15"~o 1o'0o 1 'gl 17"6a x "53 ~4"38

2'fi2 '55 I "03 1'Oo "63 i'io

8 t4 ia 14 la 4

Io'99 6'83 2-o~ 8'80 1'76 to'67

13"65 TO5 2"2i 9"co 2"o2 1i'o4

l o" 18 6'61 i '7 o 8 53 I'57 lO"15

3"47 "44 .51 '67 "15 "89

S a m p l e ~ o . ~-~. Moistur% . . . . . . . . . ,Soluble [)hosphoric acid. Rev. '" Available I n s o l ~tb le "" Total "'

. . . . . . . . .

. , . . . . . . . .

. .

.

189r.

Three Samples

,@ul Oul.

_

N o . ~.

A super phosphate.

~

N o . ~. N o . 3.

A complete A complete

"

(Containing

cottoa-secd

: =i

.

.

i . . . . . . . . pliosph'or'ic ae!d ....

I

.

" c,

.

.

difficuh to oxidize.) .

.

.

.

" ~'

6"z~

i

2I

. i

21

9"26 4"75

." .' .' !

,,, '

. acid .... " . .

2i 21

"

[ i

XT54 12"79

[

4'e9 x'o4 t"64 i'34 ±'14

9'37 6"46 ,'3 o

12'55 6'87 z'~5

7'44 5"80 o'87

i

yli x'o7 x'28

I

:6 22 22

!

• • •I

~

i

..:io

2z

i

m'lO

'1 . i . . . I • • " . . " I "

Difference.

5'06 8"77 4'19 16"96 H'42

,~.,2 1o 37 i

S a m p l e Nd__ 3. Moisture, . . . . . . . . . . Soluble~. phosphoric acid Insoluli~.e " " Total ~ " " Availal}!e " "

Lowest.

9'65 9"8~ 5'83 18'3o 13"56

. .

,

Highest.

'

~6

I

S a m p l e ¢Vo 2 . Molstur}i . . . . Soluble~ phosphoric Iusolub|~ " Avaflat~le

AVERAGES. . . .

,

S a m p l e , 2Vo r,

a'ot~l ~

meal and other substances

Number of : DetermiAverage. nations. ;

;

SMool iusbt l e. . . . i n solub', Total Available :

fertilizer fertilizer.

,9>6

i

9"

,.,6 o'86

.................

J I5 ~2 a3 23 23

6"15 6'42 2"94 1"z'2~ 9'27

i ! i

11"47 7'o7 4"37 x3"4o 9'92

4"38 5'83 2"31 ~x'57

!

7"o9 1"o8 2"o6 ~'83

7"20

]

2'72

,

C/le;9lic(r/ Section.

Dec., 1892.]

461

I892. t:our .S'am2les Sen[ Oul.

No.

~,

Super phosphates

containing

N o . 2. N o . 3-

Regular phosphate. Dissolved steamed bones,

N o . 4.

Thomas

Keystone

(iron and alumina)

phosphate,

slag, AVERAGES.

Number of Determinations.

Sample

Average.

Highest.

Lowest.

Difference.

2'39

x'67 7'23 x6'27 7"56

o'72 x'98 0"46 a'77

2"I 4 I3"x 5

0'96 ~'4q 1'28

8"03

2"55

N o . x.

Moisture, . . . . . . . . . . Sohlble phosphoric acid, Insoluble " "' "Yotal " Available "

Sample

. . . . . .

. .

22 2i 2i 23

1"92 7"92 17'1~

~I

9 20

9 "2I 17"73 m'23

22 2x 21 23 2I

--2"52 5't6 ~3"95 8'79

3"so 5-8o 14"43 ~o'58

2i ~I 2i 23 21

2.39 8"ot zi'94 13"93

.No. 2.

Moisture, . . . . . . . . . . . Soluble phosphoric acid, . lnsoIuble " "Fotal " A.vailable "

Sample

--

3'37

Ara. 3 .

Moisture . . . . . . . . . . . . Soluble phosphoric acid, . . Insoluble " Total "' "" . . . Available "

2 "6I 2~'7 2

1"75 6"72 ~1"22

16"95

xi'47

H'x5

.......

Sample

0'86 4"43 i-5o 5"48 i.............

N o . 4.

Moisture, . . . . . . . . . . . Soluble phosphoric acid .... Insoluble " . . . Total " " . , • Available " . - -

~7 3 17 x7 [7

--

--

--

--

Ii.53 x8-4o 6'87

1328 i9.s4 9"96

to'st 17"69 4"94

3"x7 t'45 5 'o2

RECAPITULATION. Difference

1888, I889, 189o, ~89I, ] 89~ )

. . . .

. . . .

. . . .

. . . .

. . . .

.

.

.

.

in available

. . . . . . . . . . . . . . . . .

.

.

. . . . . . . . . . . . . . . .

.

.

.

phosphoric

. . . . . . . . . . . . . . . . .

.

.

. . . . .

. . . . .

acid in the samples

. . . . . . . .

.

.

.

z '48 I "08 1'co 2"I4 2"77

sent out by the association.

o'7x t "92 0'67 o'86 2 '55

o' 7 s "3 ~ --

2"7~ 5"48

----5"o~

These figures speak for themselves and need no comment of mine. To say that they are satisfactory would be untrue. If you compare the results of the last five years, they apparently s h o w a m o v e m e n t from bad to worse, but this is only apparently. The samples of the first four yea rs were mainly acid rocks, which are the easiest to handle, while the later reports are

462

6/zemica!

Sect,on.

[ ]. F. I.,

co mp o s e d of more c o m p l i c a t e d samples. T h i s is especi al l y the case w i t h the samples of this year. [See full r e p o r t of P r o f e s s o r Lord, t abl e herewith.] S a m p l e No. i c o n t a i n e d c o n s i d e r a b l e K e y s t o n e p h o s p h a t e , an i r o n a l u m i n a h i g h g r a d e p h o s p h a t e , w h i c h has gi ven rise to a g r e a t m a n y c o n t r o v e r s i e s b e t w e e n chemists. No. 2 is a r e g u l a r m i xt ur e. No. 3 is an i n c o m p l e t e l y dissolved bone, a m a t e r i a l which always pr es e nt s t h e g r e a t e s t obstacles to p r o p e r filtration. If you e x a m i n e the results of No. 3 closely, w i t h differences of o v e r five per cent. a w d l a b l e p h o s p h o r i c acid, y o n m i g h t a s s um e an e x t r a o r d i n a r y reason. W e f o u n d in o u r l a b o r a t o r y t h a t we had to q u a d r u p l e the filtering p a p e r b ef o r e we could h a v e a clear a m m o n i a c i t r a t e solution, and are satisiied t h a t the main reason for t h e e x t r a o r d i n a r y differences lay r i g h t there. S a m p l e No. 4, t he T h o m a s slag, r e p r e s e n t s a n e w class of p h o s p h a t e s of lime, a q u a d r i b a s i c p h o s p h a t e . It will t ake f u r t h e r s t u d y to a s c e r t a i n if this class of p r o d u c t s can be m e a s u r e d w i t h the same rllle as t he bibasic p h o s p h a t e in t h e c o m m o n r u n of t h e fertihzers. I h a v e to call y o u r a t t e n t i o n to t h e g r e a t difference in t h e d e t e r m i n a t i o n of m o i s t u r e : Sample No. n--Highest, . . . . . . . . . . . . . . . . . Lowest, . . . . . . . . . . . . . . . . . Difference. . . . . . . . . . . . . . . Sample No. 2.--Highest . . . . . . . . . . . . . . . . . . Lowest. . . . . . . . . . . . . . . . . . Difference. . . . . . . . . . . . . . . Sample No. 3.--Highest . . . . . . . . . . . . . . . . . . Lowest,. . . . . . . . . . . . . . . . . Difference. . . . . . . . . . . . . . .

~3"o6 2.76 io.3o 2o.13 9.40 io 73 i3.53 5.90 8.63

T h e a b s o l u t e l y u n s a t i s f a c t o r y r e s u l t s of t he d e t e r m i n a tion of m o i s t u r e c a u s e d t h e association to discuss t h e reason for it at g r e a t l e ngt h, a n d to t h e n e g l e c t of t he m'ain question of the sl~ortcomings in t h e p h o s p h o r i c aci d d e t e r m i n a tion'. T1~e brief: t i m e d e v o t e d to t hi s y e a r ' s r e p o r t w a s

•

=i

.

e . .

~.

2~.

,.

.

"

.

"

~.

.

-

"

-:

.

-

.

. - "

.

/ . .

.

.

.

•

~ . .

•

•

. . . .

,~

to

2- ~

V

....................

o .,: c&d d - i

.~

-.

! t

d 0;~

,,; o~ ~; 42

c .; 6, . ; - ; .d

, "~. ~ -. "-. ~. "t ": ". ~0. ~ . ~ % ~ -

' d

Moisture.

Water

- - ~ -

Solu-

.'X

z

. . . . . . . . . . . . . . . . . . .

"

"°'~;~o

:,~

~" d

'rot.L

q~ q ¢q . . . ,~' , . o° : 'o,.o.., ° : : ~ °o"0 ~ " a ~ " " " v " ",.o ~ " ~ ~ ~ . ~ ..v. u2, u, ~ o,

~-,~J d d ~ ' 5 ~ j ~ '

d,*' ,,: d * '

d 03

--,;u; ,';.~'

~

C i t r a t e AI*tmoniaSol-

(~ ©

.~ /

,d ~,~; d d ~ i ~ . i - J

d..,t & d - ~ ~,;

d

" 5, d , d

Moisture.

~o

?, d

.d 6 , ~ u.;-.; - ~ ; ~; ,~; 6 d c & c~.; 6, d d d

[

....

Insoluble.

a o

z

9 ~

2.2

,~

~

P

~,~zc~2.~,~22.ccJ~J2z.~ -J ~ d , d , d

~ d ~" d , d d d o ~ - d . ~ , d , o ' * - ' ~ -d ~

Total•

oq

. . . . . . . . . . . . . . . . . . . . . . . . . .;

~J

' d ~; ~3,,~; d d . d o ' ~ d ~'~.,/ c~;---/

} o',.~"

0

Available.

I Z ,-8

-

,; ' ' -d~" -; d - d E

~"

~,

,o'~/,.=-"

o~d

,o ~ , 0 ~

;- d - - ~ , ~ ' ~ ' * : ~ ' * - ' ~ "

. . . . . . . .

[ [ $,~" 6,*-"

ble,

m

."

'

]~',d~'c~

Insoluble.

] ~ , ~ o' ,.o,c 5 co, " .,; ~-..o,o-~ ' =& . ,~~ - J

"

~. ~, ,' ~d . ~

Available.

oo

P ,d

•

o

- o - - -

o. &l

]

" I I l~l

,S ~ , o ~ . ~

o

o

o~o~.q

o o o

"" I ~od .~d ,od ~o ' do

I I , I

o~,~o~o~ooo~oo

o

~

[ I ]

Moisture.

Water

blc.

Solu-

"
P

[

Dec., 1892.]

6"/temical Section.

463

absorbed w i t h o u t v e n t i l a t i n g the serious irregularities in the results o b t a i n e d on phosphoric acid. W h a t can be the reason for the u t t e r failure of last year's researches on phosphoric acid ? The samples sent o u t by Professor Lord were prepared with the u t m o s t care, which i n s u r e d absolute uniformity. Sho::ld we assume t h a t the balances have not been r i g h t l y adjusted? Professor Payne charges m a n u f a e t u r e r s w i t h using bricks for weights. Have some of the g e n t l e m e n made proportionate mistakes in analysis? T h e failure to reach closer results in moisture shows very plainly t h a t the necessary care has not been taken in the work, and when in the simplest d e t e r m m a k i o n of all analytical work such blttnders are possible, we need n o t wonder at the differences in other more complicated determinations. A n a l y t i c a l work will always bear the stamp of individn ality, and no absoh: te identical results can be obta{ned, but the differences should not rise above a narrow limit. T h e proposition, made at the 189o session of the society, by Mr. Charles Gibson, of Chicago, to c h a n g e the ot?icial m e t h o d of phosphoric acid d e t e r m i n a t i o n by m a k i n g the a m m o n i a c i t r a t e solution slighffy alkaline (p. 17o), caused me to have a series of researches m a d e in my laboratory to establish to a certainty if such an addition of a l n m o n i a would work d e t r i m e n t a l l y to the interest of acid p h o s p h a t e s derived from lime phosphates. T h e result of n u m e r o u s analyses has d e a r l y demons t r a t e d t h a t it is n o t possible to show any difference between the results obtained w i t h a neutral solution of citrate of a m m o n i a a n d a slightly ammoniacal solution. As an example, I will g~ve only two analyses made with our own acid p h o s p h a t e : N e u t r a l £'oluttk~n ot Citrate of A m mo~t t~z.

Hmmontacal Solu. tion o f C i t r a t e , Spect]ic G r a v r t y I 9 o . a d d e d to , o o co. C i t r a t e o f A m monia.

.Vo. r

N o . 2.

.No. *.

No. e.

I3'34 2"24 I5'66

12'66 2"62 t 5"28

I3"5 I 2"t7 15 68

Total available phosphoric acid, . I2"66 Phosphoric acid . . . . . . . . . 2"62 Total phosphoric acid . . . . . . 15'28

VoI,. CXXXIV.

3t

464

C/zemical

~%c/i~m.

[ J. F. 1.,

S a m p l e No. i is a b s o l u t e l y i d e n t i c a l in i t s r e s u l t s . S a m p l e N o . 2 s h o w s o n l y a d i f f e r e n c e of o ' o 7 . B e i n g s a t i s f i e d t h a t in t h e c h a n g e to a M i g h t a m m o n i a c a l s o l u t i o n of c i t r a t e of a m m o n i a f r o m t h e s t r i c t n e u t r a l n o d i r e c t h a r m will b e d o n e to t h e v a l u a t i o n of p h o s p h a t e s d e r i v e d f r o m p h o s p h a t e s of l i m e , o u r c u r i o s i t y w a s a r o u s e d to see w h a t a c i d i t y w o u l d slnow in t h e s a m e m a t e r i a l . ,~,'an@le :Vo. L

.',)~mple NO. 2.

o'Zq (;r~;,n,,;ne ~ ) ' l r l c z'oo (;:'a;';t~'ne t)Vr;"c Ac/d tJ zoo (~" A c i d to ~,o(a o f C/grate ~..I ntmo(. {IJatc o/" A ~z-

Total awtilable I~hosphoric acid . . . . . . Insoluble phosphoric acid, . . . . . . . Total phosphoric acid, . . . . . . . . . In(:rease of awtilable phosphoric acid,

~2"85 2'43 I5'28

~3-7o 1"98 15'6;

o'J 9

0'29

T h e i n c r e a s e of tile a v a i l a b l e p h o s p h o r i c a c i d u n d e r s u c h s t r o n g a c i d i t y as is p r o d u c e d 1))7 t h e a d d i t i o n o f o'75 grin. a n d i g r i n . citric a c i d to ioo of t h e n o r m a l c i t r a t e of a m m o n i a s o l u t i o n is o n l y o'~ 9 a n d o'2 9 p e r c o u t u r e , a v a r i a t i o n w h i c h is g e n e r a l l y c o n c e d e d to b e p e r m i s s i b l e in a n a l y t i c a l w o r k , as s h o w n b y all p r e v i o u s r e p o r t s of t h e s o c i e t y , p r o v e s to o u r s a t i s f a c t i o n t h a t t h e c l a i m so o f t e n m a d e , t h a t t h e c h a n g e of t h e a m m o n i a c i t r a t e s o l u t i o n f r o m n e u t r a l to acid c a u s e s g r e a t d i f f e r e n c e s in t h e r e s u l t s o f p h o s p h o r i c a c i d d e t e r m i n a t i o n s is n o t b o r n e o u t b y c a r e f u l researches. I n o r d e r to t e s t t h e s t a b i l i t y of t h e c i t r a t e of a m m o m a s o l u t i o n , m y a s s i s t a n t , Mr. B e r g a m i , p r e p a r e d , O c t o b e r , I89O, a b o t t l e of n o r m a l c i t r a t e of a m m o n i a s o l u t i o n , w h i c h h a s b e e n k e p t in o n e - h a l f l i t r e b o t t l e s , g l a s s s t o p p e r e d , in a closet, a n d f r o m t i m e to t i m e t e s t e d ; t h e l a s t t e s t w a s made a few months ago, a n d proved the absolute n e u t r a l i t y of t h e s o l u t i o n . i n o r d e r to p r e v e n t t h e f o r m a t i o n of f u n g u s in t h e s o l u tion, w e h a v e , d u r i n g t h e l a s t f e w y e a r s , a d d e d to a q u a n t i t y of a b o u t t w o l i t r e s , o ' I g r a m m e of s a l i c y l i c acid. W i t h o u t i m p a i r i n g t h e n a t u r e of t h e n e u t r a l s o l u t i o n in t h e l e a s t ,

this minimum quantity has successfully

prevented the

Dec., ~892,]

Chemical 5"
465

formation of t h e f u n g u s and t h e r e b y destroyed the possibility of changing" the neutral condition to acidity. This p r o v e s to our satisfaction that the claim of unreliability of the citrate of a m m o n i a solution (p. 179, 18o, Rep. of I89o ) is not well founded, if all necessary precautions are taken in p r e p a r i n g the solution, and .keeping the same in not too large b o t t l e s well stoppered, as r e c o m m e n d e d long ago by Prof. P a u l W a g n e r , of Darmstadt. The claim, m a d e b y the advocates of the ammoniaeaI citrate of a m m o n i a solution, that the slightest acidity will impair t h e correctness o,f the analysis in alumina p h o s phates or producers, was ahnost incredible, and the publication of the analysis by Mr. Williams, pp. I78-I79 of the last report, proves that the fault m u s t lie s o m e w h e r e else and not in the normal neutral solution of citrate of al~l]lOllia. T h e r e are n u n : e r o u s other points in the determination of availabIe phosphoric acid, which might let in small variations ; t e m p e r a t u r e variations in the water-bath, the washing of thc portion insoluble in citrate of ammonia, m a y influence the results, b u t I do not hesitate a m o m e n t to say that if the official m e t h o d s were carefully executed b y a c o m p e t e n t analyst, such discrepancies w o u l d n o t be possible, even in case of iron and alumina phosphate. T h e A s s o c i a t i o n of Official Agricultural Chemists has given us the v e r y b e s t m e t h o d s for the investigation of fertiliz e r s - m e t h o d s that are accepted, with a single exception, over the whole U n i t e d States (New Jersey alone determines a w d l a b l e phosphoric acid at a temperature of 4°0 C., instead of 65 ° C., falling t h e r e b y one-half per cent. lower in average result). T h e association has now the imperative d u t y to establish the fact, t h a t it only needs careful and competent workers to m a k e such results as are laid before yon to-night, a b s o l u t e l y impossible. T h e fact t h a t differences of two per cent. and six per cent. i n s o l u b l e phosphoric acid are possible in test samples prepared with care for the very purpose of a trial of methods is calculated to u p s e t all confidence in the so-called control work of the A g r i c u l t u r a l Experiment Stations.

466

U/to,flea~ £-cc[zo,.

~_J.F. T..

'lPhe difference in results as shown by the reports on phost)horie acid has very serious consequences for the fertilizer trade at large. T h e stations ]lave a s s u m e d the roll of arb{trators b e t w e e n b u y e r and seller. T h e y have gone further, and act a s advisers for tlle ra;mer by e s t a b l i s h i n g v a l u a t i o n s based on chemical an a]ysis. 71 will not ventilate to-night the real value of these valuations, but take facts as I t~nd them. T h e m a r k e t w d u a t i o n as a d o p t e d by ttle Gastern a n d Middle S'ta t e s is, I bc!ieve, seven and oneq~alf or e i g h t cents, per u n i t available phosphate. S u p p o s i n g it is e i g h t cents, and take sample No. 3~Phe first analyst makes available phosphoric acid 16"95 per cent. ~ 8 ~35'6o X 2o $2 7" I2 valuation per 2,ooo pounds.

T h e second an~dvst m~tkes available phosphoric acid 11"47 X ~q

91'76 X 2o $i8.35 pei" ton.

Or difference in v a l u a t i o n of $8.6 7 per ton. On w h i c h analysis shall we b u y ? is a question which r e a d i l y will c o m e to the farmer. S u p p o s i n g Sample No. 3 r e p r e s e n t s a b r a n d g u a r a n t e e d t h i r t e e n per cent. of available phosphoric acid. In several S o u t h e r n States a falling off of ten per cent. o f the g u a r a n t e e d analysis makes the goods liable to confiscation. In this case two analyses of S t a t e chemists, the s e c o n d and sixteenth, will b r a n d the goods as to be c o n d e m n e d u n d e r the law. But if the m a n u f a c t u r e r s h o u l d h a v e b e e n misled by one of the n u m e r o u s h i g h results, a n d p u t h i s g u a r a n t e e high, he m a d e h i m s e l f a criminal in half t h e States of which yo,a h a v e the r e t u r n s before you. As long as the results of c h e m i c a l analysis are so u n c e r tain, as s h o w n b y the work of t h e official a s s o c i a t i o n

Dec., I892.]

(./zc~nica/ Scctzon.

467

under the most faw)rable examination, the public should be extremely careful in forming judgment on a single report of a station if the same should show a remarkable difference between g u a r a n t y a n d results. The fertilizer trade has been m a l t r e a t e d b y suspicion, perhaps, more t h a n a n y other trade. T h e trade has been s u r r o u n d e d by an endless chain of different State laws; some of which are in conflict with the Constitution of the U n i t e d States, and these laws are, to a great extent, based on the idea of the infallibility of chemical control. How infMlible the States' control can be, I have shown you to-night by the work presented. The work of the Association of Agricultural Chemists deserves to be h i g h l y c o m m e n d e d for the good it has done, b u t the association m u s t go further, before it can hope to be recognized as the arbitrator in the fertilizer trade. The association should influence State legislation t h r o u g h its members, to the end t h a t the laws r e g u l a t i n g the trade shall be made to conform with the practical results of their work. The influence of the association should be exerted likewise in t h e legislation of New Jersey, to effect the repeal of an a n t i q u a t e d d i c t u m in analytical work erroneously sanctioned by law ; and in the Southern States, where u n j u s t laws h a v e been based on the belief in the infallibility of control work of the agricultural station. 1)ISCUGSION. DR. \VM. J. YVILI.IAMS.---I have listened with much pleasure to Dr. T e r n e ' s paper on the discrepancies found in the analyses of different official chemists when engaged in analyzing the same goods, and no~ merely the same goods, but actually t h e same (divided) sample of the same goods. Dr. T e r n e has called a t t e n t i o n more particularly to the analyses of b o n e - - r a w and partially dissolved. Similar eases h a v e arisen in my experience, with even greater diserepaneies in dealing w i t h our K e y s t o n e concentrated phosphate, a e o n e e n t r a t e d phosphate of iron and alumina. While several c h e m i s t s of high s t a n d i n g in the profession,

468

C ltcmzca? .%ctzc~n.

[ J. F. T.,

b o t h official and non-ot:ficia/ cllemists, gave tile q u a n t i t y o f available p h o s p h o r i c acid fairly closel.y, as, for i n s t a n c e : I±ev C,m~.

]'~r (.,wg.

3o'6o 30'87 31"o? 3"-'35

3°. 25 3o'35 3o"37

o t h e r s could only g e t 25'22 per cent. and o t h e r s 20" 3I, t9'4o and ~9"7o pr~r cent. T h e last t h r e e especially show a difference b e y o n d any r e a s o n a b l e limit. Now, as t he v e r d i c t of an "official " c h e m i s t is final in h i s State, or at any r a t e his figures are p u b l i s h e d and b e c o m e g e n e r a l l y known, such d i s c r e p a n c i e s work g r e a t i n j u s t i c e t o m a n u f a c t u r e r s , and if t he official c h e m i s t s could m a k e s o m e c h a n g e in t h e "official" m e t h o d , w h e r e b y t h e s e d i s c r e p a n c i e s could be m i n i m i z e d , it would be a g r o a t advan rage to all concerned. ~Phe q u e s t i o n has a l r e a d y b e e n d i s c u s s e d by t h e ofticial c h e m i s t s in convention, b u t up to this t i m e no s o l u t i o n of t h e difficulty h a s been a r r i v e d at. One p o i n t s u g g e s t e d was t h a t a sl i ght a c i d i t y or a l k a lin ity of t h e " official " n e u t r a l a m m o n i u m c i t r a t e s o l u t i o n c a u s e d th e g r e a t e r p a r t of t h e s e differences. So far as m y own i n v e s t i g a t i o n s go (made ~mce t he e o n v e n t i o r t a b o v e r e f e r r e d to), I do not find t hat a sIiSz! a c i d i t y or a l k a l i n i t y o f th e s o l u t i o n m a k e s any a p p r e c i a b l e d i f f e r e n c e g r e a t e r t h a n th e o r d i n a r y errors of analysis. T find, however, t h a t a s l i g h t di fference in t h e t i m e o f e x p o s u r e of the m a t e r i a l at 65 ° C. does m a k e c o n s i d e r a b l e differences in the results. T h e i n s t r u c t i o n s now g i v e n r e a d : " C o r k the flask s e c u r e l y and place it in a w a t e r - b a t h , t h e w a t e r of wh ieh s t a nds at 65 ° C. * ~ * Raisingthe temperar a r e as r a p i d l y as pr a c t i c a bl e to 65 ° C., w h i c h is s u b s e q u e n t l y m a i n t a i n e d , di ges t for thirty m i n u t e s fro,tz tlae i~zstant of inserlion," etc. Up to I887, I think, or possibly 1888, t h e i n s t r u c tions were to this effect : Place the flask in a w a t e r - b a t h , t h e t e m p e r a t u r e of the w a t e r in which is 65 `0 C., rai se t he c o n t e n t s of t he flask up to 65 ° C. as r a p i d l y as possible, a n d maintain at tlzat temperature for t h i r t y m i n u t e s . (I c a n n o t

Dec., i8921 ]

C/zemica/ Section.

469

give at t he m o m e n t the e x a c t words, b u t t h a t is t he substance.) Now, it w o u l d a p p e a r t h a t this difference of i n s t r u c t i o n s should not be of m u c h m o m e n t , as all u s i n g t he official m e t h o d are w o r k i n g u n d e r t he s a me i n s t r u c t i o n s , and in all cases th e t i m e of e x p o s u r e to a t e m p e r a t u r e of 65 ° C. is of e q u a l d u r a t i o n , b u t such is n o t a c t u a l l y t he case. Under t h e e a r l i e r i n s t r u c t i o n s t h e c o n t e n t s of t h e flask were unif o r m i l y e x p o s e d to a t e m p e r a t u r e of 65 ° C. for t h i r t y minu t e s ; an d u n d e r t hes e c o n d i t i o n s t h e s e g r e a t d i s c r e p a n c i e s in r e s u l t s a p p e a r e d n e i t h e r so f r e q u e n t l y n o r to so g r e a t an e x t e n t . B u t w h e n the i n s t r u c t i o n s w ere c h a n g e d to t he p r e s e n t form, viz : " D i g e s t for t h i r t y m i n u t e s f r o m t he i n s t a n t of i n s e r t i o n , " t h e n t h e y b e c a m e g r e a t e r and m o r e f r e q u e n t . Th is , I think, is due to t he differences in t he c o n d i t i o n s to w h i c h th e m a t e r i a l is e x p o s e d in the w a t e r - b a t h ; t h a t is to say, th e s o l u t i o n of e x p o s e d n e u t r a l a m m o n i u m c i t r a t e r e a c h e s 65 ° C. m u c h q u i c k e r in some cases t h a n others. I m a d e i n q u i r i e s f r o m m a n y c h e m i s t s on this point, i. c., how l o n g it r e q u i r e d for t h e s o l u t i o n in t h e flasks to reach t he t e m p e r a t u r e of 65 ° C. a f t e r i n s e r t i o n in t he w at er-bat h. T h e t i m e v a r i e d f r om t h r e e to nine or t en m i n u t e s . T h a t is to say, th e t i m e d u r i n g w h i c h t h e m a t e r i a l was e x p o s e d to a temp e r a t u r e of 65 ° C. v a r i e d f r o m t w e n t y to t w e n t y - s e v e n minutes, a v a r i a t i o n w h i c h is, I believe, sufficient to a c c o u n t for th e g r e a t e r p a r t of t he d i s c r e p a n c i e s . T h i s v a r i a t i o n in t i m e can be a s c r i b e d to m a n y causes, c. £~., size of bat h, d e p t h of water, q u a n t i t y of h e a t used, t h i c k n e s s or shape of flasks or o t h e r vessel, etc., and it w o u l d a p p e a r i m possi bl e to p r o d u c e u n i f o r m i t y of conditions, and, t h e r e f o r e , uniform i t y of r e s u l t s u n d e r t h e p r e s e n t directions. I think, however, if t he i n s t r u c t i o n s were modified, so as to secure t he e x p o s u r e of t he m a t e r i a l to a t e m p e r a t u r e of 65 ° C. for a u n i f o r m fixed t i m e of t h i r t y m i n u t e s , as was done u n d e r t h e o r i g i n a l f o r m of i n s t r u c t i o n s , i n s t e a d of to a v a r i a b l e t i m e r a n g i n g f r om t w e n t y to t w e n t y - s e v e n m i n u t e s , as u n d e r t he p r e s e n t f o r m of i n s t r u c t i o n s , t h a t t h e resul t s w o u l d be far m o r e u n i f o r m and would be far m o r e s a t i s f a c t o r y to all concerned.