. . ?1';157TROTlrjCT% 01 '

TII~GO .bets ~ 2 ' 0 lillElar.~k~zi to doi;o;?ia-a .;;?la f!ako sf roackfoa between X6ah.c p h ~ 3 p h . t ~ rock e . d B ~ U F ~ C a0f.d h p ~ o & ~ c k l o l l irf ~~pX"ph03pht8 f02%=88~~ Is; ims hopsd t lmt %he rariotion ~v51.d be faat onoug'd ' c ~ parxttI tkd ~ o o k and acid f;es 2701 &md mcl epplisd ZreotQr t o Ulo a052 aa. a wet gull, or slurry, cost 8 ~ d - z 4 of a 3~oceciw+o o-mr preaont p m c t t c ~ ~ m v l & lm ez'b oxea e p " ~ ~ r e d .

> . , . . . .

. . . . . . . : . " ~.osriwini %?lot the :&m;p>c,t~ *1 iatr rock ~ r n p r ~ r ~ s ? , as - t ~ i o a ~ o i m ~ ~ I O D ~ M ~ R ,

- , %?i~:.pudca$~ ;of :'m%dulat;icn . Cepixl upat : th9 mowi-5 .cd? -,wid @dedo . With hx:roaa.?.ng -. . . - . -.xrnomta . aqr48:r 'tiAa(130iui.i l j ? ~ 3 p * d ~ 3 (CbirC : Z?$ j ;, , V L O ~ O O L J . ~ B ~ L L @ ~ ~ ~ p h t e

("Ay yo ) ; ,., R 0)' and who~~horlc ~03.6. , (L3?0,. .=a Sm*mrf. In g31era1 l l o p:w&wL . . , "" 4! . 4 :2 . . 2 , .,

. . khan' szdfmic aald 1e add08 to raw phospPmt;s ~oo?<, if i n bdiomci that som ~hosphoria mid f o jaev&tab?3 f ormeb, ~ o ~ ~ b ? - o o s of Bt;% m o m t oS a ~ i t P c t c zold q y l e d , .DepsadZng *&a on the ratio of rook t o mid, %hi@ ybocvhc\rlc ~.ciC; r a ~ o t s :d.-V;!2 the %rf e~lc9.m p h o ~ p k h to form tho 62- or rnox:~e50iu~ phoa?lra.i;s, F~oscsfom; r;ho T o m t i o n of , t l ~ ~ s s add pilclr3phaha l a , e.(; Isnsf pwtleXlyo a n c c o n r ' ~ . ~ react.2.m I:ckad of the prhxry soactton ~ f c a ~ d nhva. !?lie rate of reaction ol p310spI.ro'rlc-.

The primmy objooe' of theso te~ts uas t o d o b m h s tho time ~cquimd for aom- p l o h consumption of the a d f u r l o m i d W r myjag oondttione, Tha desired oharges of' ph08phEits rook and wld mre mamod 5nto bakers and. f l o w a d to stena for the requimd length of i;ime ~ 5 t h occaoional sti1~5ng of the c h g a , Tmy -re thdn illlutod to a b9hi.eS mlum, f i l terad, and the filtrate was m l y z e d for sulflrrio actd, Sn the arl@-d tests it was hoped Z1mt ehio could bs dons by titration 'agahelc a base, 1? rtolution of NaOH m e s ~ ~ ~ z e d agaimt the aulkrric acid to bg u88a,.It ttas r3~;Umd that the varlaus acid phosphate salts roacP,

' ' aoidic t o sons indicators and neutral or basia to othsrs, but L t was hopad that a i -' definite reference pout could be obtabed, Hmvar , even via 5 ndla9tore deneitim . .i f a t o change-at a low pH, some p~ecfp ibt ion oacmcpd boforo an end polvlt m a rerachod, i ' After several attempt6 8tith PaPiw Micatorts, it a 8 found that roliable data . oould not be, obtained by t h i n nothod.

." 3 -, I ' . . oll @sts in uMeh ~lumtrio and pvimetrfto do2emhatiorm were t tsaa found, es e q that the gravimtrio cmlyaia for ctuXato was

r~waye m h 1-T than ths vo~ttmtetrio t itratio " iides the Ixr.torfore??ce of the mioue .@.te .,this indioated;,t@, . , ." ., . , . A . . . - . , * , >

lal tds gmvimeizio detsrmioeUAw-, the tow -eto rn solutian uas preoi~itated md reported in toma 0f3o4. m e figure ino1udsd any eoluble calaimn mt if was OTma to be , To detemin.8 fhe actual mount that might be exa mcbd'9.n eolution, eulf'wilc acid ample6 of vcu- etpongthe mro f i m d to 3tand with 3&0 un t i l basio t o Utwe Bepading m -he, o r i g f n d tmagtl the f t l t r a b e amtained from 0.126 gram t o 0.185 ,m of aolubls s (:h l% >f H f l 0 ~ ) pep 100 a .a. of solution.

prase= .? - .

&a Am-

sU. chargoo for enough acid to coc?hlne r , l l .Z?o CaCOg .';o

r o m m~wn and to react w't2.h tho Fa303 bo form FO~(SO~)~. l;rr zooic malysoo 42x1s waa cal .culaM 3e651i grain of R214;O4 for a chmgo of 5 grine, Tho follarr- Ing m3w.I;~ of' act4 EUW brlsrefoss roquirod to eatfsfg ths sqmt5.rno Pm 'cho aaid213.~.t%on of the T

SL-f c Acid R3qwLmrton.t~

In Teer*u Roe 4 three aharges ware nighed out and mhed as follow t

- ... of R2S04 required

I1 - 5 gm. of rook - L1.5 0.c. t.mtor 3.5 c.e. of a k n d ~ ~ d ~ ~ 3 0 4 Ii

Tho wa'w was added to the rook fSrsL, snd then the &aired amotm'c of wc3.d vim IW In t o make a total oohtip . velum of 15 0.c. Aftor s t r tndhg hours Y(ieh o c a ~ m i d . ' st9nrhg, 85 0.0. 'of water m e addsd t o maks a total solution volume of ?LOO aoa, 1 This w s fmnedfalx+ly f i l tered , ard the fII%mto was anelpod fm aulfab, 1:

Followbg the eame procedura, f i d e n t i d aharges numbered XO, V, and V I ~aem pmparwd end f lowed to e k d oms~nlg't bof me df luting and ff lhring, Tho ~ e a u l t s

P of thio t 0 s t a m t a m ' t g d Bolw,

: i Table XI ,!

P~oduct of rook

Dlcalo5um phosphab ~ a I i w ~ 2H30 o . ~ . 6 0090

Mohr In t5.0 abom hbrdl.ation no RXlovance fs & for the aolublo CaS04 5.n the 2l2.'Grah, Z"c aexact-t momCL is no% knoam, but 5% Es probably a 2a~g0 p r b 02 %ha 2esSd2a,,l suZ5?ats as it fa only slightly grsater %bn was found t o bo present 3n %ha

3

I

for impurities S o w . po

Pbnocalo%um phoaphab Cd4(m4)2 A20

Phosphoric acid H3P04

in 5 gm, of rock

0,655

0.655

0,655

0,632

@no of rook rock

2.80

I 1,555

2.455

0.918 1 2.70

2.2 a,o,

305 a*Ca

I -

30355 1 4.75 0.0. I

fiI.t~1;.k<ss O? tho pro~.hdrc~.ry %ea"us civ g'p3:m c:slitbf SYcy in tr?*icS\ Pi. wag kpo:,.n no ? ~ Q Q ~u1fvri.0 acid wi2.s precent, In cuil.neqi~ent I;ss%c; it b0.a fc:.x~irl that t h l o rs- sddual ~ ~ I f c i t a ins alrmys *0,200 si/1CC. c.o, (5n ttrm of B$Cii) :rlls~ th.9 raactiac m s co:np3.e-k? ,wd ma, theroforo & 6 ~ 4 :i~f;~bv I'CZQYO~CB poil'l.b,

. ' Refer0n.x t o the a b ~ w tabla ;.n&lc~.tos .I;h.at; f o r all practical purpcaos fn I, 11, m, nnd V the aulfmio acid is 8ntb~Lr con~\a~[t3d 3.n 2-& hours, The ad- ...

d i t i o n d acid ohtarget3 to II anil Sf over P and X'J dooo not result in d.drt ional SIC- fate amtent in the f i l k r a t e , In If 1 LLQB VI, lr*era enough acid mu &aii40d to . t.heo=tical'fy' aonmrt tho phosphah t o ph.oapho-i.5~ acid, -the s m ~ i z acid vas. not dl cousmd, and the reaatfon . was . uot coiipleb in howso .. ,, . .

' P Following Teat Roo. 4 , a'serlez ol t e s t s L,EJ ~&.e to debmlne Lks effect of

auld ckllut.icm on the rate of reaetj on, The tkocretical amount of acid (3.5 c ,c, of sAhndard acid an 5 grm.8 of rock) t o prducs .nmccEilciun phosphah ~a3 used on aIl,tests. . Eight sai~ploe ,wepa prerhod 03 each U ~ t i o n as followst the required mount; of w.hr was added to the 5-grax c1zcve; of rook, followad by 3,5 c .o, of tho atmdard se9.d.. The chsrgea were atirrsd a t ocoasioml intervals, an3 one s q l a ' ' .was d i l ~ ~ t e d to 100 o,c, to.i;aL solut.ion velum m 3 fnmodiately filtered at tho end

. of each 15-1xLmte period. . The fllfmtss wero analyzed for. sulfato, giving data on unoons~md &id in ,l5&'ta int~r.rals up to 2 h~urs. ,. !bey are tabulated belaw* ,. i ? . .,j5-?: . ; T ,. - . - . , A .a_+..

I ' . , . ~ .::: <:J; : ,~~. , . ,y :y i : ; - .:,,;y.* :.,!,.;;> . . . . . . . . 5 ..a;. ". . < . . . , . , ..: ,. . I .. . . . . . x , . r . r n . . . ,.. ; ,... . . .. Tctb3.0 TIP . . - . . { ; .< r*::. . . , .; .d - -. . . _, .. ..,.- Y . . ,. .

. . .. . 3,

' .' , I .

'- . . I.

~ i ~ t m b w e a s

. 1 ; .

Ltr

1.045 - u

Rock 'U 5 ~ ~ U . R B I 30 [ .- 10 c.c.! 0,2:26 1 0,959 -I-- 38,4 W a t 9 r . l C 5 a . c . 1 45 [ . - - . . 10o.ce.l:39 1 0.795 -- 32.2 .I- .-..-.---

S M , acld 3 3 3 a , ~ , I 60 1 .--I-- 10 u,c.I 0.157 1 0 J%sL-../-.. 25,7 ? a M solutfan volume 5 .I 0.660 0 n a.-.sD- d w h g seaot ton Lime 1 90 1 5 1 . + A ,,,,,

PI = AS,,&& I_JI%-""l..J9 -kt&.-;-?". 0.307

Y I 3 ~ ' 3 & . & 2 f B * --.- ;...".-3,,7,--- ?-ra t ol. r?.dild9? lmfor e =0 I 1 C c,c,( 0,UD 12 A. f i l t e r J 9 - 95 c,c, --_-.-I-&*. --.W___U_a- ....-a --_I-- ... -- AS--^.& m

I i ,,,,, ,,,.,,,- -,-...A .,.,, ,,",2,,, ---------, .---..-.......-,...-. --->--

P ,. -I 6 m G i i .- a 30~7 1. 1 ~ o p c i o~tro_~c_ (123.6 -:-...s---.-a.wm

0,563 Rock - 5 pxipm 22.G ....---C ,XI..-- PC-*-.-- -- L 30 j PO cecci oJ-:Ib 1 _-----;.. ._-._._-..-._,

\k.I:.ite:. U, 6.;:; C * C + 1 45 ! 3.0 r:,c.l .0,0:25 1 0,399 1 T 5 , 3 . ...u.- r r r ~ ~ & - ~ - r - - - u . r c - . - - . : - --.-.-.--em

Std., eeid r 3.,5 Cite L , V J -I-..--WUrUUII-.-..,--*- 0,324 13.11 Tok,S t..olu.tion v o l . ~ - 7 5 J O ,-,--, I 0,252 , & - . ..,..,..";.-fi.-- 7 0 3

3 (.3 i :LOc,c,j O , O ! j 2 (*0,2.16' _-& ,,_-_-, - d - i b g rc3?,otLon %5m _ _ _ - - *

t.3 10 cj- e& 1 10 o , d OO.O:iO 1 0.210 t CKSW *i~? !S05 UL.-. - -- -- ... ,,----, 4-*..-..-..--"..

flator E . ~ A ~ ( I L J C ~ O T O U O 1 10 ooco! OoO:iO 9,210 8 5 f.'fLf;02it?g, I - - . . . - - - % 90 ceo, L .Ill-J-. I I --U_ ---.-.-----__..I__I_L.-Y..--- - - ..I.-.N.mL..-..-. U. CI.-.C-L-U-....Ir

-.-....-.-.I.. -I---

- . . - -" - To6-b 30, an.5 ckmgo ~ o n c - b i o ' i . ~ Fik.i;~e:'i Anavaos 5 of orighLL &at9 for e e ~ h a q b 'F ! T G , x Z & F p ~

~ ~ ~ 3 . v . aoia ot%U 2'1 - ~ f ~ u ' b e d kd:en 0 . 0 0 . , PlX+*ab . --- -- .1-

. Rock a 5 - g r w l 'fdb~? m 16.5 0.0.

Sfd. ao id 1 3.5 oeae Total. eolutiloxl voltEwit'

Wahr r: 26.5 U.C.

S a m t 3.5 6.6. T O W solution volwa ' a m wa0i;faa tw

T ~ O ~ai;a of T~UQ III ere p ~ c t t e d B- I. IQ ~ e o t E O ~ 7 vbra noat conaantr&oL a d d ( 5 o .c. ~olukinn ~ 6 h i . 1 ~ during -bhe raaetioa k h f L!B w d , the maoBion rat& i ~ ~ . o b v i o u s ~ olow;. -Vn~n when tho noro &lute acM is appl id , AZao, more arraklc points wsre ob%ainetI ca t h i s plot. Zn th~se p?opa.'Lf m s %he rock .zx-i:t acid' f o m a a skiff m u d that was B1QPfcuZ.t -bo rAx into a W o ~ m o l i i ~ y , Conshx-t ~ti~ring wouad mdoubLedl.y g5.m rx emookB~r curm and po~alb3.y s p e d up thcs ~eaaW.oc sab ,

In t h other tooto, a c o n n ~ . t . 09 0,200 gran of rosid~dl B ~ P ~ ~ c P " ) (PA tcmo of B2.SC34) p w 100 o.c. of eolatioa Qfs ?kpp~o&oh~dl as %ha reaotiozl nsms aanplwb.tcr, Thd C'C(S*~B I;o* Iavel ou-b Em& co:'.nc5t!o foa raac.(;"~on tims b g d 75 nTl.auteo h?dfca%-d b g "Gbt, with roforenco t o %ha iniLfkcic tiaid.., '~aaation i o p~ t s~Zlodt ly oO%pIcb a% t h i s tkw POP OU ~ ~ 2 1 f o ~ ~ APchough +ha ac:Ld &%lation has l.%t%J~ oPZast on the find. en4 gob%, tho ewms c:Row appreoiable spread fo r the SnPL.h l ~ i o d 0 of the ~ a a e t l o ~ , ~ more Bflub soXutions ohowing .&Q f a s b n t r&b , Q I I I I - - - - - - - - l - - . . - - ~ . . . - L . . , - - " . . ) - ~ . . - - - - . ) - w - - - -

(1) Aa pevlmsly nos, no oorreot9on f a mado An this figure for %b~j 801u%1-8 cd~aum sulfate p o ~ e n % ~ 5

. . : . . . '. .;:,

.I ' . . Xn: t3e 'dab, ~ X V ~ I C I X ~ % X ~ t o this pS.n-3 2:) .ag:r.:;!.cn Is?!! teen nhilio 02 (;he dL&x?:,e:~:.:.:.: :.:. of -him phi3gpklat~ 9n the prd.uats, ~~.t;hoi-$l ilo:;.i! ;;.l:~k ~ ~ d d I;* ~ P O ? ~ I : ; G ~ < l ~ f ~ l - ~ ; i;:: .-. Y gshb1:lsh thia, O ~ Q prsJb&ary ton% k~cs 'uzarl :I.:: fie tc: rt.;.:tsmb - k11o -:;.rtu-3izL ,~3,d@ c.wihbl8 .,by tb ahoYat '&ha acid. tmd;~ir::r k , '..'. r*: chmpr; WTe p?np&::.:!?. an P.'32:to;;r n

. . . .

I.), i'%qek - 5 ' wans Water - 21,5 o ,, c , ,C;'lr:xl:&ei.*ii (tc::td - 3,5 e o~ .1 ' 2) ' $:%oak- - 5 pama CIabx. - f 0,5'3 c , l . ~ : . . . . . Stnr:3ard acid - .!..,.25 ?,a?

. . . . 8 ,.

~ h n : . s b p ~ e s wars ollowod $d,'ekni i 2 ~ I ~ J C P ~ .;.i-:,i~ C * C O C , S ~ C ~ ~ S ~ ;st*C~.;.is, d:.l~rhd to I00 u 60: '.aolu%ion xvlm, Ri.l.tam12, and t9sI;ir.l ;: :x~{q?;j-, Tho .ki;sl 7 v ~ l 1 ~ h of x.~lc.ch i'iltra'&~,;~-i ,malin;rod, and the rss?.&lco tTCK.'Cj d..8.13:2 =C ?.?Big17d., I!$ XII%sf:Lba t : i . ~ ~ andy%sd~?&*"'~uli'aQe and P$5 :' D o ra:li&uc?a ?rz: 3 ;wn for ciltrabo so?.t~lfie ZJZO5 'tt,xtj. .. "-.it y . , A . . . . . . . : . hM3~zQ$3:g ::, : ;. ... ; , . ,, . ... :. . . . . .

. . . . . . .

t ~ r &pf;+~ ~ ~ ~ o 0 ~ t 02 ~ 1 ~ ; ~ j . c : nrsJ.2 (.>:;r,.lj:~ :I .),3 I\'3 ,. F? :],I:J: i*6;>!><,);> + :: ~4 ~~j.~+,:!>:ii ~ 2 ' ~i~ti5Jflbl-e Y J ~ ~ ~ ~ F ~ . ~ , $ B , ~ ~ ~ ' ~ p * ~ ~ ~ k:, !{fi!il:: ~~k~c::P:l+ *iV?~fi.t 13~ ;!r:, 5~3~!f~&i>le

.,., : , ~ ~ ~ p ~ : ? , > ~ : ~ i ~4 1t1*@!:3,'3:2!' Q2Um.t sf %1;.:',a m?fW l o acid ronsk.,?.rn :Is th.3 ?iFi:<-$,h r..l-, B W ~ . n6'b I x r ,k~lo::atc d, In qppXicat,:_c,: : ';a iL.x,.c 3 c i98 , - - - - - ..a. .. -.I ...... 4." ...............r. u -. .. u u .........a ... ............, (2) '1hi.a a2ot22t r?f ~.c-f.c!. xrin ~ . j ~ c r z ~ c z , e ~ x ~ Q : . : I?:)::: * O . + T!"m:s :?tr a:. .: r w ~ o:,' (-2216. 11- . .

C~WJ~?J~ ( S S ~ , ~ Q 111) , O,'j:? :i;z r,zl ~ q ~ y y . ! ..P; ...; :::~;;P;I~C.:. 3;~1,!1. j:;~. $::lx..? : ::I ., Tliic ;'.r . . " .. . ' , . Q ~ Q ~ ~ . : Q ~ $0 0, '75 c. ,c .. c,? :;x,.:;:c.a:iA:;. %:::.a,:

. . . . .

rl' 1 . h ~ fu%;:oj:i.l re', 2 09 ?he reao%itan bwi;~aar. <;:;.3 roc:: t:t~l:fi?::'f.c. acid cu;4.:.:;:.;.?.

t o inc:*oaso as :ram c12?.1t% acid mo c,ppli.od, \iI'bh 30 o.,c o:.? ~opabi.~n ap;. S:l.:::.. .to 5 ~YLZO 0.f ?bltjcy OF 5. rcz.Pllo aP sal~~biot? t o scl2.d o? oligl:t?y o w r 6 f;o :!, : bo

t etrsnr;"cll of $!ie r:cld appllocl K ~ E I odcn;aloi+&cl t o Is u?pm&idrn'& tlf-.c R ~ t h ~ r F,lXltir$?:.ca t..ro:!?-5. :;!:", bs ocoroxtc dm *b thn ?nrp vc?l.gll'r, of B < I & . L % ~ ~ I 2.k-t uor:i.?. ';IO:.T~I

be k;aci?.aii I:.:?' st' ::b 011 p h o s p . b o

%'ha i.~?:y~?l.t:~ :?f >'0& ?Joe 9 9adib~.tr0CZ that sl igW~3y no20 ctd.f~v%.c acid Ik. lL. :???I:'.

.~.n,?onui~.ad c..s Pllo dl?-utl.ctr: :'Lnansasad, l'ca-b Bo, 30 +haiefora, m l o %:, 31: . :k th:!.c, bi~b i . Z :.::?. ; 10t. 11-3. LhaC ?&I som end p13n.t~ xas ::.eocft.sti re (pr3 lc~e of ~:L:'.v . .!0;).

Theso testa trauld Indioeta %hat from 75 'b % &ratan 7ioUI.L ba roqu52sc!. 3?!

prrrc t lca l iy ctrjq)l..c-ts oonatmption of the W w i a auid app!.ie8,, Ib33 I ,#Y?~ ?;KC;: 1-

'!m req?ll:..od 'l;o <82;6r:nim tbe mount of free p3o:s$1o:cic ac!.Ci Il.bwzt9d. cx5 9:Lr -.eta c f rcact9r~zr v:dt;;n raw rock,