Reactions of sugar solution on certain calcium aluminates and calcium alumino-ferrite
by William W Niven Jr
A THESIS Submitted to the Graduate Committee In partial fulfillment of the requirements for the
degree of Master of Science In Industrial Chemistry
Montana State University
© Copyright by William W Niven Jr (1947)
Abstract:
The Mechanisms of the reaction of sugar solution with the calcium alu-minates, 5Ca0.3A1203 and
3Ca0.A1203 as related to the Merrimen auger solubility test for Portland cement, here been studied# A
similar study for 4Ca0.A1203.Fe203 was also attempted but wee not completed. Both aluminates
reacted with sugar solution to form metastable solutions from which solid phase precipitated on
standing. The ultimate produets of hydrolysis of 5CaO.3A12O3 by sugar solution under the conditions
examined were dissolved and precipitated hydrated calcium alumlnate of the apparent composition,
2Ca0.A1203.xH20 and precipitated hydrated alumina, without the liberation of free calcium hydroxide
at any stage of the reaction. The ultimate products of hydrolysis of 3Ca0.A1203 by sugar solution were
dissolved and precipitated hydrated alumina and calcium sucrates, the sugar solution apparently
completely hydrolysing the compound at the hydroxyl-ion concentrations obtaining in the tests and the
calcium hydroxide thus liberated then combining with the sugar. REACTIONS OF SUGAR SOLUTION ON CERTAIN
CALCIUM ALUMIKATES AND CALCIUte ALtoI NO-FKRRITS
by
m . W. NIVEN, J r .
A THSSIS
Subm itted t o th e G raduete Committee
in
p a r t i a l f u l f i l l m e n t o f th e req u irem en ts
f o r th e d eg ree o f
M aster o f S eien ce in I n d u s t r i a l C hem istry
at
Montana S ta te C o lleg e
A pprovedi
C hairm an, Examining Coiranl t t e e
Bozeman, Montana
A ugust, 1946
y /3 7 f
«• 2 •»
TABLE Cf COSTED
S e o tlo a
Page To .
I#
A b s tra c t • • • • • • • • • • •
4
II.
I n tr o d u c tio n . . . . . . . . .
6 -8
III.
G en eral E x p erim en tal Procedure
9-11
T able I .
IV .
/
K
V.
VI .
v
$
M ixing Schedule
9
S e a c tio n s Between Lime and S u g ar S o lu tio n
. .
12-19
T able I I . R esu lts o f O rig in a l T e s ts w ith CaO and
Sugar S o lu tio n . . . . . . . . . . . . . . . . .
15
Table II-A . ?»s u i t e o f T e sts w ith CaO and Sugar
S o lu tio n , U sing fiew Mixing Method . . . . . . .
14
f ig u r e I . . . . .
. ....................... . . . . . . . .
16
ISeaotions Between Aluminum hydroxide and Sugar
S o lu tio n . . . . . . . . . . . .
. . . . . . . .
20
R eactions Between 5Ca0*3Al20g and Sugar S o lu tio n • • •
T able I I I .
A eeulta o f T eats S it h 6CaO*3AlgQg and
Sugar S o lu tio n
. . . , * . . * * . . * .
ft
F ig u re 2 . • • • • • • • •
V II.
k
i
%
• •
V III.
....................... .
.
.
.
.
21-26
*
22
.
26
Veaotions Between 4CaO*Al2Qj*Fb2 O3 and Sugar S o lu tio n .
27-54
T able IV. R esu lts o f T ests W ith 4Ca0*Al20g*1 CgOg and
Sugar S o lu tio n .
. . . . . . . . .
.
. .
. . .
29
F ig u re 5 . . . ..................................................... ....
SS
F ig u re 4 . . .................. . . . . . . . . . . . . . . . .
54
R eactions Between SCaOeAl2 Og and Sugar S o lu tio n . • • •
Table V.
S o lu tio n
56-44
R esults o f T e sts W ith SCaOeAl2 Og and Sugar
36
F ig u re b . . . . . . . . . . . . . . . . . . . . . . .
39
F ig u re 6 . . . . .
41
................................... ......................................
81393
m
F igure
7 . . . . . . . . . . .
m
...........................................
T able V I. I n te r p o la te d Kol T e tlo s o f P r e e lp lta to e
From SGaOeAl2O5 E x tra c ts • . . . .......................... ....
IX.
44
.
44
D leoueelon o f d e s u it e .
46-66
A.
S ig n ific a n c e o f H ydroxyl-Ion C o n c e n tra tio n . • • •
46-48
B#
N ature o f S o lu tio n s o f Cement Compounds. • •
49-51
C»
Sum m arisation o f T eaetlons . . . . . . . . . . . .
•• .
62-66
1.
S e rie s I . . . . . . . . . . . . . . . . . . .
52
2.
S e rie s 2 . . . . . . . . . . . . . . . . . . .
52
5.
S e rie s
4.
S e r ie s 4 . . . . . . . . . . . . . . . . . . .
5.
S e r ie s 5
62-64
.
6
4
-
6
64
6
X.
Acknowledgements . . . . . . . . . . . . . . . . . . .
57
X I.
L i te r a tu r e C ited and C onsulted . . . . . . . . . . . .
58
- 4 I.
ABSTMCT
The swohaniema o f th e re a o tio n s o f e u g a r s o lu tio n w ith th e o&loium a lu m ln a to s, SCaOeSAlgOg and SCaOeAlgOs, aa r e la te d t o th e M errlman su g ar
s o l u b i l i t y t e s t f o r P o rtla n d cem ent, have been s tu d ie d ,
A s i m i l a r stu d y
f o r 4CaOeAlgOgeBWgOg was a ls o atte m p ted b u t was n o t c o m p le ted .
Both
alu m in a tea re a c te d w ith su g a r s o lu tio n to f o r a m e ta s ta b le s o lu tio n s from
w hich s o lid phase p r e c i p i t a t e d on s ta n d in g .
The u ltim a te p ro d u c ts o f
h y d ro ly s is o f BCaOeSAlgOg by su g a r s o lu tio n u n d er th e c o n d itio n s exam­
ined were d is s o lv e d and p r e c ip ita te d h y d ra te d calciu m a lum inate o f th e
a p p a re n t c o m p o sitio n , ZCaOeAlgOg*x% 0, and p r e c ip ita te d h y d ra te d
a lu m in a , w ith o u t th e l i b e r a t i o n o f f r e e c alc iu m hydroxide a t any stag e
o f th e r e a c t i o n .
The u ltim a te p ro d u c ts o f h y d ro ly s is o f SCaOeAlgOg
by su g ar s o lu tio n were d is s o lv e d and p r e c ip ita te d h y d rated alum ina and
calciu m s u o r a te e , th e s u g a r s o lu tio n a p p a r e n tly c o m p letely h y d ro ly sin g
th e compound a t the h y d ro x y l-io n c o n c e n tra tio n s o b ta in in g i n th e t e s t s
and th e calciu m hydroxide th u s lib e r a te d th e n com bining w ith th e s u g a r.
«» 5
ii# mmwcnos
Th« problem o f r e a d ily d e te rm in in g th e deg ree t o which e q u ilib riu m e o n d i%
tio n s have been a t t a i n e d in th e k i l n in th e m anufacture o f P o rtla n d cement
has y e t t o be e a t l e f a e t o r i l y s o lv e d .
Q u a n tita tiv e ch em ical a n aly se * and
th e s ta n d a rd p h y s ic a l t e s t e o f P o rtla n d cement cannot a lo n e In d ic a te
w h e th er e q u ilib riu m c o n d itio n s were a d e q u a te ly approached an ti, f r e q u e n tly ,
th e t h e o r e t i c a l compound co m p o sitio n o f th e cem ent, a s computed from th e
chem ical a n a l y s i s , may be o nly a rough ap p ro x im atio n o f th e a c tu a l co n d i­
tio n s .
The f a c t t h a t e x is t in g methods f o r e x a c t d e te rm in a tio n o f t r u e cement
c o m p o sitio n a re n o t r e a d ily a d a p ta b le f o r ro u tin e a p p lic a tio n t o th e
problem o f d e te rm in in g cement q u a l i t y has led to th e developm ent o f th e
s o - c a lle d " su g a r s o l u b i l i t y t e s t " as proposed by Serrim an ( 8 , 9 , 1 0 )* ,
which i s i n e f f e c t an a d a p ta tio n o f e a r l i e r t e s t methods f o r th e d e te r ­
m in a tio n o f f r e e lima in cem ent.
T his t e s t has been in c o rp o ra te d in to a t
l e a s t one c o n tr a c t s p e c i f i c a t i o n f o r th e purchase o f P o rtla n d cement (12)
and c o n s is ts b r i e f l y o f th e fo llo w in g i
F if te e n grams o f p re p a red cement a re shaken f o r two h o u rs w ith
100 ml o f a 18% su g a r (s u c ro s e ) s o l u t i o n , a f t e r w hich t i e s u s ­
p e n sio n is f i l t e r e d .
A 25 ml a l i q u o t o f th e f i l t r a t e i s t i t r a ­
te d w ith 0.5S h y d ro c h lo ric a c i d , f i r s t to a p h e n o lp h th a I e in end
p o in t and th e n t o a c l e a r p o i n t .
Cements which re q u ire more th a n
8 .0 ml o f a c id t o th e p h e n o p h th a le in end p o in t and more th a n 10.0
ml o f a c id to th e c l e a r p o in t a re c o n sid e re d o b je c tio n a b le .
♦Numbers i n p a re n th e s e s r e f e r t o re fe re n c e s l i s t e d a t th e end o f t h i s
p a p e r.
Menrtiwm, from h ie s tu d ie s o f the e f f e c t * o f su g a r s o lu tio n on P o rtlan d
c s s e a t , a r r iv s d i n p e r t a t th e fo llo w in g e e noI u s io n s t
(a ) tinsound eecaent w i l l ba broken down alm ost c o m p le te ly
by th e su g a r s o lu t i o n , w hereas t h i s c o n d itio n i s n o t
observad w ith sound oeamnte#
(b ) A eer.en t having low r e a c t i v i t y w ith s u g a r s o lu tio n has
been c a lo in e d to th e e x te n t t h a t i t w i l l rem ain re a so n ­
a b ly s ta b l e i n th e p re sen c e o f w a te r d u rin g th e opera­
tio n s o f m ixing and p la c in g c o n c re te *
(« ) A cesaent t h a t lias been a p p re c ia b ly p re h y d ra te d , e i t h e r
w hile in th e form o f o lin lc e r o r by th e a d d itio n o f
w a te r d u rin g th e f i n a l g r in d in g , w i l l e x h ib it h ig h
r e a c tio n w ith s u g a r .
Baaed on th e s e c o n c lu s io n s , he has proposed t h a t th e a c tio n o f su g ar s o lu
t i o n on cem ent m y Sdrve a s an index o f th e degree o f c a l c i n a t i o n and p re
h y d r a tio n .
i‘he s e r r itia n s u g a r s o l u b i l i t y t e a t has been th e s u b je c t o f much c o n tro ­
v e r s y , w ith th e r e s u l t t h a t c o n s id e ra b le work m e be-yn done t o d eterm ine
i t s m e rits ( I , 2 , 1 6 ).
Howov e r , no c o n c lu s iv e d e te rm in a tio n s have been
made o f th e chem ical r e a c tio n s th a t ta k e p la c e betw een su g ar s o lu tio n arb
th e v a rio u s compound c o n s titu e n ts o f r o r t k n d cem ent.
Baaed on a b e l i e f
tii&t no f i n a l c o n c lu sio n s a s to t h e m e rits o f th e t e s t can be reached
u n t i l mors i s known o f th e c h em istry o f th e t e s t , i t has boon th e purpose
o f th e p re s e n t I n v e s tig a t io n to d eterm in e a s much of t h a t c h e m istry as
a v a lIu b Ie titie -would p e rm it, w ith o u t a tte m p tin g t o a r r iv e a t any c o n c lu sio n s
as t o th e m e rits o f the t e s t I t a o l f e
Duo t o th e f a c t t h a t th e sta n d a rd t e s t
f o r lo se on I g n it io n Ie c o n sid e re d a more ad eq u ate t e a t f o r e x c e s siv e p r e h y d ra tio n o f cement th a n th e s u g a r s o l u b i l i t y t e s t , no s p e c i a l c o n s id e ra tio n
has been g iv e n In th e p r e s e n t in v e s t ig a ti o n t o th e r e a c tio n s betw een su g ar
s o lu tio n and h y d ra tio n p ro d u c ts , o th e r th a n th e h y d ra tio n p ro d u c ts t h a t
n orm ally form u n d er th e c o n d itio n s o f th e t e a t #
P o rtla n d cem ent i s g e n e r a lly conceded t o c o n s is t e s s e n t i a l l y o f th e com­
pounds, SCaOeSlOig , ZCaGeSiO g, SCaOeAlgOg, and ICaOeA1%OgeI mgOg, in major
p r o p o r tio n s , and th e minor b u t n o t i n s i g n i f i c a n t c o n s t i t u e n t s , CaSO4 , MgO,
f r e e 0*0, and a l k a l i s , th e l a t t e r p ro b ab ly i n complex co m b in atio n w ith
c alc iu m oxide and s i l i c a o r alum ina#
I n a few P o rtla n d cem en ts, th e com­
pound, BCaOeSAlgOs, may e x i s t an d , ein o e t h i s compound i s p ro b a b ly an i n t e r ­
m ediate in th e k i l n r e a c tio n betw een calciu m oxide and alum ina t o form
SCaOeAlgOg, i t baa a l s o b een c o n sid e re d in th e p re s e n t stu d y #
ilhen w a te r i s added to cem ent, h y d ro ly s is o r h y d ra tio n o f th e v a rio u s cement
compounds r e s u l t s , w ith th e fo rm atio n c h i e f l y o f calciu m hydroxide and hy­
d ra te d s i l i c a t e s , a lu su n a te e and f e r r i t e s .
Kuoh work has been dona on th e
n a tu re o f th e s e re a c tio n s and only th o se r e s u l t s d i r e c t l y r e la te d t o th e
r e s u l t s o f th e p re s e n t in v e s t ig a ti o n w i l l be review ed in th e fo llo w in g ap­
p lic a b le s e c tio n s o f t h i s paper#
In th e c ase o f r e a c tio n s betw een s u g a r
s o lu tio n and th e cem ent compounds, i t Is n o t n e c e s s a r ily to be expected
t h a t th e same r e s u l t s w i l l o b ta in , p r im a r ily because o f seco n d ary r e a c tio n s
betw een c alc iu m hydroxide and su g ar t o form suor a t e s .
The a u th o r has found
in p re v io u s u n p u b lish e d work t h a t th e r e a c tio n s betw een SCaOeSiOg and
I
~ S «»
SCaOeSiOg and su g ar s o lu tio n a re a p p a r e n tly no d i f f e r e n t th a n between
w a te r and th e s e compounds•
S ta n d a rd 26 ml a liq u o ts o f e x t r a c t s from su g a r
s o l u b i l i t y t e s t s on each o f th e pure s i l i c a t e s re q u ire d o n ly 1.6 0 ml and
1.50 m l, r e s p e c tiv e ly , o f s ta n d a rd a c id t o t i t r a t e t o a p h e n o lp h th a I e in
end p o in t and th e r e was no evidence o f any u n u su a l degree o f r e a c tio n .
On th e o th e r hand, th e r e was much e v id en c e t o ln d io a te e x te n s iv e re a c tio n s
betw een su g a r s o lu tio n and SCaO-Al2Og and ACaOeAl2O5 eFe2O5 , n o t so much
from th e amounts o f s ta n d a rd a c id re q u ire d t o t i t r a t e 26 ml a liq u o ts
(8*50 ml and 11.70 ml, r e s p e c tiv e ly , t o p h e n o lp h th a I e In end p o in ts ) a s from
th e f a c t t h a t marked g e l a t i n o ccu rred i n th e m ix tu res d u rin g th e co u rse
o f th e t e s t s .
Based on th e above in fo r m a tio n , th e p r e s e n t in v e s t ig a ti o n
has been lim ite d t o SCaOeAl2Og, BCaOeSAlgO5 , ACaOeAl2Os eFe2O5 , CaO, and
Al2O5 .
At numerous p o in ts th ro u g h o u t th e fo llo w in g d is c u s s io n , th e term “ s o lu tio n "
i s u s e d , when p e r ta in in g t o e x tr a c ts o b ta in e d by th e tre a tm e n t o f cement
compounds w ith su g a r and w a te r .
No a tte m p t i s made d u rin g th e g e n e ra l d i s ­
c u ss io n s t o d i f f e r e n t i a t e between tr u e s o lu tio n s and o o llo lc ia l s o l u tio n s .
For a d e ta i le d d is c u s s io n o f t h i s a s p e c t, a s i t p e r ta in s t o th e v a rio u s
compounds, re fe re n c e is made t o S e c tIonIX n e a r th e end of t h i s p a p e r.
*• 9 w
IlU
SfflBRAL EXPS 8lK i?m L PBDCEBU @
The ootapounde used were p rep ared from C. P . r e a g e n ts , p r e c ip ita te d calcium
c a rb o n a te b ein g uaeti a s a source o f c alc iu m o x id e .
The pure cement com­
pounds were p re p a re d by m ixing th e re a g e n ts d ry In t h e o r e t i c a l p ro p o rtio n s
and c a lc in in g u n t i l no f r e e lie * was e v id e n t by th e ammonium a c e ta te t e s t .
In th o se c a se s where a sm all amount o f f r e e lim e was d e s ir e d in th e com­
pounds , th e re a g e n ts were mixed a s f o r th e pure compounds b u t th e c a lc in in g
was sto p p ed j u s t s h o r t o f com plete e q u ilib r iu m .
I t was b e lie v e d t h a t , in
t h i s w ay, c o n d itio n s o b ta in in g in ocment c o n ta in in g fre e lim e would be more
n e a r ly d u p lic a te d th a n would be th e case i f f r e e lime were added t o th e
pure compounds.
S e r ie s o f t e s t s were made a s in d ic a te d by th e m ixing sch ed u le i n Table I .
In th e o r i g i n a l S e r ie s I t e s t s w ith c a lc iu m oxide and i n th e S e r ie s Z t e s t s
w ith aluminum h y d ro x id e , th e oxide o r hydroxide in th e p a r t i c u l a r amounts
TAILS I .
MIXIKS SGHRDULE
M a te ria l added t o
s u g a r s o lu tio n
Se r ie s
Ho.
Amounts ad d ed ,
g/lOOml
For r e s u lts
see Tab I e i
I I and II-A
I
CaO
0 .0 6 0 t o 7 ,6 0 0
2
Al(OH)z
0.022 to 0 .2 2 0
S
BCaO-SAl2Os (0 .9 4 £ f r e e CaO)
BCaO-SAl2 Os (no fr e e CaO)
0.092 to 0 .5 4 7
0.366 t o 0.913
III
III
4
dCaQ-AljjOs -FegOs (0 .8 4 # f r e e CaO)
iCaO-AlgOg'PegOgfno f r e e CaO)
4 CaO-AIgOg-Feg0S ( e x tra -b u rn e d )
0.184 t o 4,664
0.914 t o 4.666
2.285 t o 4.665
IV
IV
IV
5
SCaO-Al2O5 (2 .0 4 ^ fr e e CaO)
SCaO-Al2Os (no f r e e CaO)
0.047 t o 1.371
0 .466 t o 2.283
V
V
- 10 was mixed w ith 15 g o f oonanerel& l-grade b e e t s u g a r p re v io u s ly d is s o lv e d in
d i s t i l l e d w a te r and d ilu te d t o 100 ail#
Wtesn th e &lu y in a te compounds were
mixed w ith s u g a r s o lu tio n in a lik e m anner, lumping o f th e compounds o ccu r­
red because o f ra p id r e a c tio n w ith th e s u g a r s o lu tio n #
I n o rd e r to overcome
t h i s d i f f i c u l t y i n a l l s e r i e s o f t e s t s e x c e p t S e rie s I and 2 , th e compound
i n th e p a r t i c u l a r amount was th o ro u g h ly mixed w ith 16 g o f d ry s u g a r, a f t e r
wtiioh 100 ml o.1 d i s t i l l e d w a te r were r a p id Iy added and th e e n t i r e m ix tu re
v ig o ro u s Iy shaken#
The S e rie s I t e s t s w ith calciu m oxide were th e n re p e a t­
e d , u sin g th e new method o f m ix in g , because of s l i g h t d if f e r e n c e s in pro­
p o rtio n s o f c o n s titu e n ts #
rIix in g o f a l l t e s t s was accom plished in 100 ctl sto p p ered c y lin d e r s mounted
on a w heel r o t a t i n g a t a speed o f ap p ro x im ately 40 rpm#
made a t room te m p e ra tu re , 28°C I 2 ° .
A ll t e s t s were
F i l t e r i n g d i f f i c u l t i e s in h e re n t w ith
th e t e s t s on th e a lum inates were avoided by s e p a r a tin g th e su g a r e x tr a c ts
by c e n tr if u g in g i n a l l oases#
E rro rs in o .© po sitio n o f e x t r a c t s due to
s e le c tiv e a b s o r p tio n on th e f i l t e r p ap er were a ls o avoided in t h i s m anner.
Calcium oxide was d eterm ined by t i t r a t i o n w ith s ta n d a rd a c id t o a phecolpht h a l e i n end p o in t i n S e rie s I and gravim ot r i d a l Iy in th e o th e r s e r ie s #
Al­
umina and e OBtIncd alum ina and f e r r i c oxide were determ ined g ra v im o tr i c a l l y
and f e r r i o oxide wae determ ined v o lu m e tric a lly w ith stan d a rd tita n o u s
c h lo r id e s o lu tio n anti ammonium th io c y a n a te .
when d e te rm in e d , was o b ta in e d by d iff e r e n c e #
Combined su g a r in r e s id u e s ,
The o p t i c a l r o ta to r y power o f
s o lu tio n s was determ ined i n a 200 mm tu b e by means o f a w edge-type poI a r i ^ e te r a c c u ra te t o 0 * 1 ^, V entske s c a le #
pK d e te rm in a tio n s were made e l e c t r o -
if ie tr ic a ily w ith an In stru m en t a c c u ra te t o 0 .0 6 .
With re fe re n c e to Note (2)
* 11 *
oi' t a u is il-A. actl -Sot* (7 ) o f Yablo V, tl-o g,i*aa eiw etroti# f o r th e (.a to r
wa* broken a « a r th e er.d o f th e in v e e t lg a tl o n ana ae repJLaee&eot was a v a i l ­
a b le I e t i i a e .
S e e u lts o b ta in e d w ith two o th e r a v a ila b le Bate re euula n e t
oe e o rrw la te d w ith th o so o u ta io o d w ith th e B e te r used th ro u g h o u t th e i n ­
v e s tig a tio n ; m d th e r e f o r e have been o m itte d a s being o f no v alu e#
F u r th e r d e t a i l s o f t e s t p ro c e d u res a re g iv e n i n th e re s p e c tiv e s e c tio n s
fo llo w in g #
- 12
IV*
KSACTIQHS BKTWEgS LIME ASD SDCAR SOLDTIOS
Suswrous t e x t s on o rg an io c h e m istry g iv e m ention to th e r e a c tio n between
calciu m hydroxide and su c ro se to form mono-* d i « , and tr io & lo iu e s u e r a te s ,
th e f i r s t two o f which a re s o lu b le and th e l a t t e r is in s o lu b le in w a te r ,
however* i n s p i t e o f th e im portance o f th e s e r e a c tio n s in th e re c la im in g
o f s u g a r from b e e t s u g a r m o la s se s, l i t t l e i s a p p a re n tly known o f t h e i r
d e t a i l s o r o f th e s t r u c t u r e s o f th e s u e r a te s *
Tlie r e s u l t s o f th e s e r i e s o f t e s t s w ith f r e s h l y prepared calciu m oxide and
s u g a r s o lu tio n a re g iv e n i n T ables U and I I - A .
O p tic a l r o t a t o r y powers
and pH v a lu e s o f th e e x tr a c ts from th e s e t e s t s a re p lo tte d i n fig u r e I
a g a in s t th e c o rre sp o n d in g amounts o f d is s o lv e d calcium o x id e .
Q u a n titie s o f o alelum oxide up to a p p ro x im a te ly 2*5 g gave c l e a r s o lu tio n s
a f t e r only s h o r t p e rio d s o f mixing*
In c re a s in g q u a n titie s o f calcium oxide
above 2 .6 g gave in c re a s in g q u a n t i t i e s o f s o lid phase a n d , up to 7 ,6 g ,
gave in c re a s in g q u a n t i t i e s o f d is so lv e d calciu m o x id e .
S u ffic ie n t te s ts
were made a t each c o n c e n tra tio n o f c alc iu m o x id e , w ith s u f f i c i e n t l y long mix­
in g p e r io d s , to a s s u re t h a t e q u ilib riu m was a tta in e d betw een th e s o lid and
s o lu tio n p h a s e s , a s evidenced by c o n s ta n t co m p o sitio n o f th e s o lu tio n phase*
The f a c t t h a t th e amount o f d is s o lv e d c alc iu m oxide c o n tin u e s t o in o rv as#
w ith in c r e a s in g amounts o f t o t a l calcium o x id e , even above th e p o in t where
a s o l i d phase f i r s t e x i s t s in e q u ilib r iu m , a p p e a rs to be c o n tr a d ic to r y t o
th e u s u a l co n cep ts o f in te r-p h a s e r e la tio n s h ip s a t e q u ilib r iu m .
A ll lime
used was c a r e f u l l y c a lc in e d to avoid a "h igh-burned* c o n d itio n and was e n ­
t i r e l y " s u g a r - s o lu b le " , a s in d ic a te d by th e f a c t t h a t i t w ent e n t i r e l y in to
s o lu tio n a t c o n c e n tra tio n s below 2 .5 g .
M oreover, o a rb o n a tio n eould n o t
TABUS XI - m s DUS OP OBIGISAL TESTS WITB CaO ASD SUGAR S OUfT I OS
t»0#
CaO
added,
g/lOO m l.
i
~T~
I
0 .000
2
0 .050
S
S ix in g
tim e ,
hours
Besidxie
3
"T H
pH
of
e x tra c t
T
”
CaO
d is s o lv e d ,
g/100 ml
6
A n aly sis »f Residue
O p tic a l
T ~
R o ta tio n o f
Combined
e x t r a c t . V entSugar
ske $ /2 0 0 mm Ca(Oh)2
~T"
9
8
57.7
—
6 .6 0
2
Iioce
10.95
0 .0 6 0
57.2
0 .1 0 0
2
None
11.26
0 .1 0 0
57 .0
4
0 .600
2
Bone
11.90
0.500
65.3
5
1.000
2
Bone
12.00
1.000
6 3 .4
6
1.600
2
None
12.10
1.600
61.3
7
1.900
2
Sone
12.16
1.900
49.9
8
2.600
8
T race
12.15
2 .6 0 0
4 8 .1
I n s u f f i c i e n t t o an­
a ly s e
9
3 .0 0 0
10
Inc re a s ia g
amount
12.20
2 .9 3
47 .4
I n s u f f i c i e n t to an a ly se
10
6 .000
6-72
In c re a s in g
amount
12.30
3 .4 3
45.3
94 .1
I
6 .9
I
6-72
In c re a s in g
amount
12.30
3 .5 1
4 4.1
90.6
I
9 .5
I
11
7.500
- H TABUE II-A
HRSUUS OP TESTS WITH CftO AMD SUtiAR SOLUTION,
USISti KBW MDCINti METHOD.
St
e
CaO
d is s o lv e d ,
g/100 K l ( I )
Mixing
tim e ,
hours
pH
of
e x tra c t
O p tic a l R o ta tio n
of e x tra c t,
Venteke :;-/200 ma
~T~
4
6
6.60
52.6
I
T ~
1
0 .000
2
0.044
I
10.90
62.4
5
0.094
I
11.20
62.2
4
0.134
I
11.30
62 .0
6
0.179
I
11.46
61.8
6
0.208
I
11.60
61.6
7
0.426
I
11.66
60.7
8
0.649
I
11.80
49.7
9
0 .870
I
11.90
48 «8
10
1.549
2
(2)
47.2
11
1.304
2
(2 )
46.6
12
2.236
2
(2 )
44.3
H otes i
(I)
(2 )
16 g . Bugftr p lu s 1(X3 ml w a te r ® 109.6 ml o f s o lu tio n .
Asiounte o f CftO a c tu a lly used have been reduced by the
f a c t o r 100/109.6 t o g iv e th e v a lu e s shown In t h i s
colum n.
Could n o t determ in e s a t i s f a c t o r i l y because g la s s
e le c tr o d e o f pH re t e r was. b roken and no rep lacem en t
was a v a ila b le in tim e . B esu lts o b tain ed w ith o th e r
a v a ila b le pH m eters could n o t be c o r r e la te d w ith
th o se o b ta in e d by -ufcer used th ro u g h o u t th e in v e s t 1______________ g a tio n ._______________________ _
______
pH
•IS *
4 JOO
FIGURE I
RELATIONSHIP OF DISSOLVED LIME (CaO) TO SUGAR CONTENT AND pH.
L c G E 1N D * • ■ O r i g i n a l m i x i n g m g t m o d J 0 — N e.w m i x i n g m r t m o d .
—
—
- 16
havu ta k e n p la c e d u rin g th e mixing*
Thie same c o n d itio n has been p re v io u s ly
observed by Uoubourg (13) in c o n n e c tio n w ith e stu d y o f th e s o l u b i l i t y o f
o&I e ltt» hydroxide in aqueous s u g a r s o lu tio n s in c o n ta c t w ith in c re a s in g ex ­
c e s s e s of th e s o l i d p h a se ,
Tlte o n ly a p p a re n t e x p la n a tio n i s t h a t , in th e
p resence o f g r e a te r e x c e sse s o f s o lid lim e , th e r e i s a s h i f t in th e e q u i l i ­
brium in th e s o lu tio n betw een monocaleiuB s u e r a te and d ie a le lu m s u e r a te
tow ard th e fo rm atio n o f g r e a te r p ro p o rtio n s o f th e l a t t e r ,
how ever, t h i s
m a tte r was n o t pursued f u r t h e r in th e p r e s e n t i n v e s t i g a t i o n , th e main pur­
pose in stu d y in g t h e lim e s o l u b i l i t i e s b e in g t o determ ine th e e f f e c t s o f
d is s o lv e d lime on th e o p t i c a l r o ta to r y powers and pK v a lu e s o f th e s o lu ­
tio n s .
Xhe maximum c o n c e n tra tio n o f d is s o lv e d c alc iu m oxide o f 3 .6 1 g p e r IOC ml
co rresp o n d s t o 4 .6 4 g o f calciu m h y d ro x id e .
T h is l a t t e r v a lu e ag rees w e ll
w ith th e s o l u b i l i t i e s re p o rte d by S e ie b erg (14) and by Cameron and P a tte n
(1 3 ) , when computed t o a com parable b a s i s , b u t is c o n s id e ra b ly h ig h e r th a n
th e v a lu e re p o rte d by iw in d ers and Van O eld er (1 3 ), f o r t e s t s made under
s i m i l a r c o n d itio n s ,
!A sidues from t h e S e rie s I t e s t s w ith th e o r i g i n a l m ixing method were a n a ly ­
sed i n th e fo llo w in g m anneri
The re s id u e s o b ta in e d from th e f i r s t c e n tr ifu g in g were washed th r e e
tim es w ith sm a ll amounts o f c o n c e n tra te d amnonium h y d ro x id e in th e
c e n tr if u g e tu b e s , r e c e n tr if u g in g and d e c a n tin g a f t e r each w ashing.
The re s id u e s were th e n d rie d a t IOO0C, t r a n s f e r r e d t o weighed Ooooh
c r u c i b l e s , and washed a g a in w ith sm all p o rtio n s o f c o n c e n tra te d
ammonium hydroxide u n t i l c o n s ta n t w eig h ts were o b ta in e d a f t e r d ry -
- 17 lo g a t IOO0C.
A ll o p e ra tio n s o u ts id e th e d ry in g oven were oon-
duo te d as r a p id ly as p o s s ib le t o m inim ise e a rb o n a tio n a n d , d u rin g
d r y in g , carbon d io x id e - f r e e a i r was p assed th ro u g h th e oven.
S o lid ealoium hydroxide was found by t e s t t o be in s o lu b le in th e
c o n c e n tra te d ammonium hydroxide and lim e—e u g ar s o lu tio n s were un­
a f f e c te d by th e r e a g e n t.
A bso lu te e t h y l a lc o h o l, am a p o s sib le
w ashing a g e n t, was found t o cause a p r e c i p i t a t e o f undeterm ined
c o m p o sitio n (p ro b a b ly a calciu m s u e r a te ) t o be f o r c e d from th e
e x tra c ts .
The weighed washed re s id u e s were d is s o lv e d in a m easured ex cess
o f s ta n d a rd h y d ro c h lo ric a c i d , th e ex cess th e n being b a c k - t i t r a t e d
to a p h e n o lp h th a le in end p o in t w ith s ta n d a rd sodium h y droxide
s o lu tio n .
The w eig h t o f caloiun; h y d ro x id e in th e re s id u e s was ob­
ta in e d from th e amount o f a c id re q u ire d t o re a c t w ith th e sam ple,
and th e w eig h t o f combined s u g a r in th e re s id u e s was th a n o b ta in e d
by d i f f e r e n c e , assum ing t h a t trio & le lu m s u o ra te has th e form ula
S eao eC ^H azO iieSHgO, a s re p o rte d by MaeKensie ( 7 ) .
The form ula o f h y d ra te d lim e , when d r ie d a t IOO0C, was cheeked by
a d d in g an e x ce ss o f w a te r to weighed sam ples o f c alc iu m oxide and
d ry in g to c o n s ta n t w e ig h t a t IOO0C.
The form ula was found to be
e x a c tly GaOe HgO o r Ca(0H)g.
As in d ic a te d in Table I , s t a r t i n g amounts o f 6 .0 g . and 7 .6 g o f e a loium
oxide y ie ld e d re s id u e s c o n te ln in g 6 .9 - 1$ and 9 .5 - 1# o f combined s u g a r ,
re s p e c tiv e ly .
L e sse r amounts o f e a le iu s i oxide y ie ld e d re s id u e s to o sm all
i n amount t o be s a t i s f a c t o r i l y a n ely se d f o r s u g a r | how ever, i t i s reaso n ­
— 18 a b le t o e x p e c t t h a t oven th e s m a lle r re s id u e s co n tain ed s l i g h t amounts o f
combined s u g a r .
T h e re fo re , th e s o lid phase In e q u ilib riu m w ith th e I l e e -
s u g a r s o lu tio n may be c o n sid e re d t o c o n s is t c h ie f ly o f c alc iu m h y d ro x id e ,
to g e th e r w ith r e l a t i v e l y s m a ll p ro p o rtio n s o f tr tc a lc iu m s u e r a t e . In th e
range o f c o n c e n tra tio n s and u n d er th e c o n d itio n s covered by th e p re s e n t In ­
v e s tig a tio n .
The curves in fig u r e I f a r o p t i c a l r o ta to r y power v e rs u s amount o f d is s o lv e d
liiae a re p rim a rily o f im portance in c o n n e c tio n w ith s i m i l a r cu rv es o b ta in e d
w ith th e cement compounds. In s o f a r as th e p re s e n t in v e s t ig a ti o n Is c o n e s re ­
a d , and w i l l be d is c u s s e d l a g r e a te r d e t a i l l a t e r .
The d e c re a se In r o ta ­
to r y power noted w ith in c re a s e d amounts o f d is s o lv e d lim e , p r i o r to th e
p o in t where a s o lid phase i s p re s e n t a t e q u ilib r iu m , must be due e n t i r e l y
t o a l e s s e r r o ta to r y power o f d is s o lv e d c s e t Inad s u g a r , as compared t o t h a t
o f d is s o lv e d f r e e s u g a r .
I t i s n o t c o n sid e re d t h a t s u g a r combined In s o lu ­
t i o n a s s u e r a te has l o s t a l l I t s r o ta to r y power because o f th e f a c t t h a t
even th e s o lu tio n s c o n ta in in g th e maximum amount o f d is s o lv e d l i r e show
pronounced r o t a t i o n .
This p ro p e rty should sa rv a th e r e f o r e a s a means o f
d e te c tin g h y d ro ly s is o f cem ent compounds by s u g a r s o lu tio n to lib e r a te
calcium h y d ro x id e .
The p lo ts f o r r o ta to r y power g iv e a p p ro x im a te ly s t r a i g h t
lin e s up t o th e p o in t where s o lid phase a p p e a rs .
Ihe c o n c e n tra tio n o f d i s ­
so lv ed lime where s o l i d phase f i r s t p e r s i s t s a t e q u ilib riu m c o in c id e s
ap p ro x im a te ly w ith a mol r a t i o o f lim e to s u g a r o f 1 :1 .
T his would I n d ic a te
t h a t I n i t i a l fo rm a tio n o f dia& loivja sue r a te end p ro b ab ly a l s o o f tr lc a le iu m
su er a te ta k e s p la ce p r i o r t o th e com plete tle ln g - u p o f a l l s u g a r m olecules
as inonooaloiuto s u e r a t e .
A p p a re n tly , a m onooalciuE s u c ra to molecule can dan-
19
b in e more r e a d ily w ith a d d i t i o n a l lime t o form a more b a s ic s u e r a te th a n
can a f r e e s u g a r m olecule eomuine w ith lim e t o form monocaloium s u e r a te .
However, f u r t h e r c o n s id e r a tio n o f t h i s p o s s ib le r e a c tio n Bechanlem has no t
been con sid ered p e r tin e n t to th e p re s e n t in v e s t i g a t i o n .
As was th e c ase i n c o n n e c tio n w ith th e curve f o r o p tic a l r o t a t o r y power,
th e curves i n f ig u r e I f o r pH v e rsu s d is s o lv e d lime a re o f p rim ary impor­
ta n c e i n th e p re s e n t i n v e s t ig a ti o n o n ly i n e o n n e e tio n w ith c o n s id e ra tio n
o f r e a c tio n s w ith th e cement compounds and w i l l be d isc u sse d i n g r e a te r
d e ta il la te r .
#
to
Bnrmmt Kmnmm Mrroiw
SUGAR S O im IO t
Because o f tW am p h o teric n a tu re o f h y d ra te d a lu sd n a , t t » p o s s i b i l i t y o f
a r e a c tio n betw een aluminum hydroxide and su g ar s o lu tio n was c o n sid ered *
A s e r i e s o f t e s t s ( S e r ie s 2 ) was th e r e f o r e made. In v o lv in g f r e s h ly p r e c i­
p ita te d alumimim hydroxide and s u g a r s o l u t i o n ,
r e a c tio n was o b ta in e d .
how ever, no e v id en c e o f a
Both th e o p t i c a l r o ta to r y power and th e pH o f th e
e x t r a c t s from in c r e a s in g am ounts o f aluminum hydroxide rem ained unchanged
fro® th e c o rre sp o n d in g v a lu e s f o r th e o r i g i n a l p u re eu g er s o l u t i o n , from
which th e c o n c lu s io n i s drawn t h a t , a t l e a s t a t th e low by rox>I - io n con­
c e n tr a ti o n e x i s t i n g in th e s e s o l u tio n s , aluminum hydroxide i s n e t s u f f i ­
c i e n t l y b a s ic t o combine w ith s u g a r .
— 21 —
VI*
RSACTIONS BETWEEN SCaO^SAl2 O5 AND SUGAR SOLUTION
afcll* (16) r e p o r ts t h a t w a te r r e a c ts w ith SCaOeSAl2O5 t o form a met e s t a b l e
s o lu tio n o f aonooalelU K a lu m in a te , CaOeAlgOg, p lu s d is s o lv e d oalelum hy­
d ro x id e , and t h a t , upon s ta n d in g , a s o lid phase ap p ears c o n s is tin g o f hy­
d ra te d t r i e a l o i u d a lu m inate p lu s h y d ra te d a lu m in a .
These r e a c tio n s can be
re p re s e n te d as fo llo w s 1
SCaOeSAl2O3 1- H2O
S(CaOeAl2Ogxl^O) + 2Ca(0H)g—^
SCaOeSAl2O5 ^ B 2 Oj+ Al2O3 eZH2O)+ SCa(OB)2
The r e s u l t s o f t e s t s w ith BCaOeSAlgOg and su g a r s o lu tio n a re shown in T able
III.
No s i g n i f i c a n t d if f e r e n c e s were n o ted betw een th e r e s u l t s o b tain ed
w ith BCaOeSAl2Og c o n ta in in g 0.94% f r e e lime and th e r e s u l t s o b tain ed w ith
th e compound c o n ta in in g no f r e e lim e .
The compound, in th e v a rio u s am ounts,
was mixed f o r th e tim es in d ic a te d w ith th e s u g a r s o lu t i o n .
The c l e a r ex­
t r a c t s o b ta in e d from c e n tr if u g in g th e s e m ix tu re s were th e n te s t e d f o r o p t i ­
c a l r o ta to r y pow er, pH, d is s o lv e d alum ina and d is s o lv e d lim e .
Below c o n c e n tra tio n s o f a p p ro x im a te ly 0 .2 2 3 g o f th e a lu m in a te p e r 100 ml
o f s o l u t i o n , th e alum inate was found t o e n t i r e l y d is s o lv e w ith in a m ixing
tim e o f 6 hours and no s o lid phase s e p a ra te d from th e e x t r a c t s on S ta n d in g .
C o n c e n tra tio n s o f th e a lum inate from 0.228 g t o 0.686 g p er 100 ml o f s o lu ­
t i o n r e s u lte d In s u b s t a n t i a l l y com plete s o lu tio n o f th e alu m in at e ; how ever,
a t th e h ig h e r c o n c e n tr a tio n s , secondary p r e c i p i t a t i o n r e a c tio n s s e t i n
p r i o r t o 6 h o u rs , th u s re n d e rin g com plete s o lu tio n im p o s s ib le .
T h e re fo re ,
t e s t s were mad* w ith d i f f e r e n t m ixing tim e s , as in d ic a te d i n Table I I I , a t
e a c h o f t h e h ig h e r c o n c e n tra tio n s in o rd e r t o d eterm ine th e com position of
e x tr a c ts p r i o r t o th e o c cu rren c e o f th e seco n d ary r e a c tio n s .
In th e t e s t s
w ith th e h ig h e r oonoentr a tio n s o f a lu m in a te and s h o r te r m ixing p e r io d s .
TABIB I I I - RESULTS OP TRSTS KITH SCaOeSAl2Og ASC SOCiAH SOLUTION
SCaOSAlEO5
added,
No. ^lOOml
W
I
2
3
C om position o f E x tra c t
T o ta l
d is ­
solved, AlgOg ,g/KCbl CaO.g/lOQfil M ol-R a tio ,
CaOAl9Ox
gA<»Bl
B
A
B
B(S)
A
A(S
9___ 10
5
6
7
3
I'
M lxin g
tim e,
h rs.
Mol-Rati
o f p re­
PB o f
cip itate E x tra c t
OaO/AfeO S
I ’
A
B
12
11
Is
O p tic a l dota­
tio n o f E x tr a c t,
V entske % p e r
200 nan
A
B
14 “ IT”
I
0.092
6
0.092
0.048 Se p p t 0.044 No ppt 1.67 No pp t No pp t 10.50
So p p t
6 2 .6
Se p p t
2
0.228
6
0.228
0 .1 1 9 So p p t 0 .109 Ho ppt 1.67 So pp t Ho ppt 10.35
No p p t
5 2 .6
No p p t
S
S -a
0*865
0.566
6
4-|
0.537
0.344
0.166 0 .1 2 1
0 .176 (4)
0 .171 0.152
0.168 (4 )
1.88
1.73
1.98
(4)
1.68
(4)
10,95
11.00
(6)
(4 )
52 .2
5 2 .3
62 .2
(4)
4
0.412
6
0 .5 8 9
0 .195 0.122
0 .194 0 .142
1.81
2 .12
1.27
11.00
(6)
52.3
62 .3
6
6~a
b-b
0.457
0.458
0.468
6
0.442
0
.429
#&
4
0 .4 1 4
0.227 0.124
0.219 (4 )
0,217 0.153
0.215 0 .1 4 1
0 .2 1 0 (4 )
0.197 0 .158
0.7 2
1.74
1.66
2 .0 6
(4)
1.89
1.28
(4 )
1.26
11.00
11.06
11.00
(6)
(4)
10.70
52 .4
6 2 .3
52.2
6 2 .4
(4)
6 2 .0
6
6 -a
6-b
0.647
0 .6 6 0
0 .5 4 9
6
*£
4
0 .5 1 4
0.497
0 .4 8 9
0 .2 6 1 0.128
0.248 0.115
0 .257 0.147
0 .263 0.145
0.249 0 .1 2 4
0.252 0 .1 5 4
1 .76
1.82
1.6 4
2 .0 4
1.99
1.9 0
1.4 9
1.6 1
1.2 9
11.06
11.05
11.06
(S)
10.95
10.86
6 2 .4
52 .2
62.2
62 .4
61 .6
6 1.6
7 -a
0 .6 8 6
2
0 .4 6 9
0 ^ 4 1 0 .1 3 1
0 .218 0 .1 4 0
1.64
1.95
1.2 9
10.95
10.85
5 2 .4
6 2 .0
8-a 0.915
2
0 .5 7 4
0.297 0 .1 5 1
0.277 0 .1 6 1
1.6 9
1.94
1.44
11.00
10.96
6 2 .5
61,0
0 .1 5 0
0 .1 4 2
1.72
1.99
1.39
Averages
Notes*
10.86
( I ) Buebers n o t fo llo w ed by l e t t e r s a re f o r t e s t s u sin g SCaOSAl^Os c o n ta in in g 0.94> trmm
CaOe O ther t e s t s a re w ith SCaOeSAlzOs c o n ta in in g no f r e e CaOe
(2 ) IS g su g ar p lu s 100 »1 w a te r = 109*5 ml s o lu t i o n . Amounts o f BCaOeSAl2 Og a c tu a lly
used have been reduced by th e f a c t o r 100/109*5 t o g iv e th e v a lu e s shown in th is column*
(S ) Column A f o r o r ig i n a l e x t r a c t s $ Column
(4 ) E x tra c ts s p i l l e d a f t e r p r e c ip ita tio n *
B f o r e x t r a c t s a f t e r p r e c ip ita tio n * _______ (S) I n s u f f i c i e n t e x t r a c t t o determ ine*
-ESe q u ilib riu m p ro b a b ly was n o t a tta in e d in th e i n i t i a l s o lu tio n p r o e e s e .
Use o f amounts o f SCaOeSAl2O8 i n e x cess o f 0 .2 2 8 g p er 100 ml o f s o lu tio n
r e s u lte d in m e ta sta b le e x t r a c t s c o n ta in in g in c re a s in g amounts o f d is s o lv e d
lime and a lu m in a , from w hich s o l i d g e la tin o u s m a te r ia l s e p a ra te d on s ta n d ­
in g .
The g r e a t e r th e amount o f th e a lu m in ate u s e d , th e so o n er d id th e
s o lid phase a p p e a r.
To compare th e com positions o f th e o r i g i n a l e x t r a c t s w ith th o se o f th e ex­
t r a c t s o b ta in e d a f t e r seco n d ary p r e c i p i t a t i o n had ta k e n p la c e , p o rtio n s o f
th e o r i g i n a l e x t r a c t s were s e t a s id e in t i g h t l y sto p p ered f l a s k s .
Com­
p le te n e s s o f p r e c i p i t a t i o n was determ in ed by c e n tr if u g in g th e m a te r ia l a t
i n t e r v a l s and th e n s e t t i n g a s id e th e new c l e a r e x t r a c t s .
T hle pro cess was
re p e a te d u n t i l new e x t r a c t s were o b ta in e d , from w hich no f u r t h e r p r e c i p i t a ­
t i o n would o c c u r.
A t o t a l p e rio d o f two weeks was found s u f f i c i e n t in a l l
cases•
The mol r a t i o , CaO to Al2O5 , o f th e o r i g i n a l BCaOeSAl2 O5 i s 1.(37.
As in d i­
c a te d i n column 9 o f T able I I I , th e v a lu e s o f t h i s mol r a t i o in th e o r ig i n a l
e x t r a c t s ranged from 1 .6 4 t o 1*68, w ith an av erag e v alu e o f 1 .7 2 .
In g e n e r a l,
th e lo n g e r th e m ixing p e rio d th e h ig h e r th e mol r a t i o , which f a c t is i n d i ­
c a tiv e t h a t some secondary r e a c tio n p ro b a b ly to o k p la c e d u rin g th e lo n g e r
m ixing p e r io d s .
T h e re fo re , th e d if f e r e n c e betw een th e av erag e r a t i o o f 1.72
and th e v a lu e o f 1.67 f o r th e o r i g i n a l a lu m in ate may be c o n sid e re d n e g lig ­
i b l e , and th e s ta te m e n t may be made t h a t , p r i o r t o th e o c cu rren ce o f seco n ­
d a ry p r e c i p i t a t i o n , th e r e i s no change i n mol r a t i o betw een t h e s o lu tio n
phase and th e s o l i d alum inat e .
With re fe re n c e t o Column 14 o f T able I I I , v a ry in g am ourts o f d is so lv e d
** 24 “
feCti.C.'wnljjOg lifetl no e f f e c t on th e o p t i c a l r o ta to r y power o f th e o r ig in a l ex­
t r a c t s , th e r o ta to r y power o f a s o lu tio n c o n s is tin g o n ly o f 16 g o f su g ar
and 100 ml o f w a te r b ein g 6 2 .6 ^ , V entske s c a le *
From the e f f e c t s o f d i s ­
so lv e d lin e on th e r o ta to r y power o f s u g a r s o l u t i o n , a s n o ted in S e c tio n IV ,
ab o v e, t h i s c o n sta n c y o f r o ta to r y power o f su g ar e x t r a c t s from SCaOeSAlgOg
i s c o n sid e re d c o n c lu siv e ev id en ce t h a t no f r e e I ia e was fo rc e d in th e ex­
t r a c t s by th e h y d ro ly s is o f th e e lim in a te , and t h a t th e c alc iu m oxide ex­
is t e d in th e e x t r a c t s combined w ith alum ina*
A ll e x t r a c t s from w hich s o lid phase s e p a ra te d on s ta n d in g had approxim ate­
ly th e earns c o m p o sitio n a f t e r e q u ilib riu m was a t t a i n e d , th e av erag e com­
p o s i t i o n b e in g 0*142 g o f calciu m oxide and 0*150 g o f a lu m in a p e r 100 ml
o f s o lu tio n *
The mol r a t i o , CaO t o AlgOg, i n th e se e x t r a c t s a f t e r p r e c ip i­
t a t i o n was in ev ery case e q u a l to a p p ro x im a te ly 2*00, th e a c t u a l average
v a lu e b e in g 1,99»
As was th e ease f o r th e o r ig i n a l e x t r a c t s , th e o p t i c a l
r o ta to r y power o f the e x tr a c ts a f t e r p r e c i p i t a t i o n was unchanged from t h a t
o f th e pure s u g a r s o lu tio n *
T h e re fo re , no f r e e lime was formed i n th e ex ­
t r a c t s d u rin g th e p r e c i p i t a t i o n p ro cess and a l l th e d is s o lv e d calcium oxide
must have e x is te d i n m o le c u lar co m b in atio n w ith alum ina*
The v a rio u s v a lu e s o f th e pE o f th e e x t r a c t s have been p lo tte d in f ig u r e 2
a g a in s t th e c o rre sp o n d in g amounts o f d is s o lv e d ealoium o x id e , alo n g w ith
a im ila r v a lu e s f o r C aO su g ar s o lu tio n s from fig u re I f o r comparison*
The
pH o f th e o r ig i n a l BCaOeSAlgOg e x tr a c ts approaches a lim it in g v alu e o f
11*00 t o 11*06.
The pii o f th e e x t r a c t s a f t e r p r e c i p i t a t i o n i s f a i r l y con­
s t a n t , th e av erag e o f th e f iv e d e te rm in a tio n s made b e in g 10*86.
S lig h t
b u t d e f i n i t e re d u c tio n s in pH were b ro u g h t a b o u t by th e sec o n d a ry r e a c tio n s .
An e x p la n a tio n o f th e f a c t t h a t th e BGaOeSAlgOs e x tr a c ts e x h ib it c o n sid e ra b le
11.50
IlO O
pH
I
1050
M
CU
I
IODO
0.100
0.200
C aO,
GyZlOO MU
FIGURE 2
CALCIUM OXIDE CONTENT OF EXTRACT VS pH
LKGLND:
• - R es ul ts
a - R esults
from ori gi nal e x t r a c t s .
from e x t r a c t s a f t e r p r e ­
c i p i t a t i o n . (Not included i n curve )
0300
26
h y d ro x y l-io n c o n c e n tr a tio n , even though th e e lim in a te ie n o t hydrolyzed t o
g iv e fre e c alc iu m h y d ro x id e , w i l l be g iv e n in S e c tio n IX-A, below .
The mol r a t i o s , CaO t o AlgOg, o f th e p r e c i p i t a t e s formed from th e o r ig in a l
e x t r a c t s , a s shown in column 11 o f Table I I I , a re r a th e r e r r a t i c , undoubt­
e d ly due t o th e f a c t t h a t th e y were d eterm in ed by d if f e r e n c e and th o f a c t
t h a t th e amount# o f p r e c i p i t a t e formed were s m a ll w ith r e s u l t a n t la rg e
e r r o r in th e r a t i o from r e l a t i v e l y sm a ll a n a l y t i c a l e r r o r .
The average o f
th e v a lu e s , w hich vary o v e r a range from 1.25 t o 1 .6 1 , i s 1 .5 9 .
D ire c t
a n a ly s is o f the re s id u e s was n o t a tte m p te d because o f d i f f i c u l t i e s and
e r r o r s to be e x p ec te d in p u rif y in g the s m a ll amounts o f such a g e la tin o u s
m a te ria l.
I n view o f th e c o n s i s t e n t r e s u l t s o b tain ed in th e d e te rm in a tio n s
o f th e mol r a t i o s o f th e e x t r a c t s , b o th b e fo re and a f t e r p r e c i p i t a t i o n , i t
i s to be expected t h a t th e mol r a t i o o f th e p r e c i p i t a t e s w i l l have a con­
s t a n t v a lu e .
S ince th e mol r a t i o o f th e e x t r a c t s in c re a s e d from 1.72
(average v a lu e ) t o 1.99 (average v a lu e ) d u rin g th e p r e c i p i t a t i o n p ro c e s s ,
a mol r a t i o o f 1.59 (av erag e v a lu e ) sh o u ld be a c lo s e a p p ro x im a tio n f o r
th e p r e c i p i t a t e s .
This co rresp o n d s t o a p ro p o rtio n o f c alc iu m oxide to a l ­
umina o f 4 tools t o 5 mo I s , and a l l th e lime m ust be In com bination w ith
a lu m in a , a lth o u g h a l l alum ina i s n o t n e c e s s a r ily in co m b in atio n w ith lim e .
A f i n a l su m m arisatio n o f t h e r e a c tio n s Involved betw een BCaOeSAlgOs and
s u g a r s o lu tio n w i l l be g iv e n in S e c tio n IX-C, below .
- 27 ? II.
REACtIOHS WtWREI tC aO 'A lgQgeFegO5 AM) SOOAS SOLUTION
Lapin (4) r e p o r ts t h a t w a te r r e a c ts w ith ACaOeAl2 OgeFs2O5 t o f o m a g e l
unci c r y s t a l lin o h y d rated t r i e s loium a l u o l m t e , which p ro c e ss may be re ­
p re s e n te d as fo llo w s $
ACaOeAlgO3 e Ie 2 O8 -- Xhg O — — g e l * SCaOe r. I2 Og eCBL5O >
SCaOeAl2 O5 eSEgO
(Il)
Ihe number o f m olecules o f w a te r o f h y d ra tio n in th e t r i calciu m a lu rn irn te ,
as re p o rte d by L apin, i s p ro b a b ly v e ry s u s c e p tib le t o th e c o n d itio n s o f
fo rm a tio n .
Ih e r e s u l t s o f t e s t s w ith 4Ca0eAlg0geFe2O5 and su g ar s o lu tio n a r e shown in
fa b le IV.
Th* r e s u l t s o b ta in e d from th e compound c o n ta in in g 0 .8 4 ^ fre e
c alc iu m oxide a re d i s t i n c t l y d i f f e r e n t from th o s e o b ta in e d w ith th e com­
pound c o n ta in in g no fr e e lim e .
T his is no d o u b t in d ic a tiv e t h a t , i n so
complex a m olecule as t h a t of 4 CaOeAl2O5 e Ie 2O5 where th e r e a re two d i f f e r ­
e n t a c id ic c o n s ti tu e n ts (Al2 O5 and Fe2 O5 ) and two k in d s o f c o o rd in a tin g
atoms (A1-atoms and Fe-a to m s ), com plete e q u ilib riu m i n c a l c i n a t i o n i s v ery
e s s e n tia l.
The mechanism o f th e fo rm a tio n o f 4 CaOeAl2O5 eFc2Og m ight w e ll
be t h a t o f fo rm a tio n o f , f i r s t , a calciu m alum .ne.te acd a calcium f e r r i t e
a n d , seco n d , t h e i n t e r a c t i o n o f th e s e l a t t e r compounds t o form th e complex
4 CaOeAl2O5 eFe2O5 .
I f such i s th e c a s e , d e te rm in a tio n o f f r e e lime is le s s a
m easure o f th e com pleteness o f c a lc in a tio n i n t h i s in s ta n c e th a n i t i s f o r
th e ealolum a lu m in a te s .
In view o f th e p o s s i b i l i t y t h a t a n e g a tiv e f r e e lime t e s t m ig h t n o t im ply
com plete c a l c i n a t i o n o f th e 4 CaOeAIgO5 eFe2 O5 , a p o rtio n o f th e m a te ria l
c o n ta in in g 0,84% f r e e c alc iu m oxide was h e a te d fo r two s u c c e s s iv e p erio d s
«* 28 ••
o f 7 ho u rs each a t IZSO0C, w hereas a h e a tin g p erio d o f two hours a t th is
te m p e ra tu re was s u f f i c i e n t t o j u s t e lim in a te a l l fr e e lim e .
T e sts h o e.
9 - e , 9 -d , and lO-o in T able IV p e r ta in t o t h i s s o - c a lle d " e x tr a burned"
m a te ria l.
In t h i s c o n n e c tio n , i t i s o f a t l e a s t p a ssin g i n t e r e s t t o n o te
t h a t 4CaO»AlgOg*FegOg, upon long h e a tin g a t 12S0°C, underw ent a d ecrease i n
volume o f a p p ro x im a te ly o n e - th ir d o f t h a t o f t h e o r i g i n a l d ry powder, b u t
t h a t , upon c o o lin g to room te m p e ra tu re , the m a te r ia l "d u ste d " and re tu rn e d
to i t s o r ig i n a l volum e.
This phenomenon, which took p lace c o n s id e ra b ly
below th e fu s io n p o in t, has n o t been p re v io u s ly re p o rte d i n th e l i t e r a t u r e
to th e w r i t e r ’ s know ledge•
The t e s t pro ced u re f o r t h i s s e r i e s was s u b s t a n t i a l l y th e earns as t h a t f o r
SCaOeSAlgOg, e x c e p t f o r th e a d d itio n a l a n a ly s e s f o r f e r r i c o x id e .
In t h i s
c o n n e c tio n , d e te rm in a tio n s were made o f th e p o s s ib le red u cin g e f f e c t o f
su e ro se on f e r r i c s a l t s by m ixing known q u a n t i t i e s o f f e r r i c s u lp h a te w ith
sugar s o lu tio n .
So e v id en c e o f re d u c tio n to th e fe rro u s c o n d itio n was
found•
As in d ic a te u i n Table IV, no a p p re c ia b le r e a c tio n o ccu rred betw een a p p a re n t­
ly pure 4CaQ*Al20j5eFogOj and su g ar s o lu tio n below amounts o f 2 .2 8 g o f th e
s o l i d compound p e r 100 ml o f s u g a r s o l u t i o n .
However, th e d ecid ed d is s i m i l ­
a r i t y betw een r e s u l t s w ith 2 .2 8 g . and more o f th e m a te r ia l c a lc in e d j u s t t o
th e p o in t o f e lim in a tio n o f f r e e c alc iu m ox id e and r e s u l t s o b ta in e d w ith th e
" e x tra -b u rn e d " m a te r ia l b rin g s up a q u e s tio n a s to th e t r u e n a tu re s o f th e s e
m a te ria ls .
Both m a te r ia ls were p rep ared from th e same su p p ly o f p a r t i a l l y
e a le in e d s to c k , c o n ta in e d no f r e e lime a f t e r c a l c i n a t i o n , and receiv ed id e n ­
t i c a l tre a tm e n t e x c e p t f o r th e d if f e r e n c e i n le n g th o f c a l c i n i n g .
The
- 29 -
TABIS IT - KBSULT S QF TESTS WITH hCaQ. A lpO y FepO^ ASU SUQAB SOLUTIOS
Tote.l
C om position o f B x tra o t
-jCaO• M aO tFegOt
I ln g dig Mol R a tio CaO /A lg O j/lb g O j
tim e, s o lv e d ,A lg 0 t,g /1 0 0 ml FegO^,g/lOOml CaO,g/lOOnl
a id e d ,
g/100
ml
‘
g/100 ml b 'u r e
So.
A (3 )
B(3)
A B
A B
A
B
(I)
(? )
10
11
H---6
7
8
9
I?
.
5
I
5
3
as9«W
M
H»
I
0.181
6
0 .0 1 8
0.06
(U) 0 .0 0 0
( I ) 0.016
(U)
—«•
2
0.275
6
1.025
0.00%
(U) 0 .0 0 0
(U) 0 .
;
(U)
—
3
0 .3 6 6
6
0.047
0.019
(U) n .0 0 0
(U) 0 .0 2 s
(U)
—
—
U
0.^5%
6
0 . vi
0 .0 2 1
%
(U) 0 .
(U)
—
—
5 ,
o.6%u
6
0 .1 5 7
O.0U9
\
(U) 0.037
(U)
1 .3 8 /1 .0 1
6
6—a
6—b
0 .9 1 5
0 .9 1 4
0 .91k
6
5
8
0 .119
0 .0 0 ]
I. » 8
0 .0 6 0
e. 0.000
(U) 0.007
(U) 0.052
(U) 0.003
(U) 0 .0 0 8
(U)
(U)
(U)
I . 5 8 /1 .0 0 /0 .i g
7
7—a
7 -b
1.368
1.370
1.371
6
5
8
0 .1 9 1
0.005
0 .0 0 8
0 .0 9 3 0 .0 8 2 0 .0 1 3
(U) 0 .0 0 0
0 .0 0 0
(U) 0 .0 0 0
0.0< ■
0 .0 1 3 0.085 0 .0 8 1
(U) 0.005
(U)
(U) 0 .008
(U)
1 .6 7 /1 .0 0 /0 .0 9
g
SwB
Mt
1.828
1.826
l.B ? 6
6
5
8
0 .2 8 8
0 .6 0 8
0 .0 1 6
I . lip I . - . h
(U) 0.0 0 0 5
0 .0 0 1
(5 ) 0.0005
0 .0 0 5
2.285
. .2 .- 9 3
? .- a u
?.?8 3
?.-S3
6
5
8
8
8
r>.? I
0 .019
0.C ■
0 .3 1 9
0 .3 1 0
6
5
g/
5
0 .793
0 .1 2 6
0 .1 5 8
0 .6 ? 6
9
9—a
9 -b
9 -o
9 -d
10
1 0 -a
in - b
IH-C
otmg;
U.56U
U.566
.566
U;565
(I)
(")
.
(U) 0 .0 0 0
Mol—R a tio —
CaO/AlpOt/lb ^ O i
pH of
in
p re c ip ita te
B
A
B
IU
15
.
13
.. ...
9.S 5
(U)
5 2 .6
(U)
10.05
(U)
5 2 .5
(U)
—
10.15
(U)
5 2 .U
. .
—
10.25
(U)
5 2 .6
(U)
1 0 .Uo
(U)
.$
(U)
10.55
10.05
10.05
(U)
(U)
(U)
.U
5 ^ .5
(U)
(U)
(U)
5 2 .7
(U)
(")
.
1 . 7 0 / l .o n / O .l l
—
—
In e p fM c ia n t
—
—
10.75 10.65
10.10 (U)
10.15 (U)
5 2 .6
.6
5 2 .5
1 1 .so 10.50
10.15 (U)
10.20
5 *0
10.95 in .8 5
10.20 (U)
1 0 .Uo
10.75 (6 )
10.75 (6 )
5 2 .0
5 - .5
5 ^ .5
5 2 .1
5 2 .0
5 1 .6
(U)
11.00 10.75
' . 7 5 1 0 .T5
10.75 10.50
10.80 (6 )
5 1 .0
5 - .9
5 2 .1
5 2 .0
U9.U
5 .U
5 2 .U
(6 )
.111
(U)
(5 )
1 .8 9 /1 .0 0 /0 .1 6
—
—
.1 /1 .0 0 /0 .1 7 i . " 5 / i . i i / n . i o
0 .1 6 2 0 .133
(U)
0.005
(5 )
>.05
;1
0.167
0 .1 5 2
(6 )
0 .0 5 0 O.oUR 0.121 0.153
n.0 0 0 5
(U) 0.013
(U)
0 .0 0 1
(5 ) 0 .0 3 6
(5 )
".12
(6 ) 0.1U3
(6 )
(6 )
0 .1 1 9
(6 ) 0 .139
2 .0 3 /1 .0 0 /0 .1 9
.1 9 /1 .9 0 /0 .1 3 1 .7 6 /l.n r /o .o U
" ." 1 3 -.1'::1.118 1 .'9 2
,111
0 .1 3 7
(6 )
0.310
i.l'T
0 .0 1 1
%M 3
0 . 0 U0
M 0 .2 1 7
n .n ig 0.197 0.079
0 .0 1 1 0 .1 0 8 0 .0 8 5
(6 ) 0 .2 7 8 (6 )
.0 9 / 1 .0 0 /c . 1
% U 9 /i.o o /o .o 6
I . U ; /1 .1 0 /0 .0 6
1 .6 3 /1 .0 0 /0 .OS
.
(U) 0 .005
(5 ) 0 .011
I . 7 / l .T O / n ." i
1 . 5 6 'l . o o / n . r r
1 .6 6 /1 .0 0 /0 .0 8
—-
(5 )
(6 )
(6 )
O p tic a l Rota­
tio n o f S x t r a c t ,
V entske $ p e r
200 mm
A
B
16
17
**’—1
(5 )
(6 )
(6 )
. /1 .0 0 /0 .3 2 1 .7 6 /1 .0 0 /0 .1 0
1 .5 7 /1 .0 0 /0 .0 7 1 .2 9 /1 .0 0 /0 .ou
.1 ... '
. '■ .IT
.
(T)
(U)
5 2 .5
(6)
(6)
Iiunbera n o t fo llo w e d by a l e t t e r a r e f a r t e s t e u s in g UCaO• AlpOt• Fe--O-? c o n ta ln ir ,: . & ' ■ f r e e CaO. O th er t e s t s a re " i t h UCaO.AlpO^• FegO^
c e n t ia ln g no f r e e CeO. See eorauentfi in t e n t f o r - i f fe re n c e s betw een Uoe. $ -c , 9 -d , 10-c and 9-"» 9 -b , IOn, 1 0 -b .
-ugar + IOOml w a ter = 1 0 9 .U
' I hi >n. Amounts o f UCaO*AlgOyFegOi; a c t u a l l y u sed h a re been r * -Iuced by th e f a c t o r 1 0 0 /1 0 9 .5
to g iv e th--= r - l u . I ' ^ i c: Uj _n.
Column A f o r o r i g i n a l e x tr a c ts } Column 3 f o r e ^ t r - c t r - f t e r p r e c l u i t - t i o n . ( r>) " l i g h t amount o f c r y s t a l l i n e p r e c i p i t a t e s , l n s u f f i -i l t ^ t c f - r r - i .
\U) I;, w '
^ U.
to
-'w n t to - - iy
c o lle c te d on b n - f '
^ a l l s of
serialt th e p r e c i p i t a t i o n r e c tio n to re a ch e q u ilib riu m .
fla s k .
30
m a te r ie l e a lo in e d f o r th e s h o r te r p e rio d i s d e f i n i t e l y th e more s ta b l e i n
th e p re se n c e o f s u g a r s o l u t i o n , a s ev id en ced by i t s d e c id e d ly low er s o lu ­
b i l i t i e s f o r g iv e n m ixing p e r io d s .
F a c i l i t i e s and tim e were n o t available
f o r d e te rm in in g w h e th er e i t h e r o f th e s e m a te r ia ls was t r u l y pure 4CaO*
AIgO j• IegOge
I t i s co n sid e re d t h a t a p e tro g ra p h ic o r X -ray d i f f r a c t i o n
ex am in atio n i s n e c e s sa ry f o r t h i s purpose#
I t m ight be t h a t th e phenomen­
on o f volum e-change and " d u s tin g " m entioned above fo r th e e x tra -b u rn e d
m a te r ia l i s ev id en ce o f an u n s ta b le c o m b in a tio n ef th e c o n s ti tu e n ts ( a t h ig h
te m p e ra tu re w ith r e s u l t a n t s h rin k a g e ) fo llo w ed by d eco m p o sitio n in to an
alum l n a t e and a f e r r i t e ( a t low te m p e ra tu re w ith r e s u l t a n t " d u st In g " ).
In
any e v e n t, the e x tra -b u rn e d m a te r ia l more c lo s e ly resem bles th e m a te ria l
c o n ta in in g 0.84% f r e e calciu m o x id e , in s o f a r a s i t s r e a c tio n w ith s u g a r
s o lu tio n i s c o n c e rn e d , th a n i t does th e m a te r ia l c a lc in e d j u s t t o th e
p o in t o f e lim in a tio n o f f r e e lim e*
Tiie r a t e o f th e i n i t i a l r e a c tio n between th e 4CaOeAIgOgeFegOg m a te ria ls and
s u ^ a r s o lu tio n i s s low, as compared t o t h a t betw een e i t h e r BCaOeSAlgOg and
s u g a r s o lu tio n d is c u s s e d in S e c tio n VI o r SCaOeAlgOg t o ns d is c u s s e d in
S e c tio n V I I I , b elo w .
There i s no ev id en ce o f com plete s o l u t i o n , e i t h e r tr u e
o r c o l l o i d a l , a t any c o n c e n tr a tio n , even w ith th e s m a lle s t amounts o f th e
m a te r ia l used in th e in v e s t i g a t i o n .
The amount o f m a te r ia l d is so lv e d l a a
f u n c tio n o f th e le n g th o f th e m ixing p e rio d b u t , as in d ic a te d i n columns
6 , 7 , and 9 o f T able IV , th e i n i t i a l r e a c tio n i s n o t one o f s o lu tio n o f th e
o r i g i n a l m a te r ia l as s u c h .
The p ro p o rtio n of f e r r i c oxide going in to s o lu ­
t i o n i s , i n a l l c a s e s , much le s s th a n th e c o rre sp o n d in g p ro p o rtio n s o f a l u ­
mina and calciu m o x id e .
L ik ew ise, th e r a t i o s o f calcium oxide to alum ina
a re » e t th e eaune in th e e x tra c t® as i n th e o r i g i n a l m a te r ia l* .
Kvidenoe o f th e h y d ro ly s ia o f a l l th r e e type* o f ^ a O eAlgOseFfcgO5 m a te r ia l
in v e s tig a te d oonsoe from th e v e ry lim ite d amounts o f f e r r i c oxide d i s s o l ­
v e d , th e changes in mol r a t i o o f calciu m oxide t o alum ina in th e o r ig in a l
e x t r a c t s as in d ic a te d i n column 11 o f T ab le IV , and the re d u c tio n s in
o p t i c a l r o ta to r y power o f th e e x tr a c ts w ith in c re a s in g am ourt# o f t o t a l
d is s o lv e d c alc iu m oxide a s in d ic a te d i n column 16 o f Table IV .
In f ig u r e 3 , th e r o ta to r y power and pH v a lu e s o f e x t r a c t s from dCaO'AlgOg*
M*gOg m a te r ia l c o n ta in in g no fr e e lim e have been p lo tte d a g a in s t th e c o r­
re sp o n d in g amounts o f t o t a l d is s o lv e d calciu m oxide p e r 100 ml o f s o lu tio n .
F ig u re 4 i s s im ila r t o f ig u r e 3 , e x ce p t t h a t i t i s f o r m a te r ia l c o n ta in in g
0.84% f r e e c alc iu m o x id e .
Both of th e s e f ig u r e s i l l u s t r a t e th e su b sta n ­
t i a l l y com plete h y d ro ly s is o f t h a t p o r tio n o f th e -ICaOeAlgO5 eFcgOg m a te r ia l
t h a t is d is s o lv e d , as evid en ced by th e f a c t t h a t th e re d u c tio n s in r o ta to r y
power o f th e o r i g i n a l e x t r a c t s w ith in c r e a s in g amounts o f t o t a l d is so lv e d
calciu m oxide a re a p p ro x im a te ly th e same a s th o se f o r CaO-eugar s o lu tio n s .
With re fe re n c e to f ig u r e 4 and th e seem ingly u n u su al re d u c tio n s i n r o ta to r y
power o f th e e x t r a c t s a f t e r p r e c i p i t a t i o n , re fe re n c e i s made t o th e e x p la n a ­
t i o n in S e c tio n V I I I , below , o f a s im ila r phenomenon in th e c a se o f e x t r a c t s
from SCaOeAlgOg.
The r e s u l t s shown in columns 11 and 12 o f T able IV f o r th e mol r a t i o s , CaO
t o AlgOg, o f th e e x tr a c ts b e fo re and a f t e r secondary p r e c i p i t a t i o n , and th e
v a lu e s shown i n column 13 f o r s im ila r mol r a t i o s o f th e p r e c i p i t a t e s , show
d e f i n i t e tre n d s w ith changes in amounts o f s t a r t i n g m a t e r i a l s ,
however,
th e s ig n if ic a n c e o f th e s e r e s u l t s can n o t be p ro p e rly e v a lu a te d in view o f
— 32 —
th e q u e s tio n a b le n a tu re o f th e m a te r ia ls t e s t e d .
K im l sucka r i s a t i o n o f
th e r e a c tio n s betw een pure ^rCaO-Al2O3 e FegO3 and su g a r s o lu tio n i s r o t
p o s s ib le from th e r e s u l t s o f th e p re s e n t i n v e s t i g a t i o n .
12.00
R o t a t i o n , V e. n t S K t %
11.00
iaoo
pH
A
C4
I
o.ioo
0.300
FIGURE. 3
T AND p H _V S . CaO CONTENT OF EXTRACT FROM 4 C a O ^A l2 O3 1F e 2 O3
1EEW :
-A -
-A -
-Ro t a t i o n
of
o r ig i n au
E.ATRACTS
■Ro t a t i o n
of
e x t r a c t s
a f t e r
■p H
O F
ORIGINAL.
-p H
OF
EXTRACTS
-C aO - S u
GA R
P R tC IP I TAT ION
EXTRACTS
A FTtR
SOUUT IO
N
PRECIPITATION
0 .4 0 0
12.00
55
8.00
o .lo o
odbo
0.200
0500
0 .4 0 0
C a O , g/ io o m l
FIGURE 4
SUGAR CONTENT AND pH VS. CaO CONTENT OF EXTRACT FROM 4CaO1AI2O3 -Fe O3 AND FREE LIMB.
L E G E ND*—° —
" R otation of original e x t r a c t s c
^
R o tatio m of e x t r a c t s a f t e r p r e c i p i t a t i o n
—p H o f o r i g i n a l e x t r a c t s
—f H OF EXTRACTS AFTER T-RtciFJTATION
----------- CaO S u g a r so l u t io n
—a —
- 56
V III.
R ACTIONS BBtWWSB SCaOeAlgOg AND SUGAR SOLUTION
A alU (16) r e p o r ts t h a t w a te r re a c ts w ith SCaOeAlgOg so r a p id ly t h a t th e
p ro g re s s o f th e r e a c tio n can n o t be follow ed e x p e r im e n ta lly .
However,
K le in and P h i l l i p s (5 ) r e p o r t t h a t th e s e t t i n g o f SCaOeAI2O^ i s due to th e
fo rm a tio n o f th e h y d ra te w ith o u t th e fo rm a tio n o f h y d rated a lu m in a .
Irre s­
p e c tiv e o f whet tier o r n o t hydrolysis o f th e compound occurs when i t f i r s t
comes i n c o n ta c t w ith w a te r , i t i s a p p a re n t t h a t th e f i n a l a lu m ln a te p re ­
c i p i t a t e i s th e same ks t h a t o b ta in e d from th e etl<er calcium a lu m in ates as
re p o rte d by S e l l s (1 6 ) , nam ely, th e h y d ra te d t r Icalt=Ium a lu m ln a te .
This
most b a s ic o f th e calciu m a la m in a te s known t o e x i s t i n th e system CaO-AlgOg
th e r e f o r e must be th e most s ta b le in th e p re sen c e o f w a te r .
Tiio r e s u l t s o f t e s t s w ith SCaGeAlgOg and s u g a r s o lu tio n a re shewn in T able
V.
So a p p re c ia b le d if f e r e n c e i s noted between t e s t r e s u l t s o b tain ed w ith
th e a l u ml na t e c o n ta in in g 2*04%. fre e calciu m oxide and r e s u l t s o b tain ed
w ith tlie alu m ln ate c o n ta in in g no f r e e c alc iu m o x id e , undou b ted ly due to th e
h ig h r e a c t i v i t y o f th e e lim in a te i t s e l f .
th e t e s t procedure f o r t h i s s e r i e s wae th e same as t h a t f o r GfaOeBAlgOg, e x ­
c e p t t h a t th e e a g e r wee ground t o a powder p r i o r to w eighing and m ixing w ith
th e compound, in o rd e r to a s s u r e more in tim a te m ixing and f u r t h e r reduce th e
tendency t o lump when w a te r is add ed .
Q u a n titie s o f th e alu m ln a te up to 0.915 g p e r 100 ml o f s u g a r s o lu tio n went
e n t i r e l y i r t o s o lu tio n w ith in 16 m in u te s.
However, a s o lu tio n o f 0,913 g
o f th e alumina.t e s t a r t e d seco n d ary p r e c i p i t a t i o n s h o r tly a f t e r th e 15-m inute
m ixing p e rio d , n e c e s s ita tin g t h a t th e pB and pola rim e try d e te rm in a tio n s be
made very r a p i d l y .
In view o f th e f a c t t h a t 16 m inutes was a b o u t th e m in i-
TABLE V - EBSeiJS O f TESTS JlTB SCaO-AlgQs ASD StiOAE SOUJTIOB
Bo.
(I)
SCaOe
Al2Og
ad d ed ,
g/lOOml
(2 )
p
Mix­
ing
tim e,
h rs.
T o ta l
d is ­
solved,
s/
IOCtel
S
C om position o f E x tra c t
AlgOg ,g/lCQal CteO ,i/lOOml M oI-R atio ,
C aoA L 1Ox
A(5, 8 (3 )
A
B
A
B
5
9
10
I
M ol-S et.
!o p tic a l io ta -l
o f Pre­
t io n o f E xtract
pH ClI
c i p i t a t e , E xtra, 51
Pentske % p er
OeO/Ateoa
200 b»
B
A
B
A
B
IS
14
U
I
0.047
i
0 .047
D.018 Ho p p t 0 .0 2 9 Bo ppt 5 .0 0 Bo pp t Ho ppt
10.60
(7 )
52.8
52 .7
2
0.092
i
0 .092
3.035 Ho ppt 0.057 Ho ppt 5 .0 0 So pp t So p p t
10.76 10.60
62.7
6 2 .7
5
0 .229
i
0 .2 2 9
3.086 0.085
0.143 0 .1 4 1
3 .0 0
11.10 11.00
6 2 .5
62.3
4
4 -a
0.458
0 .456
i
t
0 .4 6 8
0 .4 5 6
3.175 0.171
3.172 0.171
0.285 0 .2 8 4
0.284 0.267
5 .0 0
5.00
11.30 11.50
11.30 (7 )
62.2
62 .1
52.2
52.2
6
6 -a
0 .899
0.915
i
*
0 .899
0.915
3.559 0.176
3.545 0.166
0 .5 6 0 0.543
0.668 0.316
3 .0 0
5 .0 0
3.5 6
5 .6 0
2.42
2 .5 3
11.35 11.35
11.40 (7)
61 .7
61.7
49.6
4 9 .1
6
6 -a
1.571
1.570
(4)
(4 )
1.371(5) 0.517 0.161
1*370 (5) 0.517 0.146
0 .864 0 .3 4 5
0.853 0.515
5 .0 0
3 .0 0
3 .8 9
3 .9 0
2 .6 9
2 .6 4
(6 )
(6 )
(7)
(7)
(6)
(6)
4 7 .0
4 5.8
7 -a
2.283
(4)
0 .2 8 0
(6 )
4 .4 1
*—
(6)
(7 )
(6)
38.5
S o tes *
(6)
(6 )
0.116
(6)
—
( I ) Buebers n o t follow ed by l e t t e r s a re f o r t e s t s u sin g SCaOeAlgOs c o n ta in in g 2.04& fr e e
QaO. O th er t e s t s a re w ith SCaO-AlgOs c o n ta in in g no fr e e CaO•
(2 ) 15g s u g a r + IOOml w a te r * 1 0 9 .Bcl o f s o l u t i o n . Amounts o f SCaO-AIgOg a c tu a lly used
have been reduced by th e f a c t o r 100/109.6 to give th e v a lu e s shown in t h i s column.
(5 ) Column A f o r o r i g i n a l e x t r a c t s $ column B f o r e x tr a c ts a f t e r p r e c i p i t a t i o n .
(4 ) M a te ria ls shaken in a f l a s k f o r about 6 m inutes and th e n p e rm itte d t o s ta n d f o r p re ­
c ip ita tio n .
(6 ) Assumed, from th e f a c t t h a t th e alu m in ate went in to s u b s t a n t i a l l y com plete s o lu tio n
a t ab o u t S m in u te s , follow ed by s t a r t o f secondary p r e c i p i t a t i o n a t about 5 m in u te s.
(6) Im p o ssib le t o d eterm in e because o f seco n d ary p r e c i p i t a t i o n . 7
(7) Could n o t determ in e because o f broken g la s s e l e c t r o d e . See C osaents in t e x t . _______
37 Bum tim e t h a t could bo used t o r a x la g « d s t a r t i n g th e t e s t a , «md th e f a c t
t h a t l a r g e r ^m atiL tW e o f 3 C * 0 * c a u s e d secondary p n s# lp l* # * lo # to
s t a r t e?@a so o tie r. I t mis n o t p o s s ib le t o t e s t o r ig i n a l ex't r a o ts from l a r g e r
q u a n t i t i e s o f th e s o l i d a lu m ie a te th a n 0*913 £ p er 100 ml o f su g ar s o lu tio n *
th e r e f o r e , t e s t s w ith la r g e r q - .e n t i t l e e o f th e compound than, t h i s were made
only to o bserve th e n a tu re o f th e e x tr a c t* o b ta in e d a f t e r th e seco n d ary p re ­
c i p i t a t i o n r e a c tio n h id reached csep lsstio o #
w ith re fe re n c e t o th e two t e s t s w ith 1 .3 ? g and 2*28 g o f pure 3CaO*AlgOs
p e r KX3 &1 o f s o l u t i o n , ties f i r s t showed a lm o st eosaplete s o l u t i o n w ith in
a b o u t 3 m in u te s , follow ed by i n i t i a t i o n o f p r e c i p i t a t i o n a t ap p ro x im a te Iy
6 m in u te s , and th e aeaond s t a r t e d p r e c i p i t a t i o n w ith in a p p ro x im a te ly 2 mi Ba­
te s .
I t was n o t p o s s ib le t o d eterm in e w hether o r no t th e i n i t i a l p ro c e ss o f
s o lu tio n c o n tin u e i t o s e e p l s t l o n in t h i s
latter
t e s t a t tlie e a s e tim e th a t
th e seco n d ary prooese o f p r e c i p i t a t i o n wee underway*
Use of amounts of SCaCaAlgOs in excess of 0*229 g per 100 ml of solu tion re­
al. Had in fi* testa b le extracts oocti- lnlnc InereMng amount* o f dissolve# lime
a«d alumina, from which so lid gelatinous material separated on standing*
The amount# o f p r e c i p i t a t e fu m ed from s t a r t i n g amounts o f t h e a lum lnato
o f 0*329 g and
*468 g were o n ly « H fJb t.
I t I* o f i n t e r e s t t o note t h a t
t h i s " th re s h o ld " amount o f 8CaO*AlgOg n e c e s sa ry f o r t h s form at Ion of r e t a s t a o l e e x tr a c t* i s a |)p ro x i® a te ly th e se e s a s t h a t f o r SeaOeSAlgOs * The p re ­
c i p i t a t i o n r e a c tio n f o r t h i s a lam inate was eon* ld e ra b ly mere ra p id th a n f o r
e i t h e r SCaOeSAlgOs o r ACaOe A1%O5 • fe£Og , one week b e in g s u ff I o i e e t In a l l
o a se s f o r com plete p r e c ip ita tio n *
The mol r a t i o , PaU t o AIg Oy, o f th e o r i g i n a l SCaOeAlgOs i t 3.00*
A* l e d i e a -
te d in column 9 o f Table V, th e v a lu e s o f t h i s r a t i o f o r th e o r ig i n a l e x t r a c t s f r e e SCaO^Al2 O3 d id n o t change w ith in th e range o f amounts p o s sib le
t o s tu d y , due t o th e com plete s o lu tio n o f th e m a te r ia l.
S it h re fe re n c e to column 14 o f Table V, v a ry in g amounts o f SCaOeAl2O3 had
u i s t i c c t e f f e c t s on th e o p t i c a l r o ta to r y powers o f th e e x t r a c t s .
This is
more c l e a r l y i l l u s t r a t e d in f ig u r e 6 , w h erein both th e r o t a t o r y power and
th e pH o t th e e x t r a c t s a re p lo tte d a g a in s t th e c o rre sp o n d in g amounts o f
t o t a l d is s o lv e d calciu m oxide p e r 100 ml o f s o lu tio n .
The re d u c tio n in
r o ta to r y power o f SCaOeAl2Os e x t r a c t s i s ev id en ce o f th e o ccu rren ce of
l y d r o l y s is o f th e compound t o l i b e r a t e calciu m hydroxide w hich, in tu r n
combines w ith th e s u g a r i n th e s o lu tio n #
However, as in d ic a te d in fig u r e
6 , th e re d u c tio n i n r o ta to r y power w ith in c re a s in g amounts o f t o t a l d i s ­
so lv ed calciu m oxide i s n o t as g r e a t f o r th e SCaOeAl2O5 e x t r a c t s as f o r th e
CaG-sugar s o l u t i o n s , th u s in d ic a tin g t h a t th e a lum inate was n o t e n t i r e l y
h y d ro ly sed w ith in th e 20-m inute p e rio d t h a t i t was in c o n ta c t w ith th e
s u g a r s o lu tio n p r i o r to m easuring th e r o ta to r y pow er.
I? i s p ro b ab le t h a t
lo n g e r c o n ta c t p e rio d s would have r e s u lte d in more com plete h y d ro ly s is
(see th e d is c u s s io n o f th e seco n d ary p r e c i p i t a t i o n r e a c tio n be low) b u t th e
-sarly o ccu rren ce o f th e seco n d ary p r e c i p i t a t i o n re a c tio n p re c lu d ed a stu d y
of th is p o s s ib ility .
Ihe pH o f th e o r i g i n a l e x t r a c t s , a s in d ic a te d in column 12 o f Table Y and
i n fig u r e 5 , in c re a s e d w ith in c re a s in g amounts o f t o t a l d is s o lv e d calciu m
oxide b u t n o t to th e e x te n t noted w ith CaO-sugar s o l u t i o n s .
T hia i s a g a in
a t l e a s t p a r t i a l l y due t o th e lim ite d e x te n t o f h y d ro ly s is w ith in th e 2 0 m inute c o n ta c t p e rio d .
I t was n o t p o s s ib le to d eterm ine th e pH o f o r i g i n a l
12.00
11.00
10.00
-6 2
1
9 .0 0
OOOO
0 .4 0 0
C a O , C / IOO ML.
FIGURE. 5
SUGAR CONTENT AND pH VS. CaO CONTENT OF EXTRACT FROM SCaO-Al2 O3
LEGEND'
...... - R o t a t i o n
'“ R o ta tio n
0
~~a
or
original
extracts
or
extracts
after
pH o r original
------- p H o r e x t r a c t s
-------------- C a O - S
uoar
precipitation
extracts
after
solu tio n
f r e c ip it a t io n
-
40
-
e x t r a c t s c o n ta in in g s o re th a n 0.915 g o f t o t a l d is s o lv e d ^ lu a ijia ta o r o f
e x t r a c t s whioh had re a c te d more th a n a p p ro x im a te ly 20 m in u te s , because o f
tJ » e a r l y o eourrencc o f seco n d ary p r e c i p i t a t i o n .
F u rth e r d is c u s s io n a I th e s ig n if ic a n c e o f th e pH v a lu e s o f th e e x tr a c ts w i l l
be g iv e n In S e c tio n IX-A, below .
U nlike th e r e s u l t s o b ta in e d w ith e x t r a c t s from SCaO-SAl2 O3 , th e e x tr a c ts
i-om S'aO-AlgOj from which s o l i d phase s e p a ra te d on s ta n d in g d id n o t a l l
approach th e same co m p o sitio n a f t e r e q u ilib riu m was a t t a i n e d .
As in d ic a te d
In columns 6 and 8 o f T able V, b o th th e d is s o lv e d alum ina and d is s o lv e d
CaIoIum o x id e , in th e e x t r a c t s a f t e r p r e c i p i t a t i o n , re a ch a maximum and
th e n d e c re a se w ith f u r t h e r in c re a s e s in amounts o f o r ig i n a l SCaG-Al2C^#
F u r th e r , a s in d ic a te d in column 10 o f Teble Y end a s i l l u s t r a t e d in f ig u r e
6 , w herein th e mol r a tio s o f th e e x t r a c t s b e fo re and a f t e r p r e c i p i t a t i o n
a re p lo tte d a g a in s t th e c o rre sp o n d in g t o t a l a ro u n ts o f d is s o lv e d alum ina
and calciu m o x id e , th e mol r a t i o s (CaC t o Al3 O3 ) o f th e e x t r a c t s a f t e r p re ­
c i p i t a t i o n Biarkaly in c re a s e w ith in c re a s in g amounts o f o r i g i n a l SOaO-AlgO3 .
I js c o n n e c tio n w ith th e s e r e s u l t s , th e seem ingly u n u s u a l o p t i c a l r o ta to r y
powers o f th e e x t r a c t s a f t e r p r e c ip ita ti o n must a lso b e c o n s id e re d .
As
shown in f ig u r e 6 , th e e x tr a c ts a f t e r p r e c i p i t a t i o n , upon sta n d in g f o r ene
week, showed w r y d ecid ed dec re a r es In r o t a t o r y power.
In f a c t , th e se dy­
e r s e e s a re much g r e a t e r th a n can be acco u n ted fo r from th e amounts o f d i s ­
so lv ed calciu m oxide in th e s o l u t i o n s .
E x p la n a tio n o f th e seco n d ary p r e c i p i t a t i o n r e a c tio n o f SCaO-Al2O3 e x tr a c ts
e n t i l e sn e x p la n a tio n o f th e above- e e a t io c sd u n u su al r e d u c tio n in r o ta to r y
power of th e e x t r a c t s .
W ferrin g t o th e r o ta to r y powers o f CaO-augar s o Iu -
Ex t r a c t
of
Ca0/A l2_05
Mol - R a t i o
4..00
3.00
2 .00.
0.00
1.00
T b rA L . D i s s o l v e d
g
/
ioo
2.00
ml
FIGURE 6
THE RATIO OF CaO TO A l 2 O3 VS. TOTAL GRAMS OF SCaO1AlgO3 DISSOLVED.
LE,GEND: • " B e.FOPE.
o- A f t e r
PRECIF
itation
frecifitation
<2
tilvns i l l u s t r a t e
in f ig u r e I , a t t e n t i o n i s in v ite d t o the f a c t th a t th e
p e rio d o f s ta n d in g t r i o r to t e s t i n g was Z hours f o r a l l u&Osug&r s o lu tio n s
c o n ta in in g le s s th a n 2 .5 g . o f ea l e i u a 6x16*.
A lthough amounts o f sale lu te
oxide o f le s s th a n 2 .6 g were oMupI e tely d is s o lv e d w ith in 2 h o u rs , i t s i g h t
be t h a t a p r e c i p i t a t e o f t r i o s lo iu s s u e r a te would have fen ced from t i e s ,
bad th e y been p e rm itte d to s ta n s f o r a s u f f i c i e n t l y long t i a ; e .
In ur-y e v e n t,
th e doo.etedly g r e a t e r r e d u c tio n in o p t i c a l r o ta to r y power o f t i n BCaOeAlgOs
e x t r a c t s a f t e r p r e c i p i t a t i o n , a s compared to t h a t o f C nO eugar S o lu tio n s ,
can 6@ e x p la in e d on th e b a s is t h a t , in t.-x c a se o f th e e x t r a c t s , su g ar no t
c n Iy ocabineti in so lu tio n , w ith o a lo iu a h y d roxide bu t a l s o p r e c ip ita te d from
s o lu tio n as in s o lu b le t r i c a lc iu m sue r a te d u rin g tiiC 1-weok p e rio d o f s ta n d lo g .
A f u r th e r e x p la n a tio n , in v o lv in g th e e o m b in atio a o f hyUr a te d alum ina
and s u g a r a t th e r e l a t i v e l y h ig h h y b re x y l-io n e o n e o n tra tic n s e x is t in g i n th e s e
s o l u t i o n s , has sojt« m e r it b u t la c k s any e x p e rim e n ta l c o n firm a tio n .
I t a p p ea rs e v id e n t tn& t th o calciu m oxide and alum ina r e m in in g i n s o lu tio n
a f t e r p r e c i p i t a t i o n was com plete were a c t eosin aied w ith each o th e r b u t t h a t ,
r a t h e r , th e calcium oxide was eotifcined w ith su g ar enu th e alum ina was p re s e n t
aa fr e e d is s o lv e d a luninum hydroxide b ecau se o f tiss r e l a t i v e l y h ig h h y d ro x y lio n c o n c e n tr a tio n .
A lthough, as p re v io u s ly n o te d , i t was n o t p o s sib le to
d eterm in e th e p i v a lu e s f o r s e v e r a l o f th e e x tr a c ts a f t e r p r e c i p i t a t i o n
because o f the only a v a ila b le g la s s e ls a tr o d o b ein g b ro k e n , i t n ig h t w e ll be
tlm t th e Sinr,,ed re d u c tio n i n amount o f d is s o lv e d alum ina in th e ease o f t a c t
bo* 7 -a i s a s s o c ia te d w ith a re d u c tio n i n tlie pH o f t i » e x t r a c t .
Ihe re d u c ­
t i o n in amount o f d is s o lv e d calcium oxide i n th e case oi th e same t e s t is
p ro b a b ly due t o a n Inerw ase i n th e amount o f liis s p r e c ip ita te d a s sue r a t e .
-
45
-
A lthough th e p r e c i p i t a t e s from th e SCaO-Al2O3 e x tr a c ts hav
ap p ro x im ately
th e same c o m p o sitio n , even though v a ry in g c o n s id e ra b ly In am ounts, t h i s c o n ­
d i t i o n may be due t o the lim ite d range o f c o n c e n tra tio n s o f o r i g i n a l a Iumin a te s t u d i e d .
As in d ic a te d i n column 11 o f T able V, th e r e i s a s l i g h t in ­
c re a s e in th e mol r a t i o , CaO t o Al2 O5 , in th e p r e c i p i t a t e s , going from
o r i g i n a l amounts o f SCaO-Al2O3 o f 0 .9 0 g t o 1.37 g .
re fe re n c e is
In t h i s c o n n e c tio n ,
ade to fig u r e 7 , w herein th e mols o f d is s o lv e d calciu m oxide
and alum ina p e r 100 ml a f t e r p r e c i p i t a t i o n a re p lo tte d a g a i n s t th e c o r r e s ­
ponding o r i g i n a l amounts o f SCaO-U2O3 .
I n t h i s p l o t , one lo g i c a l assum ption
i s made; t h a t i s , i n th e c a se s o f g r e a te r amounts o f SCaO-Al2 Os where s e c ­
ondary p r e c i p i t a t i o n s t a r t s p r i o r t o c o m p letio n o f th e i n i t i a l s o lu tio n
p ro c e s s , i t i s assumed t h a t the I n i t i a l s o lu tio n c o n tin u e s t o co m p letio n
w h ile th e
r o o i p l t a t l o n r e a c tio n Is underw ay.
In t h i s w*y, th e nol r a t i o s
o f p r e c i p i t a t e s have been e stim a te d beyond th e range covered by th e p re s e n t
I n v e s tig a tio n and a rc shown in Table V I.
I t i s e v id e n t from th e s e d a ta t h a t
th e mol r a t i o in c re a s e s t o a maximum of a t l e a s t a p p ro x l a t e l y 2 .8 0 .
How­
e v e r , because o f th e e x te n s iv e h y d ro ly s is t h a t lias been found to ta k e p la c e ,
th e alum ina and o a le lu r. oxide must be p re s e n t i n th e p r e c i p i t a t e m ostly as
f r e e h / i ra te d alum ina and calcium sue r a te r a t h e r th a n as combined calcium
a lu m in a te .
A S lm U a r c o n d ito n i s p ro b a b ly a s s o c ia te d w ith th e w ell-know n
r « r y d e le te r io u s a c ti o n o f su g ar on th e s o ttin g o f P o rtla n d cem ent.
A f i n a l su m m arisation o f th e r e a c tio n s in v o lv ed betw een SCaQ-Al2O5 and
s u g a r e e I n t io n w i l l be g iv e n in S e c tio n IX-C, below .
CaO -1X
X0.0060
5.00
COMPARISON CF TOTAL MOLS
B lfore
precipitation
VS. GRAMS 3CaO*Al2 03 added
%--------- A r t e r
pr ec ipita tio n
TABLE VI
INTERPOLATED MOL RATIOS
OF PRECIPITATES FROM SCaOeA l2Ox EXTRACTS
(From F ig u re 7 , Above)
T o ta l SCaOeAlgOs ad d ed .
g/lOOml
i:8
2 .0 2
2 .4 5
2 .8 0
Mol r a t i o o f p r e c i p i t a t e .
Ca0/Al%0x
hit
2 .8 5
2 .75
2 .8 1
45
IX .
A.
DISCUSSIOIi OF BSULfS
S lg a lfio su io e o f H yclroxyl-Ion C onoantr a tio n
te n th end Bogae ( 6 ) , in stu d le e ontha h y d ro ly s is o f eompeuads W iloh .:my
ooou r in P o rtla n d o e m n t, c o n sid e re d th e h y :ro sy I - io n c o n se n t r a t Iocs of
s o lu tio n s o b ta in e d from t r e a t i n g th e anapoacde w ith w a te r a s m easures o f
th e deg ree t o W io h th e Oraapounds had been hy d ro ly sed t o l i b e r a t e d is s o lv e d
oa loium hydroxide .
The f a s t th a t, th e anhyti roua calciu m alum ina t e a ,
5CaOeSAlgOg and RCaOeAlgOg» are formed from Uio r e la t iv e l y stro n g b a se ,
CaOe end th e weak a c i d , AlyOge i s c o n sid e re d by them t o be in d ic a tiv e t h a t
h y d r o ly s is o f th e s e a lu is in a te s should ta k e p la ce by i o n i s a t i o n In to a
r e l a t i v e l y s tr o n g ly b a s ic c o n s t i t u e n t end a w eakly a c id ic c o n s t i t u e n t .
They
found t h a t s o l i d BCsOe SAlgOg and SCnOeAlgOg, witeu e x tr a c te d w ith w ater evs-r
a p e rio d o f s e v e r a l months anti when th e s o lu tio n s were re p la c e d by f r e s h
w a ter e,t fre q u e n t i n t e r v a l s , y ie ld e d s o lid nseiuue# c o n s is tin g only o f hy­
drous a lu m in a , frost w hich th e y deduced t i e com plete hy d ro I y s ic o f th e a Iuatln a te s u n d er th e s e c o n d itio n s .
However, th e y did n o t r e p o r t w h e th er th e
amount o f a lm i n a re m in in g , in each case «as tlw same a s tlis amount o f slum i n s In th e o r i g i n a l sample o f a lu m ln a te •
I t i s th e re fo re im p o ssib le t o
d eterm in e from t h e i r p u b lis h e d d a ta w hether the o r ig in a l o a laiu s) a l m i e a te a
were c o m p le tely h y d ro ly se d to calciu m h y d roxide and hydrous alum ina o r
w h eth er th e y were o n ly p a r t i a l l y h y d ro ly sed to more b a s ic PoIu b la e.Ium ina te n w ith th e exo- »s a lum ina rem aining behind a t r e s id u e .
As p re v io u sly m entioned i n t h i s p a p e r, K e lls (16) found U ta t F-CaDeSAlgCgt
re a c te d w ith w a te r to form a m etes ta b Ie s o lu tio n o f CaOeAlgOj and Ca(OB)g,
from w hich h y d ra te d t r i e s leium a Ivuelnatc and h y d rated a lu a in a p r e c ip ita te d
on sta n d Inge
I t l a s i g n i f i c a n t t h a t , d u rin g th e co u rse o f th e secondary
p r e c i p i t a t i o n r e a c tio n , th e Itydroxy 1 -io n c o n c e n tra tio n oi th e s o lu tio n
j imse s u b s t a n t i a l l y in c r e a s e d , even th o u g h th e c o n c e n tra tio n o f t o t a l d i s ­
so lv ed I i r n was m arkedly re d u c e d .
D uring th e seco n d ary r e a c tio n , i t was
n e c e s sa ry t h a t p a r t o f th e lim e , which o r i g i n a l l y e x is te d i n th e s o lu tio n
i n a n uneoiiibined s t a t e , combined w ith CaOeAl2 O3 t o form th e p r e c ip ita te d
SCaOeAl2 Og eXli2O.
These r e s u l t s in d ic a te t h a t th e fo rm a tio n o f r e l a t i v e l y
h ig h ly io n is e d calciu m hydro x id e and a w eakly Io n ise d a c id o r a c id s a l t
by h y d ro ly s is i s n o t th e o n ly p o s s ib le e x p la n a tio n f o r th e h ig h pH v a lu e s
observed in such s o l u t i o n s .
i t .s b y i leved t h a t th e above d is c u s s io n len d s credence t o an assum ption
by th e w r i t e r t h a t , in th o se oases where b o th fre e Ume and lim e combined
w ith alum ina e x i s t in s o lu t i o n , th e f r e e lim e may w e ll be th e c h ie f c o n t r i ­
b u to r t o th e h ig h pH v a lu e s o f such s o l u t i o n s , b u t t h a t io n is a tio n o f a
h y d ra te d d is s o lv e d calciu m &lum inate may a ls o be a c o n tr ib u tin g f a c t o r .
In th o s e e a s e s where o n ly combined lime e x i s t s in s o l u t i o n , a s was found
w ith su g ar e x t r a c t s o f SCaOeSAlgO3 in th e p r e s e n t i n v e s t ig a ti o n and as was
found in th e c ase o f e y g ar e x tr a c ts o f th e calcium s i l i c a t e s in p rev io u s
unpuLlis.-tod work by th e w r i t e r , th e e n t i r e h y d ro x y l-io n c o n c e n tra tio n must
came from i o n i s a t i o n r a t h e r th a n h y d ro ly s is o f th e h y d ra te d d is s o lv e d com­
p ounds.
I t i s b e lie v e d t h a t th e fo rm a tio n o f h y d ro x y l ions by i o n i s a t i o n o f d i s s o l ­
ved h y d ra te d a lum inate can tie i l l u s t r a t e d in th e fo llo w in g m an n eri
hoBocalcium a la m in a te , CaOeAl2 O3 , as found by Wells (1 5 ) t o e x i s t
in w a te r s o lu tio n s from BCaOeSAl2O5 and o th e r calciu m alum ina t e e .
- 47 -
i s a complex m olecule w ith th e A1-atoms undou b ted ly p la y in g the
o o o rd in a ti; g r o l l .
The fo rm a tio n and s t r u c t u r e of t h e u n i t CaO*
AlgOg group oar. be d e p le te d a eo o rd io g t o th e Lewis th e o ry o f
v a len c e (6 ) as fo llo w s*
(III)
(OaOsAl2 O5 )
By f u r th e r a d d itio n s o f CaOt a lu m in a te s o f in c re a s in g b a s i c i t y
could be i l l u s t r a t e d •
However, th e B tanoosloiue a lu s ln e te
s tr u c tu r e a d e q u a te ly s e rv e s th e p r e s e n t purpose i f i t I s borne
in mind t h a t t h i s r e p re s e n ts only th e b a eio s tr u c tu r e o f th e
ooBiourd and t h a t each Al-Btom 1» p ro b a b ly e u rrounded by s ix
0»aton$ In the c r y s t a l l a t t i c e ,
A lum lnate m olecules c o n ta in in g
mere th a n one Al,.Og group In th e b a s ic s tr u c tu r e can n o t be s a t i s ­
f a c t o r i l y i l l u s t r a t e d on paper by means o f th e lew is p i c t u r e .
The above s tr u c tu r e f o r AL-O5 is b e lie v e d to be a re a so n a b le
r e p r e s e n ta tio n o f t h a t compound, by re a so n o f th e am p h eterIc
n a tu re o f i t s h y d r a te .
T hus, h y d rated a lumina oan be p ic tu re d
ac fo llo w s , a c c o rd in g t o th e Lewis Theory*
m
From whioh H-I one and (A lO g)-Ions o r (OH)-Ione and A 1-ions may
r e s u l t , depending on w h eth er i o n is a tio n ta&es p la c e a t “A" o r
bB ".
*
46
»
th e e I e p I e e t b y d re te o f iaonoc»loiu» e lu » d K * te, t h a t I s ,
(^0*A lg0ge% 0 , CMfcii re e e e m b ly be p ic tu re d a s follow **
H
Ca
where ttw hydroxyl io n lroos th e w a te r i s a tta c h e d t o th e
C a-ato s a od th e hydrogen io n from th e w a ter ie a tta c h e d
t o one o f t i # Al-atome th ro u g h act oxygen lin k a g e *
The groups surrounded by d o tte d Iln e e in th e form ula immedia­
t e l y above 1» th e b a s ic a lum lnat# group and i t k b e lie v e d t h a t
t h i s group B ust be o on#idered a s a w eakly a c id ic c o n s ti tu e n t in
such a compound*
Ga th e o th e r b an d , t i * -C a : 0 . M group im­
m e d ia te ly above i t must be c o n sid e re d r e l a t i v e l y s tr o n g ly
b a s ic , from s liie li i t fo llo w s U iat i o n i s a t i o n o f t h i s l a t t e r
group a t wA" t o g ive a h y d re x y l-lo a must be s tr o n g e r th a n
i o n i s a t i o n o f tiie a lum inate group a t "B* t o g iv e a hydrogen
ion*
T h e re fo re , i f th e above i s a re a so n a b le r e p r e s e n ta tio n
o f a c t u a l c o n d itio n s , i t i s to be e x p e c te d t h a t c o n s id e ra b le
h y d ro x y l-io n c o n c e n tr e tio n can a r i s e in such s o lu tio n s sim ply
by I o n is a tio n o f th e h y drated a lu m in a te •
-
49
-
B - N ature o f S o lu tio n s o f Cennnt Compounds.
P h i l l i p s (11) hfts s tu d ie d th e n a tu re o f s o lu tio n s o f SCaO-AlgOg in w ater
uno r e p o r ts t h a t a etr a il amount o f th e alum inat.e goes in to t r u e s o lu tio n
b u t t h a t most o f t h e a lu s d n a te goes in to c o l l o i d a l s o l u t i o n .
The r e s u lts
he o b ta in e d w ith SCaO-AlgOg can be re a so n a b ly ex p ected t o a p p ly in g e n e ra l
a l s o f o r o th e r c alc iu m a lum inate s o l u t i o n s .
The phenomenon o f th e fo rm atio n o f g e la tin o u s p r e c i p i t a t e s from e x tr a c ts
from th e cement compounds s tu d ie d in th e p re s e n t i n v e s t i g a t i o n , and as
n o ted by o th e rs in th e case o f w ater s o lu tio n s o f th e compounds, i s p ro ­
b a b ly a s s o c ia te d w ith th e a t l e a s t p a r t i a l l y c o llo id a l n a tu re o f th e ex ­
tra c ts .
The pronounced " s u p e r- s a tu ra te d * c o n d itio n o f th e s e e x t r a c t s ,
can h a rd ly be ex p ected o f e n t i r e l y tr u e s o l u t i o n s .
F u r th e r , th e speed
w ith which th e p r e c i p i t a t e s form ln d lc s te s more a p ro c e ss o f g e la tio n o r
c o a g u la tio n th a n o f p r e c i p i t a t i o n from tr u e s o l u t i o n s .
F u r th e r , th e slow
r a te o f h y d ro ly s is noted i n t h e o r i g i n a l e x t r a c t s from BCaOAlgOg, which
co n tin u ed to ta k e p la ce even a f t e r c l e a r e x t r a c t s were o b ta in e d , in d ic a te d
t h a t th e i n i t i a l s o lu tio n p ro c e ss was p ro b a b ly fu n d am en tally c o l l o i d a l in
n a tu re .
F in a l l y , th e v e ry g e la tin o u s n a tu re o f th e p re c ip ita te ® is in d i­
c a tiv e o f c o l l o i d a l p r o c e s s e s ,
how ever, tim e and s u ita b le equipm ent were
n o t a v a ila b le d u rin g th e p re s e n t in v e s t ig a ti o n f o r an a d eq u a te stu d y o f
c o l l o i d a l phases t h a t m ight be p re s e n t in th e v a rio u s e x t r a c t s and s o lu ­
ti o n s s tu d ie d .
The d is c u s s io n s th ro u g h o u t t h i s p ap er have been concerned c h ie f ly w ith two
ty p e s o f r e a c tio n s , f i r s t , th e i n i t i a l r e a c tio n o f s o lu tio n o f th e p a r t i ­
c u l a r compound in th e su g a r s o lu tio n e n d , n e x t, th e seco n d ary re a c tio n o f
- 60
p r e c i p i t a t i o n o f s o lid phase from th e s e e x t r a c t s which were s » te s ta b le #
In th e case o f th e I n i t i a l r e a c tio n , th e r e was no ev id en ce e x c e p t f o r th e
c a lc iu m o x id e -s u g a r s o lu tio n s t h a t an e q u ilib riu m p o in t was e v e r reached
betw een s o lu tio n and s o lid p h a s e .
T his i s in d ic a tiv e t h a t th e I n i t i a l re ­
a c ti o n o f s o lu tio n Ie p rim a rily c o l l o i d a l In n a tu r e , b e in g more a p ro c e ss
o f c o l l o i d a l d is p e r s io n o r p e p tiz a tio n th a n o f tr u e s o l u t i o n .
On th e
o th e r h an d , i n th e seco n d ary r e a c tio n o f p r e c i p i t a t i o n , d e f i n i t e e q u i l i ­
brium p o in ts were a tta in e d o r in d ic a te d betw een s o lu tio n and s o lid ph ase,
a s evidenced by th e tendency o f e ac h m e ta sta b le e x tr a c t to go to a p o in t
o f c o n s ta n t com position*
The secondary r e a c tio n th e r e f o r e ap p ears t o in ­
v olve a t r u e s o lu tio n in e q u ilib riu m w ith a g e la tin o u s s o lid p h a se , which
would n e c e s s ita te t h a t p a r t o f th e m a te r ia l t h a t o r i g i n a l l y e n te re d th e
e x tr a c ts in th e c o l l o i d a l s t a t e be c o n v erted to th e m o le c u la r s t a t e .
A f u r t h e r p o in t w Ioh must be borne i n mind w h ile c o n s id e rin g th e p o s s ib le
n a tu re s o f th e s o lu tio n s s tu d ie d In th e p r e s e n t in v e s t ig a ti o n i s t h a t o f
c alc iu m a la m in a tes and dCaO+AlgOg"FegOg a r e h ig h ly complex eompouuds and
t h a t t h e i r in d iv id u a l m olecules a re n e t lim ite d In dim ension t o th e s iz e s
re p re s e n te d by th e h y p o th e tic a l form ulae used i n t h i s p a p e r.
In d e a lin g
w ith su ch compounds, th e m a tte r o f d i f f e r e n t i a t i n g betw een tr u e m olecules
and c o l l o i d a l p a r t i c l e s is p u re ly a
a t t a r o f s e l e c t i n g an a r b i t r a r y dimen­
s io n above o r below which a p a r t i c u l a r a g g re g a tio n f a l l s in to one o r th e
o th e r c l a s s .
C e r ta in ly i t i s to w e x p ec te d t h a t one c l a s s w i l l e x h ib it
t o a c o n sid e ra b le degree th e same ch em ical p r o p e r tie s a s th e o th e r .
Based on th e s e c o n s id e r a tio n s , i t i s th e o p in io n of th e w r i t e r t h a t a sh arp
d i f f e r e n t i a t i o n betw een t r u e s o lu tio n s and c o l l o i d a l s o lu tio n s in th e p re -
• 51 **
a « n t i n v e s t ig a ti o n i s n e i t h e r p o s s ib le nor n e c e s sa ry t o a d e q u a te ly i n t e r ­
p r e t th e r e s u l t s •
62 C»
S U w m riea tio n o f H eacticw **
S e r ie s I .
The r e s u lt* o b ta in e d frc® t e a t * o f S e rie s I w ith oaloiusa oxide
a re o f v a lu e i n th e p r e s e n t in v e s t ig a ti o n p r im a r ily f o r com parison w ith
r e s u l t s o b ta in e d in th e o th e r s e r i e s .
The f a c t t h a t lim e -e u p a r s o lu tio n *
show d e crea se d o p tic a l r o ta to r y power w ith in c re a s e d c o n c e n tr a tio n of d i e so lv ed lime i* c o n sid e re d u s e f u l in d e te rm in in g w hether o r n o t calcium
hydroxide has been lib e r a te d by h y d ro ly e ia from cement compounds i n su g ar
s o lu tio n *
The phenomenon o f in c re a s e i n th e a p p a re n t s o l u b i l i t y of c a l ­
cium hydroxide i n s u g a r s o lu tio n i n th e p re sen c e o f in c re a s in g amounts o f
th e s o lid phase should be a n i n t e r e s t i n g s u b je c t fo r fu tu r e i n v e s t ig a ti o n .
S e rie s 2*
Alimiinum hydroxide i s to o weak a base to form sue r a te compounds,
a t l e a s t a t th e low h y d ro x y l-io n c o n c e n tra tio n e x is t in g in w ater s o lu tio n s
c o n ta in in g o n ly d is s o lv e d s u g a r and h y d ra te d alu m in a.
e r ie a a * The r e s u l t s o b ta in e d from t e a t s o f S e rie s 5 w ith BCaOeSAlgO3
in d ic a te t h a t th e r e a c tio n s in v o lv ed may be re p re se n te d a s fo llo w s 1
I*
Bolow e o n o e n tr a tio n s where secondary p r e c i p i t a t i o n s t a r t s b e fo re
i n i t i a l s o lu tio n i s co m p lete, th e BCaOeSAlgOg goes c o m p letely
i n t o s o lu tio n w ith o u t fo rm a tio n o f calcium h y d ro x id e by hy­
d ro ly s is .
The form o f th e i n i t i a l s o lu te can be e i t h e r h y d rated
BCaOeSAlgO, o r a more b a s ic h y d ra te d a lum inate p lu s d is s o lv e #
h y d ra te d a lu m in a, th e mol r a t i o o f w hich m ixture i s th e same
as t h a t o f BCaOeSAlgOg.
2.
E x tra c ts c o n ta in in g more th a n a p p ro x im a te ly 0 .228 g o f t o t a l
d is s o lv e d calciu m oxide and alu m in a p e r 100 ml a r e me t e s t a b l e
o r " * u n e r - a a tu r a te d " .
Secondary p r e c i p i t a t i o n ta k e s p la ce
from 8uoh e x t r a c t s w ith o u t fo rm atio n o f calcium hydroxide by
• 65
h y d ro I y s is #
The s o lu tio n phase approaches a c o n s ta n t com­
pos i t I on w ith th e f i n a l s o lu te p ro b a b ly having th e fo rm u la ,
ZCaOeAlgOg, o r some m u ltip le th e re o f#
5#
The p r e c i p i t a t e from th e e x t r a c t s , w ith a mol r a t i o (CaO to
AlgO8 ) o f a p p ro x im a te ly 4*8, I s assumed t o c o n s is t o f a
h y d ra te d a lu m in a te , o th e r th a n SGaOeSAlgOg o r SCaOeAlgOg,
w hich i s s ta b le in th e p resen ce o f s u g a r s o l u t i o n , p lu s pos­
s i b l y h y d rated alum ina*
BCaOeSAlgQg and SCaOe AlgOg a re
e lim in a te d as p o s s i b i l i t i e s b ecau se o f t h e i r d em o n strated
in s ta b ilitie s .
Ko o th e r a lu m in a te a known to e x i s t i n th e
anhydrous system , CaO-AlgOj;, comply w ith th e re q u ire m e n ts o f
a mol r a t i o o f 4*3 i n th e p r e c i p i t a t e s w ith o u t f r e e calciu m
hydroxide*
However, numerous o th e r calciu m a lum lnat e a ,
m eeting th e re q u ire m e n ts o f th e co m p o sitio n o f th e p r e c ip i­
t a t e s o b ta in e d i n th e p re s e n t c a s e , can e x i s t In th e sy stem ,
CaO-AlgOg-HgO#
In view o f th e f a c t t h a t th e b a s ic form ula
o f th e s o lu te i n th e e x tr a c ts a t f i n a l e q u ilib riu m i n probab­
ly ECaOeAlgOgeXHgO, a a lm lla r b a s ic form ula f o r th e calcium
alu m in a te i n th e p r e c i p i t a t e s i s l o g i c a l .
In t h i s c a s e , th e
p r e c i p i t a t e a ls o c o n ta in s h y d ra te d a lu m in a.
4.
The fo llo w in g e q u a tio n i s b e lie v e d t o s c h e m a tic a lly re p re s e n t
th e r e a c tio n s Involved *
SCaOeSAlgOg ( s o lid ) + XHgO + (S u g ar)
SCaOeSAlgOgeXEgO ( c o l l o i d a l and t r u e s o l u t i o n ) - — »—
ECaOeAl2OgeXHgQ ( tr u e s o lu tio n ) + ECaOeAlgOgeXHgO ( g e l) +
AlgOgeXHgO ( g e l ) .
64 where "x* d en o tes any undeterm ined number o f m olecules
o f w a te r o f h y d r a tio n .
6«
In th e ease o f e x tr a c ts from BCaOeSAl2O5 a lo n e , h y d ro x y l-io n
c o n c e n tra tio n s a re not reached which a re s u f f i c i e n t l y h ig h
to cause h y d ro ly s is o f th e compound to t i e e x te n t o f l i b e r ­
a t i o n o f oaleiU B h y d ro x id e .
The maximum pH v a lu e s reached
In th e p r e s e n t in v e s tI g a t ion accom plished o n ly th e h y d ro ly s is
o f th e compound t o a more b a s ic a lu m ln a te p lu s h y d ra te d
a lu m in a .
However, t h i s does n o t p re c lu d e th e p o s s ib le hy­
d r o ly s is o f t h i s compound to th e e x te n t o f l i b e r a t i o n o f
f r e e calciu m hydroxide i n o ases where h ig h e r pH v a lu e s
th en 11.06 o b ta in .
Such c a s e s as m ix tu res o f BCaOeSkl2O5
w ith SCaQeAl5 O5 , a l k a l i s , o r la rg e amounts o f f r e e calcium
o x id e , o r th e ease o f BCaOeSAl2 O5 in P o rtlan d cem ent, m ight
r e s u l t in com plete h y d ro ly s is o f th e BCaOeSAl5 O5 by su g a r
s o lu tio n ; how ever, th e s e p o s s i b i l i t i e s were no t in v e s tig a ­
te d ,
S e rle a 4 .
K eaults o b ta in e d from in v e s t ig a ti o n s o f th e re a c tio n * betw een
s u g a r s o lu tio n and ^CaOeAl2O5 eFe5O5 a re n o t s u f f i c i e n t l y c o n c lu s iv e ,
because of u n c e r t a i n t i e s as to th e t r u e co m p o sitio n o f th e m a te r ia l u se d ,
to p erm it o f su m m a risatio n .
Undyr th e s e c o n d itio n s , th e r e s u l t s a re o f
v a lu e only in c o n n e c tio n w ith p o s s ib le f u tu r e s tu d ie s o f th e s e r e a c tio n s .
S e r ie s 6 .
The r e s u l t s o b ta in e d from t e s t e o f S e rie s 5 w ith BCaOeAl5O5
in d ic a te t h a t th e r e a c tio n s In v o lv ed may be re p re se n te d a s fo llo w s 1
I.
Amounts o f SCaGeAl5O5 up t o 2 .2 8 g p e r 100 ml w ent co m p lete-
56 —
Iy In to s o lu tio n p r i o r t o i n i t i a t i o n o f se c o n d -ry p r e c ip i­
t a t i o n (w ith in two m in u te s) and i t is lo g i c a l l y assumed
t h a t I n i t i a l s o lu tio n o f la r g e r amounts o f th e compound
would go t o co m p letio n a t t h e same tim e t h a t seco n d ary p re ­
c ip ita tio n is
2*
Ur
derw aye
H y d ro ly sis o f th e SCaOeAl2 Og t o th e e x te n t o f l i b e r a t i o n
o f calciu m hydroxide s t a r t s im m ediately upon e n t r y o f th e
compound i n t o s o l u t i o n , th e o n lcium hydroxide th e n combin­
in g w ith d is s o lv e d s u g a r t o form s u e r a t e s •
3#
Ix tra o ta c o n ta in in g 0*220 g o r more o f t o t a l d is s o lv e d
calciu m oxide and alum ina p e r 100 ml a re m e ta sta b le o r " su p e r­
s a tu r a te d " * Secondary p r e c i p i t a t i o n p ro g re sse s more ra p id ly
th a n in th e case o f e x tr a c ts from 6Ca0»3Alg0g,
The com posi­
t i o n o f th e s o lu tio n phase a t e q u ilib riu m ia dependent on
th e amount o f s t a r t i n g m a ts d a l, th e amounts o f d is s o lv e d a l ­
umina and c alc iu m oxide i n th e e x t r a c t s a t e q u ilib riu m going
to a maximum and th e n d e c re a sin g w ith in c re a s in g s t a r t i n g
amounts o f th e compound.
The f i n a l s o lu te s in t h e e x tr a c ts
p ro b ab ly consist o f f r e e aluminum hydroxide p lu s c alc iu m hy­
d ro x id e combined w ith su g ar as s u e r a t e s .
4.
The p r e c i p i t a t e s from th e e x tr a c ts a re assumed to c o n s is t
c h ie f ly o f h y d r-te d alum ina p lu s t r i e s Ie Iusi sue r a t e .
Kew-
e v s r , th e p o s s i b i l i t y o f th e e x is te n c e o f a s o lid calciu m
a lum inate mors s ta b le w ith re s p e c t to th e f i n a l e x t r a c t s
th a n o a loium Quorate was n o t in v e s t ig a te d .
6«
Tb* fo llo w in g e q u a tio n s a re b e lie v e d t o s c h e m a tic a lly
r e p r e s e n t th e r e a c tio n s in v o lv e d i
SCaOeAlgOg ( s o lid ) -r HgO —* - Ca(0H}g ( s o lu tio n ) +
Al(OH)s ( s o lu tio n ) ♦ Al(CE)5 ( g e l)
Ca(OH)2 ( s o lu tio n ) + C12% 2°11 (®o lu tiB ») —
CaOeC12H22O11eI^O ( s o lu tio n ) + ZCaOeC12H^g O11eZH2O ( s o lu tio n )
SCaOeC12HggO11eSHgO ( s o l i d ) .
6.
The h ig h r e a c t i v i t y o f SCaOeAlgOs w ith su g a r s o lu tio n i s con­
s id e r e d t o be due t o th e h ig h hydroxyI - io n c o n c e n tra tio n s
r e s u l t i n g i n th e e x t r a c t s .
The re v e rs e o f t h i s i s n o t the
e a s e , because th e secondary p r e c i p i t a t i o n r e a c tio n s i n th o se
t e s t s where th e pH v a lu e s w ere m easured caused no change in
h y d ro x y l-io n c o n c e n tr a tio n .
I n th o s e t e s t s where th e pE
v a lu e s of th e f i n a l e x tr a c ts could n o t be measured because
o f th e b roken g la s s e l e c t r o d e , th e r e was evidence t o in d ic a te
t h t th e h y d ro x y 1 -io n c o n c e n tra tio n s d ecreased r a t h e r th a n
in c r e a s e d .
- 6? -
X.
ACOOSLEDSEMESTS
Th* w r i t e r wiehea t o a oknot;ledge th e r e Iu ab Ie a s s is ta n c e and ad v ice
giv en th ro u g h o u t th e course o f t h i s i n v e s t ig a ti o n by D r. Hay T o o d riff
o f th e S t a f f o f th e C hew istry D epartm ent a t Montana S ta te C o lle g e .
§3 «»
X I.
UTlKtTVHS CITED AID OOBSULFED
(1)
F l i n t arid B a te a , Rock P ro d u c ts , G e t. 1940, p46.
(2 )
P e rd , P. C. A. Sead-A nnual ffcport o f Eov. 1959, Appendix 2 .
(3 )
K le in and P h i l l i p * , T ech. B tp er Ko. 4 8 , M t . Bureau o f S ta n d a rd s .
(4)
L a p ic , f r a v , I n a t , p e tr o g . a c a d . e e l . ti. 8 . S . S . , f,o. 14, B -18
(1 9 5 9 ) i K hiB , R e f e r a t . Z h u r., So. 7 , 17-18 (1 9 3 9 ).
(6)
In re h and Bogue, J . Fhye. Chem., J51, 1627-46 (1 9 2 7 ).
(6 )
Lewie, V alence and the S tr u c tu r e o f Atoms and M o lecu les, Reinhold
Bib I . C o ., (1 9 2 5 ).
(7 )
M o K sn x ie, The Sugar* and T h e ir Sim ple D e riv a tiv e s , J . B. L ip p in c o tt
C o ., P h ila d e lp h ia , p g s , (1 9 1 4 ).
(8 )
F e rrL m n , Eng. Mews R ecord, 95 , 6 6 9-672, (1 9 2 4 ).
(9)
M errim an,
took P ro d u c ts , March 1958.
(10)
m rrirn a n , Cevmtt (P ap er Mo. 5 0 8 ), World Fkigr. C ongreee, Tokyo (1 9 2 9 ).
(11)
P h i l l i p s , J . k m r , C eraaio S e e ,, £ , 706 (1 9 1 9 ).
(12)
P o rtla n d foment S p e c if ic a tio n C-S5S, Board of Water S u p p ly , C ity
o f New Y ork.
(13 ) S e i d e l l , S o l u b i l i t i e e o f In o rg an ic and l o t a l O rganic Compound*,
S Jld., V ole I , ppS 15-317, 1>. Van Kostr&nd C o ., New York (1 9 4 0 ).
(14)
A c iab e rg , B u ll. e o e . e h im ., ( 3 ) , 2 1 , 776 (1 8 9 9 ).
(16)
v e il* , J . Be*. N. B. S . , 1_, 961 (1 9 2 8 ).
(16)
W iley, Rook P ro d u c ts , J a n . 1941, 126*
MONTANASTATE UNIVERSITYLIBRARIES
3
lib.
N3T8
n6UUr
co p. 2
DATE
81393
N iven, W. W.
R e a c tio n s o f su g ar
s o lu tio n on c e r t a i n c a l ­
cium a lu m in a te s and
calciu m a lu m in o - f e r r ite
ISSUED TO
81393
*3*8
N644r
MAJN Lia
til*
762 1001 5093 5