I N O R G A N I C AND A N A L Y T I C A L C H E M I S T R Y

REACTION

OF

PEROXIDE

AND

Na2CO

3 9 1.5
T.
V.

P.
M.

H20

SODIUM
SOME

BICARBONATE

HYDROGEN

WITH

PROPERTIES

OF

COMPOUND

THE

Firsova,
Bakulina,

V. I. Sokol,
and N. N.

UDC 542.91+546.33'384.1+546.215
Stasevich

In the investigation of the interaction of p o t a s s i u m b i c a r b o n a t e with hydrogen p e r o x i d e at - l O - O ~ it

h a s been shown [1] that in the region of e q u i l i b r i u m c o n c e n t r a t i o n s of hydrogen p e r o x i d e f r o m 17-25% and
above, the only bottom p h a s e of the s y s t e m is the p e r o x o b i c a r b o n a t e KHCO4, analogous to that d e s c r i b e d
in [2-4]. The f o r m a t i o n of an additive compound of hydrogen p e r o x i d e and p o t a s s i u m c a r b o n a t e in the p r e sence of l o w e r hydrogen p e r o x i d e c o n c e n t r a t i o n s , o b s e r v e d by Kazanetskii [5], is a consequence of a s e c o n d a r y p r o c e s s of hydrolytic c o n v e r s i o n of the p o t a s s i u m p e r o x o b i c a r b o n a t e indicated above. In this w o r k
we studied the i n t e r a c t i o n of sodium b i c a r b o n a t e with hydrogen p e r o x i d e according to a p r o c e d u r e analogous
to that d e s c r i b e d e a r l i e r [1].
EXPERIMENTAL
A weighed sample of sodium bicarbonate was mixed with an excess of hydrogen peroxide (with a concentration of 40-60%) in comparison with the stoiehiometric amount. The mixing was performed at room
temperature and was accompanied by an absorption of heat. To reach a state of equilibrium, the mixture
was left for 24 h at 0% During this time completeness of the conversion of bicarbonate was ensured. Then
the solid phase was freed of the mother liquor by filtration. The precipitate was washed with alcohol and
ether and dried by purging with dry air or in a desiccator over a drying agent.
A precipitate was isolated from the filtrate with alcohol, the composition of which coincided with the
composition of the bottom phase and corresponded to the compound Na2CO 3 9 1.5 H202, as it follows from
Table i. The synthesis was readily reproduced; the compound possessed fairly good stability at room

~~
300

300

J/

200
/,r

]
,oot

~o. As~o

ml02
48
q0

~oo

. 8~o"

~[_.272~55"
F

20

15

30

Ill

#5

60

Time, rain

Fig. 1

15

30

Time, rain

q5

Fig. 2

Fig. 1, T h e r m o g r a m of the r e a c t i o n p r o d u c t of sodium b i c a r b o n a t e

and hydrogen p e r o x i d e at - 1 0 ~
Fig. 2. T h e r m o g r a m of Na2CO 3 9 1.5 H202.
N. S. Kurnakov Institute of G e n e r a l and Inorganic C h e m i s t r y , A c a d e m y of Sciences of the USSR.
T r a n s l a t e d f r o m I z v e s t i y a Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1941-1944, S e p t e m b e r ,
1968. Original a r t i c l e s u b m i t t e d J a n u a r y 5, 1968.

1850

TABLE 1. Data of Chemical A n a l y s i s of the Bottom P h a s e

and P r e c i p i t a t e I s o l a t e d f r o m the F i l t r a t e with Alcohol
I
Expt. No.

Found, %
T.,oc
0

2
3
4

9 o~

--10
--10
0
0

5
6

1"
2*

N~O

CO~.

38,50
39,28
39,11
39,17
31,38,

28,00
27,83

3%30

i5,10
18,37
i5,18
17,7t
28,06
i5,00
17,82
27,90
i5,05
18,59
39,71
i8,56
20,35
40,20
18,88
19,42
27,90
15,62
18,18
27,73
15,40
17,30
Calculated for Na~COs.1.5[I20a
28,00 [ 15:28 I 17,4~

was

obtained by salting out from

31,50

38,30
39,10

*The solid phase

with ethanol.

oact

'
I
H~O (by Phase composition
difference)/
t 3 Na2C0a.1,5H~O~
The same
n

} NaHCO~.H20
NaHCO~
Na2eOa. 1,5tt202
Na~CO3.1,5H~02

the filtrate

T A B L E 2. R o e n t g e n o m e t r i c Data f o r the C o m p o u n d
Na2CO 3 9 1.5 H20 2

V.W
V,W
V,W
V.W
S
S
S
V.S

d,A

4,55
4,12
3,89
3,67
3,37
2,92
2,70
2,55

s
reed
reed
v.s
v.s
s
w
s

Jt

d,A
2,41

2,27

W
S
W
W
W

2,14
i, 97
1,88
1,68
1,61
1,54

d,A.

d,A

1,48
1,40

w
s
med
reed
v.s
w
w
w

1,05
1,03
1,00
0,973
0,943
0,897
0,871
0,852

1,35
1,31
1,23
1,24

med

1,11

1,07

T A B L E 3. D i s p e r s i o n of t h e I n d i c e s of R e f r a c t i o n
of Na2CO 3 9 1.5 H20 2
N

Nio
N,n

Ng
TABLE

486

520

555

589

620

656

co

1,421
1,517
1,536

1,419
1,513
1,531

1,418
1,510

1,417
1,508
1,523

1,416

1,52"7

1.415
11504
1,518

1,403
1,487
1,497

1,506

1,520

4. Dispersion of the Indices of Refraction of N a 2 C O 3

L, n m

JVp

N,~
N~

48~

520

555

589

1,414
1,551
1,557

1,412
1,546
1,553

1,411
1,541
1,549

1,410
1,537
1,544

620

656

co

1,409

1,410
1,531
1,539

1,396
1,506
1,513

1,534
1,541

t e m p e r a t u r e . The s e s q u i p e r o x y h y d r a t e of s o d i u m c a r b o n a t e Na2CO 3 9 1.5 H20 2 w a s p r o d u c e d f o r the f i r s t

t i m e f r o m s o d i u m c a r b o n a t e in [6], a n d w a s l a t e r p r o d u c e d f r o m s o d i u m o i c a r b o n a t e [7-9]. M a k a r o v and
C h a m o v a , who i n v e s t i g a t e d the s y s t e m N a 2 C O 3 - H 2 0 2 - H 2 0 , d i d not d e t e c t t h i s c o m p o u n d [10].
In e x p e r i m e n t s at - 1 0 ~ (see T a b l e 1, e x p e r i m e n t s 5 and 6), the s o l i d p h a s e had a c o m p o s i t i o n t h a t
c a n be i n t e r p r e t e d a s a m i x t u r e of t h e f o l l o w i n g c o m p o n e n t s : NaHCO4.H20 - 49.30%1 NaHCO a - 30.10%;
Na2CO3"1.5 H20 2 - 17.15%1 H2O -- 3.45%, F i g u r e 1 p r e s e n t s t h e t h e r m o g r a m of t h i s m i x t u r e . The e f f e c t s
in t h e t e m p e r a t u r e r a n g e 4 5 - 1 0 2 ~ p e r t a i n to s o d i u m p e r o x o b i c a r b o n a t e m o n o h y d r a t e N a H C O r
[3]. T h e

1851

endothermic effect at 125-132 ~ is an effect of decomposition of the bicarbonate, while the small effects endothermic at 110 ~ and exothermic at 120 ~ - pertain to the removal of w a t e r and decomposition of the
carbonate p e r o x o h y d r a t e Na2CO 3 9 1.5 H20 2 respectively.
The t h e r m o g r a m of Na2CO 3 9 1.5 H202, containing no impurities (Fig. 2), is c h a r a c t e r i z e d by an exot h e r m i c effect of decomposition of the hydrogen peroxide of c r y s t a l l i z a t i o n at 110-140 ~ followed by an
endothermic effect of dehydration. Evidently the complete c o n v e r s i o n of sodium bicarbonate to the p e r o x o bicarbonate at - 1 0 ~ is prevented by the heterogeneous nature of the p r o c e s s and the low reaction rate,
while that at 0 ~ is prevented by the c o m p a r a t i v e l y low stability of sodium peroxobicarbonate NaHCO 4 9H20.
The data obtained are evidence of analogy of the p r o c e s s e s of interaction of p o t a s s i u m and sodium
with hydrogen peroxide, c h a r a c t e r i z e d by the formation of a peroxobicarbonate with the composition MHCO 4
(M = Na, K) at the f i r s t step, followed by its c o n v e r s i o n to the carbonate peroxyhydrate. This p r o c e s s can
be d e s c r i b e d by the following s u m m a r y r e a c t i o n s for the sodium salt:
NaHCOa + H202 ~ l'qaHCOt.H20
2 NaHC0~. HaO -+ Na2COa. t.5 H202 "-[-C02 + t.5 H20 + 0.2502

(1)
(2)

The lower the hydrogen peroxide concentration o r the higher the t e m p e r a t u r e , the m o r e probable reaction
(2) and the m o r e complete the c o n v e r s i o n of the peroxobicarbonate to the carbonate p e r o x y h y d r a t e . The
formation of p e r o x o e a r b o n a t e s with the composition MHCO 4 f r o m the bicarbonates and hydrogen peroxide
o c c u r s as a r e s u l t of nucleophilic substitution of the hydroxyl anion OH- by the hydroperoxyl anion HO~ of
hydrogen peroxide.
To c o n f i r m the individuality of the compound Na2CO3 9 1.5 H20 2, we studied some of its p r o p e r t i e s .
Table 2 p r e s e n t s the values of the interplane distances in c r y s t a l s of Na2CO 3 91.5 H20 2. X - r a y diffraction
study of the samples was p e r f o r m e d on URS-55 apparatus in copper radiation with a nickel filter in an
RKD c a m e r a . The relative line intensity was estimated visually.
The density of Na2CO 3 9 1.5 H202, d e t e r m i n e d by the p y c n o m e t r i c method in toluene, at 25 ~ is 2.129
g / c m 3. The compound Na2CO 3 1.5 H202 is obtained in the f o r m of c o l o r l e s s , r a t h e r large and w e l l - f o r m e d
c r y s t a l s in the f o r m of elongated p r i s m s . The c r y s t a l s of Na2CO3 9 1.5 H202_possess indirect and direct
extinction. In a conoscopic investigation, a distinct figure of a biaxial c r y s t a l is observed. All this p e r mits us to conclude unambiguously that c r y s t a l s of Na2CO 3 9 1.5 H202 belong to the monoclinic s y m m e t r y
group. The indices of r e f r a c t i o n of Na2CO 3 9 1.5 H202were determined by an i m m e r s i o n method. The data
obtained on the indices of r e f r a c t i o n and density were used to calculate the m o l e c u l a r r e f r a c t i o n of this
compound. The calculation was p e r f o r m e d according to the L o r e n t z - L o r e n t z formula:
Rm ~

M n2 - t
d n~-~-2

where n is the index of r e f r a c t i o n , a v e r a g e d and extrapolated to k~; d is the density of the substance; M
is the m o l e c u l a r weight.
The d i s p e r s i o n of the indices of r e f r a c t i o n was m e a s u r e d in m o n o c h r o m a t i c light at six wavelengths.
Extrapolation of the indices of r e f r a c t i o n to X~ was p e r f o r m e d according to the Wulf graphical method [11].
The r e s u l t s of the d i s p e r s i o n m e a s u r e m e n t are cited in Table 3.
The values of the indices of r e f r a c t i o n , extrapolated to ~ , were extrapolated according to the f o r mula: fi~ =~] NgNmNp. The value of ~r found f r o m this is 1.464, while the value of the m o l e c u l a r r e f r a c tion Na2CO 3 9 1.5 H202 is 25.24 c m 3.
To determine the r e f r a c t i o n of the hydrogen peroxide of c r y s t a l l i z a t i o n in this compound, it was
n e c e s s a r y to calculate the m o l e c u l a r r e f r a c t i o n of anhydrous sodium carbonate. In the l i t e r a t u r e [12, 13],
t h e r e were only data on the indices of r e f r a c t i o n and density of Na2CO 3, which we also used to m e a s u r e
the dispersion. The data on the d i s p e r s i o n of the indices of r e f r a c t i o n of Na2CO 3 a r e cited in Table 4.
The value found for ~
of Na2CO 3 is 11.71 c m 3.

according to the f o r m u l a cited above is 1.472, while the m o l e c u l a r r e f r a c t i o n

The r e f r a c t i o n of the hydrogen peroxide of c r y s t a l l i z a t i o n , calculated f r o m the difference between

the m o l e c u l a r r e f r a c t i o n s of Na2CO 3 91.5 H20 2 and Na2CO 3 and related to one molecule of H20 2, is 5.75 cm 3.
This value is in good a g r e e m e n t with the l i t e r a t u r e data for p e r o x y h y d r a t e s of sodium phosphates [14] and
for liquid hydrogen peroxide [15].
1852

CONCLUSIONS
i. In the reaction of sodium bicarbonate with 40-60% hydrogen peroxide at -I0 ~ preparations containing about 50% by weight sodium peroxobiearbonate NaHCO 4 9 H20 in a mixture with unreacted bicarbonate were obtained.
2. The formation of an additive compound of hydrogen peroxide with a bicarbonate with the composition Na2CO 3 9 1.5 H202 in the temperature region 0-20 ~ is a consequence of a secondary process of intramolecular conversion of the peroxobicarbonate monohydrate NaHCO4"H20,
accompanied by liberation of
carbon dioxide.
3. Sodium c a r b o n a t e p e r o x y h y d r a t e Na2CO 3 91.5 H202 w a s isolated in p u r e f o r m , and its p h y s i e o c h e m i cal p r o p e r t i e s w e r e studied: density, indices of r e f r a c t i o n , m o l e c u l a r r e f r a c t i o n , r e f r a c t i o n of the h y d r o gen p e r o x i d e of c r y s t a l l i z a t i o n , interplane d i s t a n c e s , and l i m i t of t h e r m a l stability.
LITERATURE
i.
2.
3.
4.
5.
6.
7.
8.
9.
i0.
ii.
12.
13.
14.
15.

CITED

T.P. Firsova, Author's Certificate No. 199,109, July 8, 1966; Byul. Izobr. No. 15, 22 (1967),
T.P. Firsova, Author's Certificate No. 141,853, September 14, 1961; Byul. Izobr. No. 20, 17 (1961).
T.P. Firsova, A. N. Molodkina, T. G. Morozova, and I. V. Aksenova, Zh. Neorgan. Khimii, 9,
1066 (1964).
V.I. Sokol, E. Ya. Filatov, V. M. Bakulina, and T. P. Firsova, Izv. Akad. Nauk SSSR, Ser. Khim.,
1163 (1968).
P.N. Kazanetskii, Zh. Russk. Fiz.-Khim. O-va, 34, 388 (1902).
S. Tanatar, Bet., 3_22, 1544 (1899).
V.W. Slater and W. S. Wood, British Patent 568,754, April 19, 1945; Chem. Abstrs., 43, 369D
(1949).
V.M. Slater and W. S. Wood, U. S. Patent 2,448,056, August 31, 1948; Chem. Abstrs., 39, 28518
(1945).
J.H. Young, U. S. Patent 2,541,733, February 13, 1951; Chem. Abstrs., 45, 4896H (1951).
S.Z. Makarov and V. N. Chamova, Izv. AN SSSR, Otd. Khim. N., 255 (1951).
R. Wulf, Z. Phys. Chem., 2_~I, 368 (1933).
W.F. Waldeek, G. Lynn, and A. E. Hill, J. Amer. Chem. Soc., 54, 928 (1932).
T.W. Riehards and Sh. W. Hoower, J. Amer. Chem. Soc., 3_%7, 95 (1915).
E.D. Ruchkin and O. A. Ukraintseva, Zh. Strukt. Khim., 4, No. 6, 923 (1963).
W. Shamb, C. Satterfield, and R. Wentworth, Hydrogen Peroxide [Russian translation], IL (1958),
p. 230.

1853