CHAPTER - 2

T H E R M A L D E C O M P O S IT IO N O F C O P R E C IP IT A T E D
A M M O N IU M C O P P E R C H R O M A T E
A N D B A R IU M C H R O M A T E
CHAPTER - 2

T H E R M A L D E C O M P O S ITIO N OF C O P R E C IP IT A T E D A M M O N IU M CO P PE R
C H R O M A T E A N D B A R IU M C H R O M A T E

2.1 IN T R O D U C T IO N

T h e rm a l d e co m p o sitio n of a m m o n iu m copper c h ro m a te is one

of the m ost im p o r t a n t steps in the p re p a ra tio n of a c tiv e copper c h r o m ite

c a ta ly s t (c o m m o n ly known as A d k in 's c a ta ly s t) by the c o p r e c ip it a t io n method

[1]. C opper c h r o m ite is an in d u s tr ia lly im p o r t a n t h y d ro g e n a tio n c a ta ly s t

because of its a b ilit y to hydrog e na te fu n c tio n a l groups in a lip h a tic as w e ll

as in a r o m a tic compounds s e le c tiv e ly . I t is e m ployed in b oth vapor phase

re a c tio n s (e.g. h y d ro g e n a tio n o f n itro b e n z e n e and n itro to lu e n e s to the c o rre s ­

ponding amines) and liq u id phase re a c tio n s (.e.g. h y d ro g e n a tio n o f ca rb o n yl

groups in aldehydes, ketones and esters to the c o rresponding alcohols, n it r o -

compounds to the corre sp on d ing amines, e tc .) [2]. It is also an e f f e r t i v e

o x id a tio n c a ta ly s t fo r the conversion o f carbon m onoxide to carbon dioxide

in a u to m o b ile exhaust emission c o n tro l [3].

B a riu m p ro m o te d copper c h r o m it e is o fte n used inthe in d u s tria l

p r a c tic e f o r the above c a t a ly t ic processes [2]. The a d d itio n o f b a riu m w/as

found [4, 5] to s ta b iliz e the copper c h r o m it e c a ta ly s t against re d u c tio n [Cu(II)

to C u d )] and p re v e n t consequent d e a c tiv a tio n , and also enhance its c a y t a ly t ic

a c tiv ity . The b a riu m p ro m o te d copper c h r o m it e can be prepared by th e rm a l

d e co m p o s itio n of c o p r e c ip ita te d a m m o n iu m copper c h ro m a te and b a riu m

c h ro m a te fro m a so lu tio n c o n ta in in g c u p r ic n it r a t e and b a riu m n it r a t e w it h

a m m o n ia c a l s o lu tio n o f a m m o n iu m d ic h ro m a te [A].

2.1.1 T h e rm a l D e c o m p o s itio n o f A m m o n iu m Copper C h ro m a te - L it e r a t u r e

Survey

A c t iv e h y d ro g e n a tio n copper c h r o m it e c a ta ly s t can be obta in ed

[ 6] by the th e rm a l d e co m p o sitio n o f a m m o n iu m copper c h ro m a te in the te m p e ­

ra tu r e range 473-573K a cc o rd in g to the re a c tio n ,

2C u(O H )N H ^C rO ^ ^ 2Cu0 .C r 2 0 3 + 5 H ^0 + N ^ f

Stroupe [7 ] studied the s tr u c tu r e o f C u C r^ O ^ and C u ^ C r ^ O ^ obta in ed

fr o m th e rm a l d eco m p o s itio n o f a m m o n iu m copper c h ro m a te by X -ra y analysis.

The d eco m p o s itio n a t r e la t iv e l y low te m p e ra tu r e gave an e q u im o la r m ix t u r e

o f CuO and C u C r 2 0 ^, w h ile a t very high te m p e ra tu re s C u ^ C r ^ O ^ was fo rm e d .

G oncharov and co-wori<ers [ 8] have re p o rte d the a p p lic a tio n of

th e rm a l d ilu t io n m ethod f o r the th e rm a l analysis o f a m m o n iu m copper c h ro m a te .

Shandilya and c o -w o rk e rs [9 ] have studied the c ry s ta l s tru c tu re

in the solid p roduct(s) o f d e co m p o sitio n o f a m m o n iu m copper c h ro m a te prepared

by p r e c ip it a t in g i t fr o m a m ix t u r e o f c u p ric sulphate and potassium d ic h ro m a te

by aqueous am m onia w it h d if f e r e n t m o la r ra tio s o f CuO and am m o n ia keeping

the s tre n g th o f p ota siu m d ic h ro m a te s o lu tio n co n s ta n t.

M iya ke [10 ] observed t h a t the d e c o m p o sitio n o f a m m o n iu m copper

c h ro m a te in a ir at a tm o s p h e ric pressure is c o m p le te d at 553K and the d e c o m ­

p o s itio n te m p e ra tu r e is independent of the a d d itio n of b a riu m c h ro m a te .

Poshkova and c o -w o rk e rs [1 1 ] c o lle c te d k in e tic data on the th e rm a l

d e c o m p o s itio n of a m m o n iu m copper c h ro m a te in the te m p e ra tu r e range of

503-547K . Semenova et ai [12 ] studied the f o r m a tio n of copper c h ro m ite

c a ta ly s t c o n ta in in g b a riu m fro m the c o m p le x x C u C rQ ^ - y C u ( O H )N H ^ C rO ^ ^

z B a C rO ^ by D T A at 593K.

D e ta ile d studies on the th e rm a l d e c o m p o sitio n o f a m m o n iu m copper

c h ro m a te have been c a rrie d out by Choudhary and P ata ska r [13, 14]. The

th e rm a l analysis o f a m m o n iu m copper c h ro m a te [13 ] was done by T G / D T G / D T A

in the t e m p e ra tu r e range 3 0 3 -1 273K. The d e co m p o s itio n was found to occur

in fo u r stages. The solid d e co m p o s itio n produ ct(s) in these stages were c h a ra ­

c t e r iz e d by chem ical? X - r a y and IR analysis. Based on the re su lts, the f o llo w in g

 106

probable m echanism f o r the o v e ra ll d e c o m p o s itio n o f a m m o n iu m copper c h ro m a te

in the above te m p e ra tu r e range was suggested.

D e c o m p o s itio n in Stage I

M a jo r r e a c tio n ;

2 C u (O H )N H ^ C rO ^ - AZ?.- j .63K ► C u O .C u C r^ O ^ + + N ^t (2.1)

M in o r re a c tio n ;

C u ( O H ) N H ^ C r O ^ ....► C u C rO ^ + H^O +N H ^ f ( 2 • 2)

D e c o m p o s itio n in Stage II

2 C u C rO ^ ■ CuO + C u C r^ O ^ + 3 [ 0 ] f (2.3)

D e c o m p o s itio n in Stage III

CuQ + CuCr^O^ . ■191} - ) ^.23K ^ ^ [q j| (2.4)

D e c o m p o s itio n in Stage IV

2CuO + C r 203 - ..11^.^.:.,127.3 Cu 2C r 20^ + [O lf (2.5)

O th e r pro ba b le side re a c tio n s

CuO + C r ^ O ^ -----7 5 3 K ^ C u C r^ G ^ (2.6)

2CuCr20^ Cu^Cr^O^ + Cr^O^ + [0]| ( 2. 7)

The d e co m p o s itio n of 7~ - ir r a d ia t e d a m m o n iu m copper c h ro m a te

v\/as also found to o cc u r in fo u r stages, w h ic h is very s im ila r to t h a t o f a m m o n iu m

copper c h ro m a te . H o w e v e r, 7~ - ir r a d ia t io n s h ifte d t o t a l w e ig h t loss and the

te m p e ra tu r e corresponding to the D TG and D T A peaks to higher values f o r

all d eco m p o s itio n stages.

 107

The k in e tic s o f th e r m a l d ec o m p o s itio n o f a m m o n iu m copper c h ro m a te

was stud ie d [1 4 ] in the te m p e ra tu r e range 548-623K . The d eco m p o sitio n

curves ( f r a c t io n a l d e co m p so itio n ^ t im e ) w e re found to be o f co m p le x shape

re v e a lin g the in it ia l process o f d e co m p o sitio n and a very sh ort in d u c tio n period

fo llo w e d by the a c c e le ra to ry and decay periods. The in i t i a l process o f d e c o m ­

p o sitio n co uld be expressed by the f i r s t o rd er ra te law and was found to be

a tru e c h e m ic a l d e co m p o s itio n process as evidened by the high a c tiv a t io n

energy (69.8 kJ gmol ). In case of m ain re a c tio n the d eco m p o sitio n data

could be f i t t e d w e ll g ra p h ic a lly to the M a m p le 's c o n t r a c t in g cube expression,

the A varam i - E ro fe e v expression and the P r o u t - T o m p k in expression based

on n u c le a tio n and g ro w th . H o w e v e r, s t a t ic a l analysis led to the s e le c tio n

o f the R ro u t -T o m p k in expression as the best ra te model fo r the d e co m p o sitio n .

The a c t iv a t io n energy f o r the m ain d e c o m p o sitio n r e a c tio n was found to be

133.8 kJ gm ol \

2.1.2 O b je c tiv e s and Scope o f Present In v e s tig a tio n

It can be noted fro m the above lit e r a t u r e survey th a t, though

the d e c o m p o s itio n o f a m m o n iu m copper c h ro m a te has been th o ro u g h ly in v e s ti­

g ated, the in flu e n c e o f the presence o f b a riu m on its d ec o m p o s itio n and the

c h a r a c t e r is t ic o f the solid p roduct(s) o f the d e c o m p o s itio n has n ot been in v e s ti­

gate d. Since b a riu m plays a very im p o r t a n t ro le in s ta b iliz in g the copper

ht
c o r o m it e c a ta ly s t, i t is very in te r e s tin g to know the in flu e n c e of its presence

on the s u rfa ce p ro p e rtie s o f the c a ta ly s t . The p resent w o rk was u nd e rtake n

w it h the f o llo w in g o b je c tiv e s :

(i) To study the in flu e n c e o f the presence o f b a riu m c h ro m a te

a t d i f f e r e n t c o n c e n tra tio n s on the th e rm a l d e co m p o s itio n
o f a m m o n iu m copper c h ro m a te
 108
(ii) To study the in flu e n c e o f b a riu m on the c h a r a c te r is tic s
(v iz . presence o f various c r y s t a llin e phases, su rface c o m ­
p o s itio n , c r y s t a lit e size and s p e c ific su rface area) of
the solid p roduct(s) o f the d e co m p o sitio n a t d if f e r e n t
te m p e ra tu re s .

The th e rm a l analysis ( T G / D T G / D T A ) o f the c o p r e c ip ita te d b a riu m

c h ro m a te -a m m o n iu m copper c h ro m a te c o m p le x [ w it h d i f f e r e n t c o n c e n tra tio n s

o f B a C rO ^ (1.4-19.8 w t % ) ] was c a rrie d o ut in the te m p e ra tu r e range o f 303-

1273K. The solid produ ct(s) o f the d e co m p o sitio n a t d if f e r e n t te m p e ra tu re s

were c h a r a c te riz e d f o r th e ir c r y s t a llin e phases by X R D , the su rface c o m p o sitio n

by XPS, the c r y s t a llit e size (or c r y s ta l g ro w th ) by SEM, and the s p e c ific surface

area by a dso rp tio n o f n itro g e n a t liq u id n itro g e n te m p e ra tu r e .

2.2 E X P E R IM E N T A L

2.2.1 P re p a ra tio n of B a riu m C h ro m a te -A m m o n iu m Copper C h ro m a te

The f o llo w in g c h e m ic a ls w ere used in the p re p a ra tio n o f b a riu m

c h ro m a te -a m m o n iu m copper c h ro m a te .

(1) C u p ric n it r a t e ( t r ih y d r a t e ) B .D .H . (L .R .)

(2) B a riu m n it r a t e B .D .H . (L .R .)

(3) A m m o n iu m d ic h ro m a te B .D .H . (L .R .)

(4) A m m o n ia so lu tio n 28% B .D .H

The c o m p le x c o n ta in in g b a riu m c h ro m a te at d if f e r e n t c o n c e n tr a tio n was

prepared by the m ethod s im ila r to t h a t described elsew here [4, 15] by co p re -

c ip it a t i n g it fro m a s o lu tio n c o n ta in in g c u p ric n it r a t e and req uired amount

of b a riu m n it r a t e w it h an a m m o n ia ca l s o lu tio n of a m m o n iu m d ic h ro m a te

a t ro o m te m p e ra tu r e and at a pH o f 7-7.5. The p r e c ip ita t e was aged fo r

3 h r. D u rin g the ageing p e rio d , the pH o f the s lu rry was adjusted by the

a d d itio n o f am m onia s o lu tio n . A f t e r the p r e c ip ita t e was aged, i t was f ilt e r e d

under vacuum using Buchner fun n el, washed w it h d is t ille d w a t e r u n t il i t was

fre e fr o m n it r a t e ions. The f ilt e r e d cake was dried in a ir oven at 333-373K

o v e rn ig h t. The d rie d mass was crushed to 200-300 mesh size and stored in

a d e s ic c a to r.
 The c o n c e n tr a tio n of b a riu m in the c o p r e c e ip ita te d co m p le x was

d e te rm in e d by a g r a v im e t r ic m ethod [16 ] as fo llo w s . The c o m p le x about

(2g) was dissolved in 30 c m ^ of 2M H C l and the re s u ltin g so lu tion d ilu te d

to 100 c m ^ . To 50 c m ^ o f the s o lu tio n was added lOg o f urea and 8g o f

a m m o n iu m a c e ta te and the pH of the so lu tio n was adjusted to 5.6-5.7 by

the a d d itio n o f am m o n ia so lu tio n . This so lu tio n was heated on a w a te r b a th

fo r 2 h r. The b a riu m p r e c ip ita t e d o u t as b a riu m c h ro m a te was a llo w e d to

s e tt le o v e r n ig h t, f ilt e r e d in a s in te re d c ru c ib le , washed w it h d is t ille d w a te r,

drie d under vacuum a t 393K u n t il the w e ig h t re m a in ed c o n s ta n t.

2.2.2 IT - ir r a d ia t io no f C o p re c ip ita te d Complfex of A m m o n iu m Copper

C h ro m a te -B a riu m C h ro m a te

/ ' - i r r a d i a t i o n o f the c o m p le x was done by ir r a d ia t in g the c o p r e c ip i­

ta te d c o m p le x (co n ta in in g 11.84 w t% B aC rO ^) by / " - r a y s using G am m a C e ll-

220 a t the dose ra te 22.65 K r c e l hr ^ f o r 72 hr.

2.2.3 T G / D T G /D T A

The T G /D T G /D T A th e rm o g ra m s of c o p r e c ip ita te d c o m p le x of

a m m o n iu m copper c h ro m a te -b a riu m c h ro m a te were c a rrie d o ut on an a u to m a tic

u n it MOM B U D A P ES T D E R IV A T O G R A P H (Type 00-102 B) w it h f o llo w in g

d e ta ils :

1. Sample size 200 mg

2. R e fe re n c e compond o L -A lu m in a

3. Sample p r e tr e a t m e n t Sample d rie d a t 353K fo r

2 hr b e fu re use

4. Sample h olde r P la tin u m c ru c ib le re s tin g

on th e rm o c o u p le lead

5. T e m p e rtu re range 303-1273K

-1
6. L in e a r h e a tin g ra te 10K m in

7. A tm o s p h e re In a ir under suction
2.2.4 C h a r a c t e r iz a t io n o f Solid P roduct(s) of D e c o m p o sitio n

Sample of the solid p roduct(s) of d e c o m p o sitio n w ere prepared

by h e a tin g the c o p r e c ip ita te d c o m p le x f o r 4 hr in a m u f f le fu rn a c e (in air)

a t d i f f e r e n t te m p e ra tu re s (v iz . 598, 673, 773, 973, and 1273K). These t e m p e r a ­

tures w e re chosen by e xa m in in g the T G / D T G / D T A th e rm o g ra m s .

2.2.4.1 X - r a y d if f r a c t i o n

The presence of various cry s ta l phases w ere studied by X -ra y

p ow dered d i f f r a c t i o n using a H o lla n d P hilip s PW/730 X -ray g e n e ra to r w ith

a N i- f i lt e r e d C uK k ra d ia tio n source and a s c in t illa t io n c o u n te r.

2.2.4.2 X - r a y p h o to e le c tro n sp ectroscopy

Surface c o m p o s itio n of the solid p roduct(s) was d e te rm in e d by

XPS using a VG s c ie n t i f i c E SC A-3 M K II e le c tr o n s p e c tro m e te r .

2.2.4.3 Scanning e le c tr o n m icrosc o p y

The size and m o rphology o fth e c ry s ta ls of the solid product(s)

w ere stud ie d w it h a C a m b rid g e Steroscan Model 150 Scanning E le c tro n M ic r o ­

scope.

2.2.4.4 A d s o rp tio n o f at liq u id n itro g e n te m p e ra tu re

The s p e c ific s u rfa ce are of the solid p ro duct(s) was d e te rm in e d

by single p o in t BET m e th o d by m easuring adsorption of n itro g e n at liq u id

n itro g e n te m p e ra tu r e and at a n itro g e n c o n c e n tr a tio n o f 0.3 m ole % (balance

H e liu m ) using a Monosorb Surface A re a A n a ly s e r (Q u a n to ch ro m e C o rp o ra tio n ,

USA) based on d yn a m ic a d s o rp tio n /d e s o rp tio n tech n iq ue .

2.3 RESUl TS A N D DISCUSSION

The c o p r e c ip ita te d mass o btained by t r e a t in g the so lu tio n o f b a riu m

n it r a t e and c u p ric n it r a t e w it h a m m c fi'n c a l so lu tio n of a m m o n iu m d ic h ro m a te

is e x pe c ted to be a m ix t u r e o f a m m o n iu m copper c h ro m a te (N H ^ C u (O H )C rO ^ )

and b a riu m c h ro m a te .
 The fo r m a tio n of b a riu m c h ro m a te during the c o p r e c ip it a t io n

was c o n fir m e d by p r e c ip ita t in g o ut c h ro m iu m in the absence o f c u p ric n it r a t e

w it h a m T io n ia ca i s o lu tio n of a m m o n iu m d ic h ro m a te under c o n d itio n s s im ila r

to those used in the p re p a ra tio n of the b a riu m c o n ta in in g a m m o n iu m copper

c h ro m a te and analysing the p r e c ip ita t e fo rm e d a fte r washing and d ry in g by

c h e m ic a l and th e rm a l methods. The th e rm a l analysis o f the c h ro m iu m c o m ­

pound showed a very n e g lig ib le w e ig h t loss ( < 1 %) in the te m p e ra tu r e range

of 303-1273K w h ich is a c h a r a c t e r is t ic of b a riu m c h ro m a te . In presence

of c u p r ic n it r a t e also, c h ro m iu m is e xpe cted to be c o p r e c ip ita te d by the

a m m o n ia c a l so lu tio n of a m m o n iu m d ic h ro m a te as b a riu m c h ro m a te . This

is fu rth e r c o n fir m e d by the decrease in the w e ig h t loss of c o p r e c ip ita te d

c o m p le x c o n ta in in g b a riu m w it h the in crease in the c o n c e n tr a tio n o f b a riu m

in the c o m p le x , discussed la t e r .

The in flu e n c e of the presence of b a riu m (as B aC rO )^in the c o p r e c i­

p ita te d co m p le x on its th e rm a l analysis and solid pro du ct(s) fo rm e d in the

d ec o m p o s itio n a t d if f e r e n t te m p e ra tu re s is discussed below .

2.3.1 T h e rm a l Analysis

2.3.1.1 E f f e c t o f b a riu m

The TG, D T G and D T A curves f o r the b a riu m c h ro m a te -a m m o n iu m

copper c h ro m a te w it h d if f e r e n t c o n c e n tra tio n s of b a riu m c tiro m a te (1.39-

19.84 w t% ) are presented in F ig . 2.1. I t can be seen th a t the d e co m p o sitio n

occurs in fo u r stages o f w h ic h stage I and III are very d is t in c t . The decom­

p o sitio n in the f i r s t stage is e x o th e r m ic (as in d ic a te d by a m a x im u m in the

D T A cu rv e ), w h ile in the o th e r stages i t is e n d o th e rm ic . The th e rm a l curves

(F ig . 2.1) are very s im ila r to those observed in case o f the d e co m p o s itio n

o f a m m o n iu m copper c h ro m a te in the absence of b a riu m [13].

 112

F IG . 2 - 1 : T G /D TG /D T A CURVES FOR DECOMPOSITION OF AMMONIUM

COPPER CHROMATE IN PRESENCE OF BARIUM CHROMATE AT

D IF F E R E N T CONCENTRATIONS
 113

The d ata on the th e rm a l analysis are given in Table 2.1. It can

be noted fro m the re s u lts th a t, in gen e ra l, the w e ig h t loss at the d if f e r e n t

stages o f the deco m p u oitio n decreases w it h the increase in the c o n c e n tr a tio n

of B a C rO ^, in the c o p r e c ip ita te d c o m p le x . This o b se rva tio n is co n sista n t

w it h the fa c t th a t B a C rO ^ does n ot decompose at the te m p e ra tu r e of the

study (3 0 3 -1 273K). The th e o r e t ic a l w e ig h t loss in the d e c o m p o sitio n accordin g

to re a c tio n (2.1), w h ic h c o m p le te s in the second stage o f d e c o m p o sitio n [13],

is e xpe cted to be 27.1, 26.5, 25.3, 24.2, 23.3 and 22.0% f o r the c o p r e c ip ita te d

co m p lex c o n ta in in g 1.4, 3.8, 8.0, 11.9, 15.3, and 19.8 w t . % B a C rO ^, respectivel^t.

The to ta l w e ig h t loss in the second stage of d ec o m p o s itio n (Table 2.1) is

q uite close to th e corresponding e xpe cted values given above. A com parison

of the TG data of the c o p r e c ip ita te d co m p le x c o n ta in in g b a riu m c h ro m a te

at the d iffe re n t c o n c e n tr a tio n w it h the one w it h o u t b a riu m c h ro m a te (i.e.

pure a m m o n iu m copper c h ro m a te ) in d ica te s th a t the m echanism o f the d e c o m ­

p o sitio n of a m m o n iu m copper c h ro m a te is not a f f e c t e d by the presence of

b a riu m c h ro m a te . H o w e v e r, the D T A / D T G peak te m p e ra tu re s or the e x te n t

of d eco m p o s itio n at d if f e r e n t te m p e ra tu re s are changed to a s m a ll e x te n t.

The D T A / D T G peaks f o r the co m p lex c o n ta in in g 7.98 w t . % B a C rO ^ are s h ifte d

co n sid e ra b ly tow ards higher te m p e ra tu r e side. The d ata on th is com p lex

was c o lle c te d re p e a te d ly in o rd er to c o n f ir m the re s u lts. There is probably

a c ritic a l c o n c e n tr a tio n of B a C rO ^ in tlie c o p r e c ip ita te d co m p lex at w hich

the d eco m p o s itio n is delayed to an a p p re c ia b le e x te n t.

2.3.1.2 E f f e c t of 7 " -irra d ia tio n

The th e rm a l curves fo r the 7 ~ -irra d ia te d b a riu m c h ro m a te -a m m o n iu m

copper c h ro m a te are presented in F ig . 2 .I d . The d e c o m p o sitio n o f / " - ir r a d ia t e d

b a riu m c h ro m a te -a m m o n iu m copper c h ro m a te also occurs in fo u r stages,

o f w h ic h stage I and 111 are q u ite d is t in c t . The d eco m p o s itio n in the f i r s t

 114
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stage is e x o th e r m ic , w h ile in the o th e r th re e stages i t is e n d o th e rm ic . The

th e rm a l d e c o m p o s itio n data are included in Table 2.1.

Com parison o f the re su lts on the th e rm a l analysis o f the co m p lex

w it h and w it h o u t / " - i r r a d i a t i o n (Table 2.1) shows t h a t due to the 7 ^ -ir ra d ia tio n

th e re is no s ig n if ic a n t change in the t o t a l w e ig h t loss at the d if f e r e n t stages

of the d e co m p o s itio n , but the te m p e ra tu r e c o rresponding to the DTA and

DTG peal< has s h ifte d to hig he r values f o r a ll stages o f the d e c o m p o s itio n .

Thus T - ir r a d ia t io n increases th e rm a l s t a b il it y of the c o m p le x and its solid

d eco m p o s itio n product(s).

It has been found fr o m an e a r lie r study [1 3 ] t h a t T - ir r a d ia t io n

of a m m o n iu m copper c h ro m a te causes an increase in the to ta l w e ig h t loss

in e v e ry stage o f d e co m p o s itio n . H o w e v e r, the ~T- ir r a d ia t io n o f b a riu m c h ro m a te -

a m m o n iu m copper c h ro m a te has been found to have no in flu e n c e on the to ta l

w e ig h t loss a t d if f e r e n t stages of the d e co m p o sitio n . These observations

p o in t to the fa c t th a t the presence o f b a riu m c h ro m a te has a s ta b iliz in g

a c tio n aga in st the e ffe c ts produced by T ' - i r r a d i a t i o n on the e x te n t o f de­

co m p o s itio n .

2.3.2 Solid Product(s) o f D e c o m p o sitio n

The solid produ ct(s) of the d e co m p o sitio n of b a riu m c h ro m a te -

a m m o n iu m copper c h ro m a te c o n ta in in g d if f e r e n t c o n c e n tr a tio n s o f b a riu m

c h r o m a t e (0-19.84 w t.% ) at 598, 673, 773, 1023 and 1273K have been c h a ra ­

c t e r iz e d fo r th e ir c r y s t a llin e phases, su rface c o m p o s itio n , m o rphology and

c r y s ta l size and s p e c ific s u rfa ce area.

2.3.2.1 C r y s ta llin e phases

XRD data on the solid produ ct(s) o f d e co m p o s itio n of a m m o n iu m

copper c h ro m a te and b a riu m c h ro m a te -a m m o n iu m c opper c h ro m a te (B a C rO ^

11.84 w t.% ) at the d if f e r e n t t e m p e ra tu r e s are presented in Tables 2.2 and

 116

TABLE 2.2

X R D d a ta on solid product(s) o f d e co m p o sitio n o f amnnonium copper chironriate

at d if f e r e n t te m p e ra tu re s

Deco m po sit ion 'd ' values c o rresponding to im p o r t a n t C ry s ta llin e

te m p e ra tu r e X R D peaks phases
(K)

d R e la tiv e in te n s ity
(%)
1 2 3 4

598 2.52 100 C u Q and

2.31 53 amorphous

673 2.52 100 C u O and

2.41 41 Cu C r „ 0 ,
L 4
2.39 45
2.31 37
2.12 24
1.87 14
1.44 24

273 2.87 26 C u O and.

2.52 100 CuCr , O ,
L. ^
2.39 37
2.32 49
1.86 14
1.45 20

1023 3.01 22 C u O and

2.87 31 CuCr „0 ,
£- ^
2.55 100
2.52 66
2.38 51
2.32 50
2.13 20
1.63 23
1.5G 26
1.44 26

1273 5.70 3.51 C u 2 ^ ‘' 2 ^ 4

2.86 33
LCuO and
2.55 13
CuCr O ,
2.47 100 2 4
2.32 4 (tra c e s )]
2.21 32
1.64 24
1.4B 21
 117

TABLE 2.3

X R D data on solid p roduct(s) of c o m p o s itio n o f c o p r e c ip ita te d a m m o n iu m

copper c h ro m a te -b a riu m c h ro m a te (11.84 w t % B aC rQ ^) at d if f e r e n t te m p e ra tu re s

D e c o m p o s itio n 'd' values corresponding to im p o r t a n t C r y s ta llin e

te m p e ra tu r e X R D peaks phases
(K)

d (A) R e la tiv e in te n s ity

(%)

1 2 3 4

598 3.98 14 BaC r 0 , ,

3.50 55 CuO and
3.40 24 amorptious
3.16 52
2.89 46
2.76 29
2.53 100

673 3.98 22 CuCr □, ,

3.51 43 CuO
3.40 29 and B aC rO ,
3.16 46
2.88 46
2.76 26
2.52 100
2.39 36
2.31 42
2.16 33
2.14 32
1.44 24

773 3.97 18 C u C r„0 ,

3.51 38 CuO, and
3.40 24 B a C rO ,
3.16 41
2.09 43
2.78 20
2.55 100
2.39 42
2.32 44
2.18 29
2.15 29
1.86 13

102 3 3.51 37 C u C r„0 ,,

3.40 24 CuO and
3.16 34 B a C rO ,
3.00 22
2.87 35
2.76 17
 iia

Table 2.3 contd.

2.33 100
2.40 30
2.32 61
2.17 26
2.13 20
1.86 18
1.71 18
1.63 33
1.50 32
1.44 30

1273 3.96 6 C u „C r„0 .

z Z 4
3.32 13
and BaCro
3.40 9
3.17 14 [C uO and
2.87 8 C u C r„0 ,
2.84 32 (tra c e s )r
2.76 7
2.34 12
2.32 7
2.46 100
2.31 6
2.17 10
1.64 23
1.48 23
2.3, r e s p e c tiv e ly . The XRD data of the solid produ ct(s) of d eco m p o s itio n

of the co m p le x c o n ta in in g b a riu m c h ro m a te at the o th e r c o n c e n tra tio n s are

q u ite s im ila r to those given in Table 2.3.

The solid p ro duct(s) o bta in ed in the d e co m p o s itio n at 568K are

m o s tly amorphous. The c r y s t a llin it y of the solid p roduct(s) was found to

increase w it h the increase in the d e co m p o sitio n te m p e ra tu r e .

C om parison of the re s u lts in Tables 2.2 and 2.3 shows t h a t the

solid produ ct(s) fo rm e d in the d e co m p o s itio n o f b a riu m c h ro m a te -a m m o n iu m

copper c h ro m a te at the d if f e r e n t te m p e ra tu re s are s im ia lr to those fo rm e d

in the d eco m p o s itio n of a m m o n iu m copper c h ro m a te at the co rresponding

te m p e ra tu re s , except the b a riu m c h ro m a te present in the solid product(s)

o f d e c o m p o s itio n o f the fo rm e r. This f a c t leads to the conclusion t h a t the

d eco m p o s itio n of a m m o n iu m copper c h ro m a te in the presence of b a riu m

c h ro m a te or in its absence occurs in the same way, th a t is the d e c o m p o s itio n

in the e it h e r case occurs in fo u r d is t in c t stages and in volves the re a ctio n s

described in S ection 2.1.1. (R e a ction s 2.1-2.7).

2.3.2.2 M o rp h olo g y and size o f c r y s t a llit e s

Scanning e le c to rn m ic ro p h o to g ra p h o f the solid p roduct(s) of the

d eco m p o s itio n of a m m o n iu m copper c h ro m a te w it h 11.84 w t . % B a C rO ^ and

w it h o u t it, at the d if f e r e n t te m p e ra tu re s are presented in Figs. 2.2 and 2.3.

(A ) E ffe c t o f te m p e ra tu r e ; C o m parison o f the SEM photographs [ a^ - a ^ and

b ^ -b ^ (Figs. 2.2 and 2.3)] reveals t h a t (i) the solid p roduct(s) o f the d e co m p o s itio n

at 598K are m o stly amorphous w h ich is co n sistp n t w it h the X R D r e u s lts j

(ii) the degree of c r y s t a lliz a t io n of the solid p ro duct(s) increases w it h the

d e co m p o s itio n te m p e ra tu r e ; ( iii) the increase in the d e co m p o sitio n te m p e ra tu r e

fro m 673-773K causes a very s m a ll change in the c r y s t a l size, but fu rth e r

increase in the te m p e ra tu r e causes a la rg e increase in the c ry s ta l size of

( a i ) O - O , w t % B a C rO ^, 598K (b,) ll.Sif, wt% BaCrO^, 598K

( a 3 ) 0 * 0 , wt% BaCrO^, 773K ^^. 3 ) 1 1 . 8 ^ , w t% BaCrO^, 773K

Fig 2 . 2
Scanning electron microphotographs of solid product(s) of decomposition of (a) ammonium
copperchromate (b) coprecipitated ammonium copperchromate - barium chromate ( 1 1 . 8 ^f%
BaCrO^^
 121

( ag) O- O, wt% BaCrO^, 1273K

F ig 2.3
Scanning electron microphotographs of solid product(s) of deconnposition of amnnonium
copperchromate (b) coprecipitated ammoniuiTi copperchromate - barium chromate (11.8^^
wt% BaCrO^)
the solid product(s). The very s ig n if ic a n t increase in the c ry s ta l size w ith

the increase in the d e co m p o s itio n tennperature above 773K points to the

o c c u rre n ce of s in te rin g a n d /o r c r y s ta l grow/th of the solid product(s) during

the d ec o m p o s itio n process.

(B) E f f e c t o f b a riu m ; i t is very c le a r f r o m com parison o f the SEM photographs

(Figs. 2.2 and 2.3) th a t the presence of b a riu m c h ro m a te s tro n g ly influ en ce s

the s in te rin g or c ry s ta l g ro w th o f the solid product(s) at higher te m p e ra tu re s

(above 773K). The s in te rin g (g ro w th of the c ry sta ls ) o f the solid product(s)

is la rg e ly reduced by the presence o f b a riu m c h ro m a te . Thus b arium c h ro m a te

acts as an in h ib ito r fu r the s in te rin g o f the copper c h r o m it e c a ta ly s t. The

in h ib itio n a c tio n is probably a re s u lt of the sepa ra tio n o f the c ry s ta ls of

copppr c h r o m it e fr o m each o th e r, caused by the presence o f b a riu m c h ro m a te .

It is known th a t the presence o f b arium c h ro m a te s ta b iliz e s the

copper chromqite c a ta ly s ts against the re d u c tio n o f Cu(Il) to Cu(l) [4,5].

H o w e v e r, the present w o rk shows t lia t the presence o f b a riu m c h ro m a te also

sta b iliz e s the c a ta ly s t against s in te rin g , w h ic h is one o f the causes o f c a ta ly s t

d e a c tiv a tio n , p a r t ic u la r ly in highly e x o th e r m ic c a t a ly t ic processes, such as

vapour phase h y drog e na tio n of n itr o a r o m a tic s to th e ir corresponding amines.

2.3.2.3 Surface area

D a ta on the s p e c ific su rface area o f the solid product(s) o f the

d e co m p o sitio n of a m m o n iu m copper c h ro m a te w it t i and w it h o u t c o n ta in in g

b a riu m c h ro m a te are given in Table 2.4.

F ig u re 2.4 shows the v a ria tio n o f t(ie s p e c ific su rface area of

tlie solid p roduct(s) of the deuo m p usitio n of a m m o n iu m copper c h ro m a te and

b a riu m c h ro m a te -a m m o n iu m copper c h ro m a te (11.84 w t % B aC rO ^) w it h the

d ec o m p o s itio n te m p e ra tu r e . In both the cases o f d e co m p o s itio n , the surface

area o f the solid product(s) decreas'.'s w it h the increase in ttie deco m p o sition

te m p e ra tu r e . H o w e v e r, the decrease in tlie su rface area of the solid product(s)

c o n ta in in g b a riu m c h ro m a te is much s m a lle r than th a t f o r the solid product(s)

not c o n ta in in g b a riu m c h ro m a te .
 123

T A B L E 2.4
'
D a ta su rface area o f solid p ro duct(s) o f d e co m p o sitio n o f (a) a m m o n iu m
copper c h ro m a te and (b) c o p r e c ip ita te d a m m o n iu m copper c h ro m a te -b a riu m
c h ro m a te [11.84 w t . % B a C r O J
4

D e c o m p o sitio n Solid product(s) of Solid product(s) of

te m p e ra tu re d e co m p o sitio n of d e co m p o s itio n o f a m m o n iu m
(K) a m m o n iu m copper copper c h ro m a te -b a riu m
c h ro m a te c lir o m a te

598 39.40 20.91

673 25.77 10.70

773 7.88 6.28

1023 1.17 3.63

1273 0.35 1.00

 124

DECOMPOSITION TE M P E R A T U R E , T(K)

FIG.2-4 : VARIATION OF SURFACE AREA OF T H E SOLID

PRODUCT(S)OF DECOMPOSITION OF ( a) A M M O N I U M
COPPER CHROMATE AND (b) C O P R E C I P I T A T E D
AMMONIUM COPPER CHROMATE AND BARIUM
CHROMATE WITH DECOMPOSITION TEMPERATURES
 The decrease in the su rface area w it h the increase in th e te m p e ­

ra tu re is expected because of s in te rin g , th a t is because of the increase

in the c r y s t a l size due to c r y s ta l g ro w th of the solid p roduct(s) o f the d e ­

c o m p o s itio n . The c o m p a risio n of the re su lts in F ig . 2.4 c le a rly in d ic a t e s

th a t the s in te rin g o f the solid p ro duct(s) is la rg e ly reduced because o f the

presence o f b a riu m c h ro m a te .

2.3.2.4 Surface c h e m ic a l analysis

Surface c h e m ic a l analysis o f the solid product(s) of the d e co m p o sition

of a m m o n iu m copper c h ro m a te w it h and w it h o u t 11.84 w t% B a C rO ^ was

done by X -ra y p h o to e le c tro n sp ectro sco py. XPS s p e c tra f o r 0 (ls), C u ( 2P ^y 2^

and C r ( 2P ^^ 2^ o f solid product(s) obta in ed by the d e c o m p o s itio n at

d if f e r e n t te m p e ra tu re s (3 9 8 -1 273K) are presented in Figs. 2.5, 2.6 and 2.7,

re s p e c tiv e ly . XPS data fo r the solid product(s) of the d e co m p o s itio n of

a m m o n iu m copper c h ro m a te w it h and w it h o u t 13aCrQ^ are given in Tables

2.5 and 2.6, re s p e c tiv e ly . The e le c tro n binding energy ) was obtained

fro m

E, ( 2. 8)
b X -ra y K in c L ic

Using the binding energy of 284.0 eV fo r carbon (Is) as in te rn a l standard

fo r e v a lu a tin g the value of (i.e. the w o rk fu n c tio n o f the s p e ctro p h o to m e te r).

The X -ra y of energy 1253.6 eV (source M g K 06 ) was used as an e x c itin g

ra d ia tio n . Tlie binding energies could be measured w it h the a c curacy of

1 0.2 eV.

The XPS s p ectra f o r 0 (ls ) (Fig. 2.5) are very broad and composed

of tw o unresolved peaks, the first corresponding to of about 529 eV

and the second corresponding to F^^ o f about 531 eV, in d ic a tin g the presence

o f oxygen in tvyo fo rm s . The f ir s t peak is a t t r ib u t e d to the l a t t i c e oxygen

(O ” "^) and the second most probably to the oxy gen chem isorbed on the su rfa ce .
 126

525 531 525 531 537

( Ejj. + Wo) (eV)

FlG.2'5 :XPS SPECTRA OF 0 (Is) OF SOLI D PRODUCT(S) OF

DECOMPOSITION OF (a) A M M O N I U M COPPER CHROMATE
A N D (b) C O P R E C I P I T A T E D AMMONIUM COPPER C H R O MA T E -
BARIUM C H R O M A T E ( B a C r 0 4 . H - 8 4 w 1 . 7 o ) AT f^'^FERENT
TEMPERATURES
 127

( E ^ + Wo) (e V )

FlG.2-6:XPS SPECTRA OF Cu(2p3/2)0F SOLID PRODUCT (S) OF

DECOMPOSITION OF (a) A M M O N I U M COPPER CHROMATE
AND (b) C O P R E C I P I T A T E D AMMONIUM COPPER CHROMATE*
BARIUM CHROMATE ( B a C r 04 .11 8 4 w t . %) A T DIFFERENT
TEMPERATURE S
 128

I ' ^ ___ I__________________ _______________________ I________________ ______

57 0 576 57 0 576 582

( t Wo) (eV)

F1G.2-7:XPS SPECTRA OF Cr {2 p 3/2) OF SOLID PRODUCT (S) OF

DECOMPOSITION OF (a) A M M O N I U M COPPER CHROMATE
AND (b) C O P R E C I P I T A T E D AMMONIUM COPPER C H R O M A T E *
BARIUM C H R O M A T E ( Ba Cr O4 ,11-84 wt.7o) AT D I F F E R E N T
TEMPERATURE S
 129

TABLE 2.5

XPS data o f solid produ ct(s) o f d e c o m p o s itio n o f a m m o n iu m copper c h ro m a te

at d if f e r e n t te m p e ra tu re s

D e co m p o s itio n
0 (Is) Cu (2 P ^ /^ ) Cr (2 P ,,„)
te m p e ra tu re
(K) A E ^/2 A E^^2 / ^ E i /2
(eV) (eV) (eV) (eV) (eV) (eV)

598 529.2 2.5 933.7 3.2 575.3 4.0

531.3 1.9

673 52B.9 2.3 933.4 3.7 575.4 3.7

531.2 1.4

773 528.8 1.9 933.1 3.6 575.3 3.7

530.6 2.2

1023 529.2 1.9 933.1 3.7 575.5 3,6

530.8 1.8

1273 529.8 2.4 931.0 575.7 575.7 3.6

531.4 2.6 9 53.6
 13f

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 It can be noted fr o m the XP5 d ata fo r c opper in Tables 2.5 and

2.6 tha t when the d e co m p o s itio n te m p e ra tu r e is increased fr o m 598 to 1273K

the (i^ f o r Cu rem ains a lm o st co n s ta n t = 933.4 ± 0.3 eV) upto

1Q23K, but fu rth e r increase in the te m p e ra tu re to 1273K results in the

s ig n ific a n t decrease in ttie Ej^,in d ic a tin g tr a n s f o r m a t io n of C u (ll) to C u (l).

The second sm a ll unresolved peak corresponding to the high E|^ f o r the

d e co m p o sitio n product(s) at 1273K (F ig. 2.6) reveals the presence o f a sm all

1
am ount of Cu(Il). These re s u lts are q u ite c o sis te n t w it h those obtained

fro m the th e rm a l analysis and X R D studies. The Ej^ fo r Cr(2P ^y^) o f the

solid p roduct(s) fo rm e d in the d e co m p o s itio n o f a m m o n iu m copper c h ro m a te

c o n ta in in g B a C rO ^ at the d if f e r e n t te m p e ra tu re s is 575.5 ±*2 eV (Table

2.5) w h ic h is very close to the value 575.6 eV found fo r C r ( lll) [16]. While

the tw o observed values fo r o f C r ( 2P ^y 2^ 575.4 ± G.4 eV and

the second about 579 eV,Table 2.6) in d ic a te the presence of C r ( Ill) and

C r(v i) in the solid p ro du cts obtained by the d e c o m p o sitio n of a m m o n ium

copper c h ro m a te c o n ta in in g B a C rO ^.

It maybe noted th a t tlie conclusion drawn fro m the XPS studies

about the presence o f Cu and C r in t;he d if f e r e n t o x id a tio n state s are q uite

consistfcjnt wi t h those d e rived fro m the th e rm a l analysis and the X R D studies.

 132
RE FE RE NCE S

1. H. Adkins and R. Connor, J. Am. Chem. Soc., ^ (1931) 1093.

2. C. L. Thomas, 'C a t a ly t ic Processes and Proven C a ta ly s ts ', A c a d e m ic

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3. G. D w y e r, C a ta l. R e v ., 6 (1972) 261.

4. R. Connor, K . F o lke rs and H. Adkins, J. A m . C hem . Soc., (1932)

1138.

H. A d k in , E. BurGoyne, H. J. Schneider, J. A m . Chem. Soc., 1]^

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11. T. L. Pashkova, I. Y a. T y u ry a e v , G. A. C h is ty a k o v a and V. M.

E l'k in o (USSR) Tr. G os.Inst. P r ik l. K h im ., ^ (1973) 34, (Russ.)
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12. B’ . B. Serrienova, R. M. M a sagutor, V. A . V eklov, E. A . K iv a ,

N e f te k h im , S int. Tekh. Prog, 1769, 89 (Russ.) E d ite d by Nusenkis,
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13. V. R. Choudhary and S. G .P a taska r, J. T h e rm a l A n a l., ']1_ (1979), 45.

14. V. R. Choudhary and S. G. P ataskar, C hem . Engg. Sci., 3 ^ (1980),

1933.

15. W. A. L a z ie r and H. R. A rn o ld , O rg an ic Synthesis C o lle c t iv e V o l.2,

Page 142, Ed. A . H. Q la tt, John Wiley and Son. Inc. N e w y o rk ,
Londofi, Sydney 1966.

16. A. C im in o , B. A. DE Angelis, A . I .u c h e tti and G. M in e lli, J. C a ta l.

45 (1976) 316.