I

NASA TECHNICAL TRANSLATION

NASA TT F-11,620

HYDRATED CALCIUM" PEROXIDES

de Forcrand

T r a n s l a t i o n of "Sur les peroxydes de calcium h y d r a t e s "

Comptes Rendus de 1'Academie des S c i e n c e s , S e r i e s -Thermochimie, Vol. 80, No. 20, pp. 1308-1311, 1900
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NATIONAL AERONAUTICS AND SPACE ADMINISTRATION

WASHINGTON, D. C. 20546
MARCH 1968

NASA TT F-11,620
HYDRATED CALCIUM PEROXIDES

de Forcrand
ABSTRACT. Four experiments were conducted on h y d r a t e d calcium
p e r o x i d e s and t h e r e s u l t i n g f l u i d was t e s t e d f o r i t s s e p a r a b i l i t y w i t h v a r y i n g numbers of f i l t e r s , and t h e c h a r a c t e r i s t i c s
o f t h e p r e c i p i t a t e were compared. E x t e n s i v e c o n c l u s i o n s on t h e
r e s u l t s are d i s c u s s e d , as i s t h e a u t h o r ' s o b j e c t o f f u t u r e
research.
/1308

Hydrated calcium p e r o x i d e s p r e c i p i t a t e when hydrogen p e r o x i d e a c t s on

s o l u t i o n s s a t u r a t e d w i t h lime i n e x a c t l y t h e same way as when b a r i t e o r
s t r o n t i a i s used.
I

1 . . The e f f e c t o f 1 / 2 H202 ( l l i t ) on CaO ( S o l i t ) .

Temperature

20'.

Final s t a t e i n calorimeter
0.666 CaOl. 732 p r e c i p i t a t e + 0.334 CaO

Heat l i b e r a t e d :

2.

1.04

d i ssolved,

[Appears t o b e something m i s s i n g - - T r . ]

/1309

Thus, a l l c o r r e c t i o n s made: + 6ca1, 877 f o r Ca02 h y d r a t e d p r e c i p i t a t e .

T h i s s u b s t a n c e forms an extremely f i n e and l i g h t powder which remains i n
s u s p e n s i o n f o r a long w h i l e and which g i v e s t h e l i q u i d t h e appearance o f
m i l k . The l i q u i d i s c l a r i f i e d o n l y slowly and with g r e a t d i f f i c u l t y a f t e r
p a s s i n g through s e v e r a l f i l t e r s , and most o f t h e P r e c i p i t a t e remains a t t a c h e d
t o t h e p a p e r p o r e s . However, I have succeeded i n c o l l e c t i n g enough of i t t o
perform an a n a l y s i s , which y i e l d e d ( a f t e r d r y i n g on porous p l a t e s )

Gaol. 842

+ 2.31 H20.

A l . 1 t h e s e ' c h a r a c t e r i s t i c s -- t h e appearance and p r o p e r t i e s o f t h e

p r e c i p i t a t e , i t s composition and formation h e a t - - a l l showed t h a t we are
d e a l i n g w i t h a compound which i s h i g h l y d i f f e r e n t from t h o s e o b t a i n e d
p r e v i o u s l y w i t h B a O and SrO (+ 25 c a l , 497 and + 26 c a l , 576 and a h y d r a t i o n
s t a t e o f 8 t o 9 H20).

In t h i s p a r t i c u l a r case, t h e s e d i f f e r e n c e s do n o t a p p e a r t o b e due t o
t h e more e l e v a t e d t e m p e r a t u r e used i n t h i s t e s t (+ 2 0 ) , because I c a r r i e d
o u t a n o t h e r s e r i e s of t e s t s a t +14O which y i e l d e d :
The f i n a l s t a t e : 0.647 Ca01.754 p r e c i p i t a t e + 0.353 C a O l f o4 d i s s o l v e d .

Heat l i b e r a t e d : + 2ca1, 940, o r , a f t e r c o r r e c t i o n : + 6 c a l , 899.

I n t h e s e l a t e r t e s t s , I immediately added d i s s o l v e d H2C12, which y i e l d e d
*Numbers i n t h e margin i n d i c a t e p a g i n a t i o n i n t h e f o r e i g n t e x t .

+25ca1,128, o r , a f t e r c o r r e c t i o n s : +21ca1,425 f o r t h e e f f e c t o f t h e d i s s o l v e d
H C 1 on t h e h y d r a t e d Ca02 p r e c i p i t a t e .
2 2
The t o t a l +6ca1,899 + 21ca1,425 = +28ca1,324, a number which i s very
c l o s e t o +27cal,960 ( n e u t r a l i z a t i o n h e a t ) , which i s a c o n t r o l .
11.

The e f f e c t o f H20 ( 2 1 i t , 5 ) on CaO ( 5 0 1 i t ) .

F i n a l s t a t e : 0.908 CaO

1.96

p r e c i p i t a t e + 0.092 CaO

Temperature 14.
2.4

dissolved.

Heat l i b e r a t e d : +6ca1,163, o r , a f t e r c o r r e c t i o n s : +6ca1,668, a number

which i s i d e n t i c a l w i t h t h e p r e c e d i n g .
The h y d r a t i o n s t a t e s h o u l d b e t h e same, because ;he
t h e same c h a r a c t e r i s t i c s .

precipitate offers

In one experiment, H2C12 d i s s o l v e d y i e l d e d +22ca1,062, o r a f t e r c o r r e c t i o n s ,

+21ca1,608 (6ca1,668 + 21ca1,608 = + 28ca1,276).
111.

The e f f e c t of 2H202 ( S l i t ) on CaO ( 5 0 1 i t ) .

Temperature + 14.5.

F i n a l s t a t e : 0.862 Ca02. 12 p r e c i p i t a t e + 0.138 C a O g S 4 d i s s o l v e d .

Heat l i b e r a t e d : +7ca1,975, o r +7ca1,523 f o r Ca02. 12.

Thus , Ca02. 12 may be c o n s i d e r e d a mixture o f d i o x i d e and t r i o x i d e :

0.88 Ca@2 + 0.12 Ca03.

In a d d i t i o n , because t h e p r e c e d i n g experiments y i e l d

+6ca1,815 as an average f o r Ca02, t h e r e s u l t i s t h a t t h e t r a n s f o r m a t i o n of

l i b e r a t e s +6ca1,735, or about t h e same q u a n t i t y o f h e a t
3
as i s l i b e r a t e d when d i s s o l v e d CaO i s transformed i n t o Ca02 p r e c i p i t a t e .

t h e Ca02 i n t o CaO

The t r i o x i d e would t h e r e f o r e b e more s t a b l e t h a n i n t h e case o f b a r i t e .

The h y d r a t i o n s t a t e o f t h e p r e c i p i t a t e i s , i n a d d i t i o n , t h e same as t h a t
i n p r e c e d i n g t e s t s , s p e c i f i c a l l y 2.07 H20.
IV.

The e f f e c t o f 3 H202 ( 7 1 i t , S ) on CaO ( 5 0 1 i t ) .

Temperature +13

and +14.
F i n a l s t a t e : 0.856 Ca02-09 p r e c i p i t a t e + 0.144 CaO15.

dissolved.

Here t h e phenomena change completely. The p r e c i p i t a t e g a t h e r s r a t h e r

q u i c k l y i n t h e form of p e a r l y lamella having t h e same appearance as h y d r a t e s of /1310
barium and s t r o n t _ i m p e r o x i d e . I t s e p a r a t e s r a p i d l y and c o m p l e t e l y , even
with a s i n g l e f i l t e r .

The h e a t l i b e r a t e d i s a l s o q u i t e d i f f e r e n t : + 22ca1,899, o r , a f t e r
c o r r e c t i o n s +24ca1,666 f o r Ca02-09. According t o t h e p r e c e d i n g , approximately
t h e same number can b e allowed f o r a h y d r a t e d Ca02 p r e c i p i t a t e under t h e same
conditions.
2

F i n a l l y , t h i s s u b s t a n c e , c o l l e c t e d and d r i e d i n t h e same manner as t h e

p r e c e d i n g s u b s t a n c e s were, has a composition o f Ca02.06 + 8.57 H20. Thus,

we a g a i n f i n d t h e h y d r a t i o n s t a t e a t 8 o r 9 H20 of t h e Ba02 o r SrO2 p r e c i p i tates.

As a c o n t r o l , H2C12 was immediately added a f t e r one o f t h e s e e x p e r i -

ments.

I found + 4.732, o r a f t e r c o r r e c t i o n s + 2ca1,911 f o r C U O ~ . ~ The

~ .

t o t a l +24.666

2.911 y i e l d s +27.577 ( i n s t e a d o f +27.960).

Then I r e p e a t e d t h e experiment with t h e same p r o p o r t i o n s o f lime (1 mol)

and hydrogen p e r o x i d e ( 3 mol) , b u t o p e r a t i n g a t + 2 0 , o u t s i d e t h e c a l o r i m e t e r .
The p r e c i p i t a t e i s p u l v e r u l e n t and f i l t e r s q u i t e slowly and i n c o m p l e t e l y w i t h
s e v e r a l f i l t e r s , and i t s composition i s CaO
1.94 +
H2'
F i n a l l y , one l a s t experiment was made t a k i n g 4H 0 f o r CaO and c o o l i n g
2 2
t h e l i q u i d s i n o r d e r t o reduce them t o t h e i n i t i a l t e m p e r a t u r e o f + l o o .
This experiment a g a i n y i e l d e d a p r e c i p i t a t e i n t h e form o f p e a r l y l a m e l l a
which r a p i d l y c o l l e c t e d and were s e p a r a t e d e a s i l y by a s i n g l e f i l t e r , and
which had a composition o f Ca02.02 + 7.62 H20. T h i s i s t h e same s u b s t a n c e

as i n t h e f i r s t experiments of I V .
From the p r e c e d i n g , i t f o l l o w s t h a t :
1. Through a m i x t u r e o f hydrogen p e r o x i d e s o l u t i o n s and b a s e s , lime
forms, as b a r i t e and s t r o n t i a , p r e c i p i t a t e s of h y d r a t e d p e r o x i d e s whose
s o l u b i l i t y i s g r e a t e r than t h a t o f strontium peroxides, b u t l e s s than t h a t
o f barium p e r o x i d e s .
2.
I n t h r e e c a s e s , t h e p r e c i p i t a t e s always c a r r i e d down p r o t o x i d e
h y d r a t e u n t i l t h e l i m i t o f 2 H202 molecules f o r one base molecule i s r e a c h e d ,

and t h a t t h e dosage o f t h e p r o t o x i d e i s g r e a t e r when t h e r e i s an excess

of t h e b a s e .

3. Between + l o o and +16', b a r i t e and s t r o n t i a y i e l d p r e c i p i t a t e s which

r e t a i n approximately 8 t o 9 H20, w h i l e t h e lime f u r n i s h e s a d i o x i d e w i t h
2 H 0 , which i s q u i t e d i f f e r e n t i n i t s appearance and i t s f o r m a t i o n h e a t .
2
4.

A t t h e same t e m p e r a t u r e s , lime y i e l d s a d i o x i d e of 8 o r 9 H20 when

we take t h r e e o r f o u r H202 molecules f o r one b a s e molecule.

5. When t h i s change i n t h e h y d r a t i o n s t a t e o f t h e calcium d i o x i d e
depends s o l e l y on t h e t e m p e r a t u r e , t h e n i n o p e r a t i n g a t +20 t h e e f f e c t of
3 H202 y i e l d s t h e h y d r a t e a t 2 H20. The c r i t i c a l t e m p e r a t u r e would t h e r e f o r e
be between 15' and 20'.
6.

The t h r e e h y d r a t e s a t 8 o r 9 H20 form and l i b e r a t e a c o n s i d e r a b l e

amount o f h e a t which i s q u i t e c l o s e :
3

Ca02...... + 24,666

7.

Ba02..

....

+ 25.497

Sr02

...... +

26.576

The a d d i t i o n o f 6 H20 l i q u i d t o t h e Ca02 +2 H 0 h y d r a t e t o change

2

i t i n t o a Ca02 + 8 H20 h y d r a t e y i e l d s + 24.666 -6.815, o r +17ca1,851, o r

I

+3cal p e r water molecule i f t h e f i r s t component i s a d i o x i d e h y d r a t e and

n o t a Ca02H2 + H202 combination, which I i n t e n d t o i n v e s t i g a t e .

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