HYDROLYSIS OF ALUMINUM SULPHATE

SOLUTIONS AT HIGH TEMPERATURES

BY

CVETKO NIKOLIC

D i p l . Ing. (Chemical E n g i n e e r i n g )
U n i v e r s i t y of B e l g r a d e , 1963

A THESIS SUBMITTED IN PARTIAL FULFILMENT

OF THE REQUIREMENTS FOR THE DEGREE

OF MASTER OF APPLIED SCIENCE

In the Department

of

METALLURGY

We accept t h i s t h e s i s as conforming t o the

required standard

THE UNIVERSITY OF BRITISH COLUMBIA

February 1971
In p r e s e n t i n g this thesis in p a r t i a l f u l f i l m e n t of the requirements f o r

an advanced degree at the U n i v e r s i t y of British Columbia, I agree that

the Library shall make i t f r e e l y a v a i l a b l e for reference and study.

I f u r t h e r agree t h a t p e r m i s s i o n for e x t e n s i v e copying of this thesis

f o r s c h o l a r l y purposes may be g r a n t e d by the Head o f my Department or

by his representatives. It i s understood that copying o r publication

of t h i s t h e s i s f o r f i n a n c i a l gain shall not be allowed without my

written permission.

Department of Metallurgy

The U n i v e r s i t y o f B r i t i s h Columbia
Vancouver 8, Canada

Date A p r i l 28, 1971

 - ii -

ABSTRACT

Normal and acid aluminum sulphate solutions containing about

6.0 gr/1 of aluminum and up to 50 gr/1 SO^ were hydrolyzed u n t i l

equilibrium was reached i n the temperature region 125-250°C. Under

the equilibrium conditions the only stable s o l i d phase observed i n

equilibrium with a l i q u i d phase of various compositions was

basic aluminum sulphate with nominal formula 3A1 0 .4S0 .9E^0.

2 3 3 A

small portion of the ternary diagrams for the system A^O^-SO^-K^Q

at 225°C and 250°C was constructed. A mixture of aluminum sulphate

and other metal sulphates, K„S0., Na S0,, Li.SO., FeSO. and CuSO.
o

2 4 2 4 2 4 4 4

i . e . was hydrolyzed at 225°C i n order to find the e f f e c t of these s a l t s

on hydrolysis.

The o v e r a l l hydrolysis reaction was found to occur according to

the chemical equation;

ekl^ + 4HS0. + 14H„0 • 3Al 0 .4S0„.9H 0 + 14H

o o o
+

4 2 2 3 3 2

The equilibrium constants at 125, 150, 175, 200, 225 and 250°C

were determined.

F i n a l l y a mechanism for the hydrolysis of aluminum sulphate was

proposed.
 - iii -

ACKNOWLEDGEMENT

The author wishes to express s i n c e r e thanks to Dr. E. P e t e r s f o r

his continuing guidance and i n t e r e s t i n t h i s p r o j e c t . H i s thanks i s

extended to f e l l o w graduate s t u d e n t s , p a r t i c u l a r l y Mr. D. Jones and t h e

t e c h n i c a l s t a f f o f the Department o f M e t a l l u r g y f o r t h e i r h e l p f u l

discussions and a s s i s t a n c e .

F i n a n c i a l support from t h e N a t i o n a l Research C o u n c i l o f Canada

i n the form o f a Research A s s i s t a n t s h i p i s g r a t e f u l l y acknowledged.

 - iv -

TABLE OF CONTENTS

Page

1. INTRODUCTION 1

2. A REVIEW OF THE LITERATURE .. . 3

2.1 The F e 0 - S 0 - H 0 System

2 3 3 2 3

2.2 The A 1 0 ~ S 0 - H 0 System

2 3 3 2 6

2.3 The M 0 - A 1 0 - S 0 - H 0 System

2 2 3 3 2 10

3. EXPERIMENTAL 12

3.1 E x p e r i m e n t a l Technique 12

3.2 M a t e r i a l s Used 18

3.3 Preparation of Solutions f o r Hydrolysis 21

3.4 Chemical A n a l y s i s 22

4. RESULTS AND DISCUSSION 24

4.1 The E f f e c t of Temperature on H y d r o l y s i s of Aluminum

Sulphate S o l u t i o n s 25

4.1.1 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s at

125°C 25

4.1.2 H y d r o l y s i s o f Aluminum Sulphate S o l u t i o n s at

150°C 28

4.1.3 H y d r o l y s i s o f Aluminum Sulphate S o l u t i o n s at

175°C 30

4.1.4 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s at

200°C 32

4.1.5 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s at

225°C 34
 - V -

Page

4.1.6 H y d r o l y s i s of Aluminum S u l p h a t e S o l u t i o n s a t

250°C 36

4.2 The E f f e c t of S u l p h u r i c A c i d C o n c e n t r a t i o n on

H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s 38

4.2.1 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s

with I n i t i a l S0 :A1 0
3 2 3 R a t i o > 3.0 a t 2 5 0 ° C . 38

4.2.2 H y d r o l y s i s o f Aluminum Sulphate S o l u t i o n s

with I n i t i a l S O ^ A l ^ R a t i o > 3.0 a t 225°C... 40

4.3 The E q u i l i b r i u m Constants 42

4.4 Ternary Diagrams f o r the System A 1 0 - S 0 - H 0 2 3 3 2 . 51

4.5 Mechanism of the H y d r o l y s i s of Aluminum Sulphate ... 55

4.6 The E f f e c t of A l k a l i M e t a l Sulphates on H y d r o l y s i s

of Aluminum Sulphate a t 225°C 56

4.6.1 The E f f e c t of L i t h i u m Sulphate on H y d r o l y s i s

of Aluminum Sulphate a t 225°C 58

4.6.2 The E f f e c t o f Sodium Sulphate on H y d r o l y s i s

of Aluminum Sulphate a t 225°C 60

4.6.3 The E f f e c t of Potassium Sulphate on H y d r o l y s i s

of Aluminum Sulphate a t 225°C 61

4.7 The E f f e c t of D i v a l e n t M e t a l Sulphates on H y d r o l y s i s

of Aluminum Sulphate S o l u t i o n s a t 225°C 65

4.7.1 The E f f e c t of Copper Sulphate on H y d r o l y s i s

of Aluminum Sulphate S o l u t i o n s a t 225°C 67

4.7.2 The E f f e c t o f F e r r o u s Sulphate on H y d r o l y s i s

of Aluminum Sulphate S o l u t i o n s a t 225°C 69

 - vi -

Page

4.8 A p p l i c a t i o n o f the H y d r o l y s i s Process 71

5. CONCLUSIONS . 74

APPENDIX I SOLUBILITY OF ALUMINUM SULPHATE 75

APPENDIX I I ANALYSIS OF THE SOLID PHASE 76

APPENDIX I I I X-RAY DIFFRACTION PATTERNS 77

LITERATURE 81
 - vii -

LIST OF TABLES

Table Page

1 Hydrolysis of aluminum sulphate solutions at 125°C... 26

2 Hydrolysis of aluminum sulphate solutions at 150°C... 28

3 Hydrolysis of aluminum sulphate solutions at 175°C... 30

4 Hydrolysis of aluminum sulphate solutions at 200°C... 32

5 Hydrolysis of aluminum sulphate solutions at 225°C... 34

6 Hydrolysis of aluminum sulphate solutions at 250°C... 36

7 The effect of excess sulphuric acid on hydrolysis of

aluminum sulphate at 250°C 40

8 The effect of excess sulphuric acid on hydrolysis of

aluminum sulphate at 225°C 42

9 Equilibrium constant f o r the reaction HSO^ J H +

+ S u
^T • 45

10 Hydrolysis constant of water 46

11 Equilibrium hydrolysis of normal aluminum sulphate i n

the temperature range 125-250°C ^7

12 Equilibrium constants for hydrolysis of aluminum

sulphate solutions with excess sulphuric acid at

225°C and 250°C 47

13 Equilibrium constants for the hydrolysis reaction of

aluminum sulphate 49

14 Solution.composition of 250°C 51

15 Solution composition at 225°C 52

I | |
16 Equilibrium constants for reaction A l + ^0 £
AKOH)^ " •+ H
4 +
56

l
 - viii -

Table Page

17 Hydrolysis of aluminum sulphate-lithium sulphate

solution at 225°C 58

18 Hydrolysis of aluminum sulphate-sodium sulphate

solution at 225°C 6 1

19 Hydrolysis of aluminum sulphate-potassium sulphate

solution at 225°C 6 3

20 Ionic r a d i i of the ions involved i n the system 65

21 Hydrolysis of aluminum sulphate-copper sulphate

solution at 225°C 6 7

22 Hydrolysis of aluminum sulphate-ferrous sulphate

solution at 225°C 6 9

I-A S o l u b i l i t y of A l ( S 0 . )
o o i n water 75
2 43

I-B S o l u b i l i t y of aluminum sulphate i n aqueous solutions

of sulphuric acid at 25°C 75

I-C S o l u b i l i t y of aluminum sulphate i n aqueous 10% ^SO^. 75

II Analysis of the s o l i d phases 76

III-A D i f f r a c t i o n pattern of the p r e c i p i t a t e obtained at

150°C 77

III-B X-Ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained

at 175°C 77

III-C X-Ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained

at 200°C 78

III-D X-Ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained

at 225°C 78

III-E X-Ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained

at 250°C 79
 - ix -

Table Page

III-F X-Ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained

from FeSO.-Al-CSO.K solution at 225°C 79

4 2 43

III-G X-Ray d i f f r a c t i o n pattern of potassium alunite

obtained at 225°C 80

II1-H X-Ray d i f f r a c t i o n pattern of sodium alunite obtained

at 225°C 80

III-I X-Ray d i f f r a c t i o n pattern of lithium alunite obtained

at 225°C 80
 - X -

LIST OF FIGURES

Figure Page

1 F e 0 - S 0 - H 0 system a t 200°C
2 3 3 2 4

2 F e 0 - S 0 - H 0 system at 140°C
2 3 3 2 ' 5

.3 A 1 0 - S 0 - H 0 system at 220°C
2 3 3 2 7

4 E x p e r i m e n t a l Apparatus 13

5 YSI-602 T e r m i s t o r C a l i b r a t i o n 14

6 Transducer Calibration 1.5

7 P r e s s u r e Dependence on Temperature 16

8 H e a t i n g Time to Reach the Working Temperature 17

9 Hydrolysis of Aluminum Sulphate at 125°C 27

10 H y d r o l y s i s o f Aluminum Sulphate at 150°C 29

11 H y d r o l y s i s of Aluminum Sulphate at 175°C 31

12 H y d r o l y s i s of Aluminum Sulphate at 200°C 33

13 H y d r o l y s i s of Aluminum Sulphate a t 225°C 35

14 H y d r o l y s i s o f Aluminum Sulphate at 250°C 37

15 H y d r o l y s i s of A c i d Aluminum Sulphate a t 250°C 39

16 H y d r o l y s i s of A c i d Aluminum Sulphate at 225°C 41

17 Phase Diagram o f the A l ^ - S O ^ H 0 System 43

18 Equilibrium Hydrolysis 48

19 The Change of E q u i l i b r i u m Constant w i t h Temperature .. 50

20 A 1 0 - S 0 ~ H 0 System at 250°C
2 3 3 2 53

21 A 1 0 - S 0 - H 0 System at 225°C
2 3 3 2 54

22 H y d r o l y s i s of Lithium-Aluminum Sulphate S o l u t i o n a t

225°C 59

23 H y d r o l y s i s of Sodium-Aluminum Sulphate S o l u t i o n a t 225°C 62

 - xi -

Figure Page

24 Hydrolysis of Potassium-Aluminum Sulphate Solution

at 225°C 64

25 Hydrolysis Yields Dependence on Ionic Radii 66

26 Hydrolysis of Copper-Aluminum Sulphate Solutions at

225°C 68

27 Hydrolysis of Iron-Aluminum Sulphate Solutions at

225°C 70

28 D.T.A. of 3Al 0 .4SO .9H O

2 3 3 2 72
 1. INTRODUCTION

The aluminum i n d u s t r y was the f i r s t t o use a p r e s s u r e hydro-

m e t a l l u r g i c a l process (The Bayer p r o c e s s ) on a l a r g e s c a l e . Caustic

soda s o l u t i o n s a r e used to d i s s o l v e aluminum from b a u x i t e s and alumina

is separated. Even though c a u s t i c s o l u t i o n s a r e not v e r y selective

and the Bayer p r o c e s s i s l i m i t e d t o low s i l i c a o r e s , alumina i s produced

commerically o n l y by t-his p r o c e s s . T h i s has imposed on the aluminum

i n d u s t r y the t a s k o f t r a n s p o r t a t i o n o f b a u x t i e s over a l o n g d i s t a n c e

because the p r o d u c i n g c o u n t r i e s do n o t have b a u x i t e s o f t h e i r own.

The p r o d u c t i o n o f aluminum i n c o u n t r i e s such as Canada and the

U n i t e d S t a t e s i s today v e r y s e n s i t i v e t o the a v a i l a b i l i t y of b a u x i t e s

from f o r e i g n c o u n t r i e s .

With a d e s i r e to r e c o v e r aluminum from c l a y m i n e r a l s , p r o c e s s e s

have been c o n s i d e r e d , f r o m time to time, t h a t a r e a p p l i c a b l e t o common

North American c l a y s f o r the domestic p r o d u c t i o n of alumina. Such

p r o c e s s e s might a l s o be u s e f u l i n the treatment o f c e r t a i n mine waters

from copper dump l e a c h i n g , which c o n t a i n d i s s o l v e d aluminum s u l p h a t e , among

other sulphate salts.

Any new p r o c e s s p r o d u c i n g alumina must compete i n p r i c e w i t h the

Bayer p r o c e s s . T h i s l i m i t s new l e a c h i n g p r o c e s s e s to cheap r e a g e n t s .

S u l p h u r i c a c i d i s the f a v o u r i t e reagent considered f o r alternate

 - 2 -

*
alumina production processes and an acid process developed by C.S.I.R.O.

has been found to produce aluminum sulphate solutions which can be

hydrolysed to y i e l d basic aluminum sulphate.

Most of the work i n hydrolysis has been done with basic aluminum

sulphate solutions, or solutions containing a l k a l i metal sulphates

and under "process conditions". Because of t h i s there i s p r a c t i c a l l y

no data on equilibrium hydrolysis available i n the l i t e r a t u r e .

Some equilibrium hydrolysis work was carried out on the Fe^O^-SO^-H^O

system. With some exceptions A^O^-SO^-H^O and Fe20.j-S0 -H20 systems 3

p r e c i p i t a t e similar compounds during hydrolysis.

The separation of basic aluminum sulphate s a l t s from aluminum

sulphate solutions i s not well understood either from a k i n e t i c or

thermodynamic point of view. This work i s concerned with hydrolysis

reactions of aluminum sulphate solutions that occur i n the temperature

range 125-250°C, and attempts were made to study both p r e c i p i t a t i o n

rates and the f i n a l e q u i l i b r i a .

Commonwealth S c i e n t i f i c and I n d u s t r i a l Research Organization -

Melbourne
 - 3 -

2. A REVIEW OF THE LITERATURE

It i s generally known that above a temperature which i s a

c h a r a c t e r i s t i c of the metal ion involved, a sulphate s a l t becomes less

soluble as the temperature i s further increased.

E.T. Carlson and C.S. Simons"^ have reported the necessity of

temperature increase from 200 to 275°C to achieve s e l e c t i v e extraction of

n i c k e l and cobalt from l a t e r i t e ore. At 200°C,even though n i c k e l and

cobalt sulphate s o l u b i l i t y was high enough to give good recoveries,

the s e l e c t i v i t y was rather poor because of the high s o l u b i l i t y of

aluminum and iron sulphates. They noticed that the SO^tA^O^ r a t i o

i n the residue was about 1:1 and suggested that Al^O^ and SO^ e x i s t

in i t as a compound.

2.1 The Fe 0 -S0 -H 0 System

2 3 3 2

At elevated temperatures f e r r i c sulphate solutions hydrolyze to

2

p r e c i p i t a t e f e r r i c oxide or basic s a l t s . Posnjak and Merwin have

studied the Fe^^-SO^-H^O system at temperatures up to 200°C. At

200°C only three s o l i d phases exist i n equilibrium with various

compositions of the l i q u i d phase. ¥e^0^ i s i n equilibrium with d i l u t e

solutions of f e r r i c sulphate. The stable phase i n equilibrium with a

somewhat higher ^concentration of sulphuric acid i n solution i s a basic

s a l t of the composition Fe„0„.2S0_.H 0. o F i n a l l y , at high concentrations

 2°3~ 3"
F e S 0 H
2° SYSTEM
AT 2 0 0 C°
 - 5 -

Fe 03 2

F i q . 2 • Fe 03- S 0 -
2 3 H 0
2 SYSTEM

AT !40C°
 - 6 -

of s u l p h u r i c acid i n s o l u t i o n the s t a b l e phase i s the normal s a l t ,

Fe 0 .3S0
2 3 3 ( F i g . 1).

With decreasing temperature the isotherms become more complicated

and at 140°C, there are f i v e s o l i d phases i n e q u i l i b r i u m with d i f f e r e n t

compositions of the l i q u i d phase ( F i g . 2). With f u r t h e r decrease i n

temperature the e q u i l i b r i u m isotherms become s t i l l more complicated.

At 130°C, f e r r i c oxide monohydrate replaces the anhydrous f e r r i c

oxide, and at 110°C anhydrous f e r r i c sulphate disappears, and two acid

s a l t s are s t a b l e ( F e ^ . 4 S 0 3H 0 and F e ^ . 4S0 .9H 0) .

3> 2 3 2

2.2 The A1 0 -S0 -H 0 System

2 3 3 2

P.T. Davey and T.R. Scott have studied the A^C^-SC^-H^O system

under process conditions i n order to determine the optimum conditions

for production of alumina. Their experiments approached e q u i l i b r i u m

to varying degrees. Solutions with i n i t i a l S 0 : A 1 0 3 2 3 r a t i o l e s s than

3.0 and high i n aluminum content were hydrolyzed at temperatures of

100-220°C. In t h i s temperature range the only s t a b l e phase observed,

i n e q u i l i b r i u m with various l i q u i d phases, was basic aluminum sulphate

of the nominal formula 3A1 0 «4S0 9H 0.

2 3 3> 2 At these temperatures,

the p r e c i p i t a t e d phase was i n e q u i l i b r i u m w i t h acid s o l u t i o n s of

aluminum' sulphate. Only a l i m i t e d number of experiments were performed

for periods of time long enough to reach the e q u i l i b r i u m . The

e q u i l i b r i u m s a t u r a t i o n curve f o r t h i s system at 220°C i s given i n F i g .

3. This s a t u r a t i o n curve was obtained by hydrolyzing aluminum sulphate

s o l u t i o n s with i n i t i a l S0„:A1„0„ r a t i o less than 3.0.

 - 8 -

4
Basset and Goodwin have s t u d i e d t h e system A l ^ - S C ^ - t ^ O a t 25°C

at this temperature c o n c e n t r a t e d s o l u t i o n s o f aluminum s u l p h a t e can be

crystallized to y i e l d e i t h e r hydrated aluminum s u l p h a t e A ^ (SO^) ^. 1 6 ^ 0

or the b a s i c s a l t A l 2 O 2 . 2 S O 2 . H H 2 O depending on S O ^ i A ^ O ^ r a t i o o f the

initial solution. These c r y s t a l l i n e m a t e r i a l s tend t o o c c l u d e mother-

l i q u o r and a r e r e a d i l y s o l u b l e i n water, which makes i t d i f f i c u l t to

remove i m p u r i t i e s by washing w i t h o u t redissolving a s u b s t a n t i a l amount

of the s o l i d phase.

5-9

T.R. S c o t t e t a l . have proposed an a c i d p r o c e s s f o r recovery

of aluminum from ores low i n b a u x i t e content and h i g h i n s i l i c a . The

stages of the new p r o c e s s a r e d e s c r i b e d as f o l l o w s :

a. D i g e s t i o n Recycled l i q u o r c o n t a i n i n g aluminum s u l p h a t e

is used t o r e c o v e r e x t r a aluminum from an o r e a t 180°C.

b. Modification A liquor from the d i g e s t i o n stage i s t r e a t e d w i t h

f r e s h b a u x i t e to g i v e a s o l u t i o n o f b a s i c aluminum s u l p h a t e w i t h

S O ^ A ^ O ^ r a t i o l e s s than 3 . 0 .

c. Reduction Modified l i q u o r i s t r e a t e d with sulphur dioxide to

reduce s o l u b l e i r o n t o the f e r r o u s s t a t e a t 100°C.

d. Hydrolysis Reduced l i q u o r i s h y d r o l y z e d a t 220°C i n the

absence o f oxygen to produce b a s i c aluminum.sulphate.

e. Calcination B a s i c aluminum s u l p h a t e i s h e a t e d , preferrably

in stages a t 1200 °C-1300°C, t o y i e l d the r e q u i r e d a-alumina and a

mixture o f sulphurous gases f o r r e c y c l i n g .

J.L. Henry, and G.B. K i n g " ^ have s t u d i e d t h e system A^O^-SO^-E^O

 - 9 -

at 60°C. A t t h i s temperature two b a s i c s a l t s were found t o be i n

e q u i l i b r i u m w i t h s o l u t i o n s o f aluminum s u l p h a t e having an S O ^ A ^ O ^

r a t i o v e r y c l o s e t o 3.0. The s a l t Al^O^.2S0.J.HH^O i s i n equilibrium

w i t h s o l u t i o n s o f pH about 2.5 and A^O^. SO^. 61^0 i s i n equilibrium

w i t h s o l u t i o n s o f pH 2 . 5 - 3 . 2 0 . A t v e r y low c o n c e n t r a t i o n s o f f r e e

s u l p h u r i c a c i d i n s o l u t i o n normal aluminum s u l p h a t e i s the s t a b l e

phase a t 60°C.

R.A. Chaves, V.V. K a v e l i n and B.P. Sobolev"'"^ have s t u d i e d the side

reactions occurring i n the s u l p h u r i c a c i d process for extracting

n i c k e l and c o b a l t from Cuban l a t e r i t e s and have r e v e a l e d the presence

of the f o l l o w i n g compounds: hematite a-Fe^O^, boehmite y-A^O^.H^O,

aluminochromite F e C C r A l ^ O ^ , b a s i c i r o n s u l p h a t e Fe^O^. 2 S O . J . H 2 O ,

basic aluminum s u l p h a t e 3 A I 2 O . J . ASO^. 9 ^ 0 and h y d r o n i o j a r o s i t e 3Fe20 .4S0.j.

3

9H 0.
2

The l a r g e s t amount o f b a s i c aluminum s u l p h a t e i s formed i n the

a u t o c l a v e where the preheated p u l p a t 250°C mixes w i t h concentrated

sulphuric a c i d , i n d i c a t i n g very high r e a c t i o n rate at t h i s temperature.

Beside aluminum and f e r r i c s u l p h a t e s a l t s , o t h e r t r i v a l e n t and

12

q u a d r i v a l e n t metal s u l p h a t e s can be h y d r o l y z e d . At room temperature

v i o l e t - c o l o u r e d chromium s u l p h a t e s o l u t i o n s a r e s t a b l e , but a t h i g h

temperatures these a r e c o n v e r t e d i n t o green complexes i n s o l u t i o n .

When S O ^ i C ^ O ^ r a t i o i n the i n i t i a l s o l u t i o n i s l e s s than 3.0 h y d r o l y z e d

chromic o x i d e i s p r e c i p i t a t e d b u t o n l y at temperatures h i g h e r than

180°C.

Even a t h i g h temperatures s o l u t i o n s o f lanthanum s u l p h a t e do not

h y d r o l y z e r e a d i l y below pH 7.
 - 10 -

Vanadium i s almost c o m p l e t e l y p r e c i p i t a t e d even i n t h e presence

of f r e e s u l p h u r i c a c i d t o y i e l d ^O,.. I n t h e absence o f oxygen a t

100°C, t h e s o l u t i o n s a r e s t a b l e , b u t p r e c i p i t a t e V^O^ a t temperatures

above 200°C.

Scandium c o u l d be s e p a r a t e d from r a r e e a r t h s p r o v i d e d t h a t t h e

s o l u b i l i t y product o f t h e scandium compound was exceeded a t t h e

temperature and i n t h e s o l u t i o n s used.

Indium can be s e p a r a t e d from z i n c e l e c t r o l y s i s l i q u o r s under t h e

same c o n d i t i o n s as f o r scandium.

T i t a n i u m and z i r c o n i u m s u l p h a t e s h y d r o l y z e r e a d i l y w i t h o u t recourse

to a u t o c l a v e c o n d i t i o n s .

2.3 The M ^ A ^ O -SOy-H^O System*

Under o t h e r w i s e t h e same c o n d i t i o n s , t h e presence of a l k a l i

m e t a l s u l p h a t e s w i l l i n c r e a s e t h e h y d r o l y s i s y i e l d o f a b a s i c s a l t from

aluminum s u l p h a t e s o l u t i o n s . V.S. S a z h i n , A.K. Z a p o l s k i i and N.N.

13

Zaklarova have s t u d i e d t h e i n f l u e n c e of ammonium, sodium, and

potassium s u l p h a t e s on h y d r o l y s i s o f aluminum s u l p h a t e s o l u t i o n s . The

degree o f h y d r o l y s i s was i n c r e a s e d i n t h e f o l l o w i n g s e r i e s : (NH^^SO^ <

Na.SO. < K S 0 . .
2 4 2 4 o

14

S. B r e t s z n a j d e r , J . B o c z a r , J . P i s k o r s k i and J . P o r o w s k i

have s t u d i e d t h e h y d r o l y s i s o f aluminum s u l p h a t e s o l u t i o n s w i t h a d d i t i o n

of sodium h y d r o x i d e a t 179-285°C f o r 0-240 min. The p r e c i p i t a t e d solid

phase was found t o be N a 0 . 3 A 1 0 . 4 S 0 7 H 0 .

2 2 3 3> 2 Excess sodium h y d r o x i d e

* M 0 = a l k a l i o x i d e ; M = L i , Na, K, NH^
2
 - 11 -

g r e a t l y i n c r e a s e d the y i e l d . H i g h e r temperature and more d i l u t e

s o l u t i o n s gave h i g h e r y i e l d s . There was little change i n y i e l d f o r

p e r i o d s l o n g e r than 30 min.

15—18

A.K. Z a p o l s k i i et a l . s t u d i e d the e f f e c t of p o t a s s i u m s u l p h a t e

from 0-167.5 gr/£ K^SO^ on h y d r o l y s i s o f aluminum s u l p h a t e s o l u t i o n

c o n t a i n i n g 308 gr/£ A l ^ S O ^ a t 170-250°C. The degree o f h y d r o l y s i s

s h a r p l y i n c r e a s e d at a l l temperatures f o r K^SO^ c o n c e n t r a t i o n from 0-1

mole/1. F u r t h e r i n c r e a s e i n K^SO^ c o n c e n t r a t i o n had l i t t l e influence

on h y d r o l y s i s . In the absence of K^SO^ b a s i c aluminum s u l p h a t e s o f

c o n s t a n t c o m p o s i t i o n (3kl^0^. ^SO^. 7 ^ 0 ) were formed. Potassium a l u n i t e

K [A1 (S0 ) (0H) ]'

2 6 4 4 1 2
>
was p r e f e r e n t i a l l y formed at 230-250°C from

s o l u t i o n s c o n t a i n i n g 1 mole of K^SO^, or more, per mole of A ^ C S O ^ ) ^ -

At temperatures 170-190°C a less basic s a l t S^SO^.3A1 0 .4S0 9H 0 2 3 3 2 was

observed. The system N a 0 - A 1 Q - S 0 - H 0 was

2 2 3 3 2 s t u d i e d a t 200°C under

process c o n d i t i o n s i n o r d e r to determine the c o n d i t i o n s f o r r e c o v e r y

19

of alumina from o r e s . The p r e c i p i t a t e d compound was found to have

a f o r m u l a v e r y c l o s e to N a 0 . 3 A 1 0 > 4 S 0 . 6 H 0 .
2 2 3 3 2

K [A1 (S0 ) (0H)

2 6 4 4 1 2 ] = K 0.3A1 0 .4S0 .6H 0.
2 2 3 3 2
 - 12 -

3. EXPERIMENTAL

3.1 Experimental Technique

A shaking autoclave ( F i g . 4) made o f z i r c o n i u m was used f o r a l l

h y d r o l y s i s experiments. The a u t o c l a v e was placed i n an aluminum

block containing f i v e heaters ( 1 0 0 W. each) to p r o v i d e good h e a t

distribution. The t e m p e r a t u r e was c o n t r o l l e d by a 71 m o d e l "Thermis-

temp" t e m p e r a t u r e c o n t r o l l e r to w i t h i n ± 6.1 °C. The temperature

c o n t r o l l e r was u s e d w i t h a Y S 1 - 6 0 2 s e n s i n g p r o b e w i t h a r a n g e o f 80 to

250°C, and was independently calibrated against a precision mercury

thermometer i n o i l f o r each temperature used. The calibration curve

is shown i n F i g . 5.

I n the low p r e s s u r e r e g i o n the pressure i n the system was

monitored by a transducer and recorded by a "Heath" servo-recorder.

For the h i g h pressure region, a pressure g a u g e was used. A calibration

curve f o r the transducer i s shown i n F i g . 6. The v a r i a t i o n of pressure

w i t h t e m p e r a t u r e i s g i v e n i n F i g . 7. The heating time v a r i e d with

t e m p e r a t u r e and t h i s v a r i a t i o n i s shown i n F i g . 8.

For each r u n , t h e a u t o c l a v e was filled w i t h 75 m l of solution

l e a v i n g a b o u t 30 c c o f gas volume i n the autoclave.

 J ?

temperature controler

tronsduc er
re c o r d e r c ooIe r sampling
tube

aotoclov e

Fig. 4- EXPERIMENTAL APAR AT US

- 16 -
•00 150 200 250 C°
Fjg. 8. HEATING TIME TO .REACH THE TEMPERATURE
 - 18 -

Samples o f h y d r o l y z e d s o l u t i o n were taken from the

c o o l i n g system and the sampling time x^as between 2 and 3

minutes depending on temperature. To make sure

that the samples r e p r e s e n t e d t h e s o l u t i o n from the a u t o c l a v e , the

first 3 ml o f s o l u t i o n from the sampling tube were d i s c a r d e d .

Immediately a f t e r the sample was taken i t was f i l t e r e d and i t s

pH measured. Most o f the h y d r o l y s i s product was p r e c i p i t a t e d on the

a u t o c l a v e w a l l s and remained i n s i d e a f t e r the l i q u i d was removed.

The a u t o c l a v e was then c o o l e d w i t h r u n n i n g water t o room temperature

and opened.

The p r e c i p i t a t e was removed from the a u t o c l a v e w a l l s m e c h a n i c a l l y

by shaking the a u t o c l a v e w i t h g l a s s b a l l s and a few m i l l i l i t e r s o f

d i s t i l l e d water. A f t e r b e i n g f i l t e r e d and washed, the p r e c i p i t a t e

was d r i e d f o r 24 h r s a t 105°C.

A f t e r the s o l i d phase was removed the a u t o c l a v e was washed w i t h

sodium hydroxide s o l u t i o n and then s u c c e s s i v e l y w i t h d i l u t e s u l p h u r i c

a c i d and water. To evaporate the r e s i d u a l water, i t was then heated

and a g a i n allowed to c o o l to room temperature.

3.2 M a t e r i a l s Used

Aluminum s u l p h a t e , c r y s t a l , r e a g e n t , B&A,

Al ( S 0 ) .18H 0; M.W.
4 2 666.45

Maximum L i m i t o f I m p u r i t i e s

Insoluble 0.005%

Free a c i d (H SO.) 0.20%

Chloride (Cl) 0.002%

A r s e n i c (As) 0.00005%
 - 19 -

Heavy metals (as Pb) 0.001%

I r o n (Fe) 0.002%

Substances not p r e c i p i t a t e d
by NH^OH as s u l p h a t e s 0.20%

Lithium sulphate, granular reagent B & A

Li S0..H.O
o M.W. 127.96
2 4 2

Maximum L i m i t of I m p u r i t i e s

Insoluble 0.010%

Chloride (Cl) 0.002%

Nitrate (N0 ) 3 0.001%

Heavy m e t a l (as Pb) 0.0005%

Iron (Fe) 0.0002%

Potassium (K) 0.05%

Sodium (Na) 0.10%

Potassium s u l p h a t e , c r y s t a l , reagent B & A

K.S0.. M.W. 174.27

2 4

Maximum L i m i t of Impurities

Insoluble 0.005%

Chloride (Cl) 0.001%

Nitrogen Compounds 0.005%

(as N)

A r s e n i c (As) 0.00005%

C a l c i u m , Magnesium
and R 0 p r e c i p i t a t e 0.020%
3

Heavy metals (as Pb) 0.'0005%

I r o n (Fe) 0.0002%

Sodium (Na) 0.005%

 - 20 -

Sodium s u l p h a t e , anhydrous, g r a n u l a r reagent B & A

Na„S0. M.W. 142.05

z 4

Maximum L i m i t of I m p u r i t i e s

Insoluble 0.010%

Loss on i g n i t i o n 0.50%

Chloride (Cl) 0.002%

Nitrogen compounds

as (N) 0.0005%

Arsenic (As) 0.0001%

Calcium, magnesium

and R 0 3 p r e c i p i t a t e 0.010%

Heavy metals (as Pb) 0.0005%

I r o n (Fe) 0.0005%
Ferrous s u l p h a t e , c r y s t a l , reagent B & A

FeSO..7H 0 o M.W. 278.03

4 2
Maximum L i m i t of Impurities

Insoluble 0.005%

Chloride (Cl) 0.001%

Phosphate (PO^) 0.001%

Copper (Cu) 0.005%

F e r r i c - I r o n (Fe'' ') 0.01%

Manganese (Mn) 0.05%

Substances not
p r e c i p i t a t e d by
NH.0H 0.050%
4

Z i n c (Zn) 0.005%
 - 21 -

C u p r i c s u l p h a t e , g r a n u l a r c r y s t a l s , B.D.H. reagent

CuSO..5H„0 M.W. 249.69

4 2

Alkalies (suphated) n o t more than 0.5%

Chloride (Cl) n o t more than 0.005%

Iron (Fe) not more than 0.08%

Aluminum "AnalaR" B.D.H.

Al M.W. 26.98

A c i d i n s o l u b l e matter passes test

Iron (Fe) 0.004%

Copper (Cu) 0.005%

Silicon (Si) 0.01%

T o t a l n i t r o g e n (N) 0.002%

3.3 P r e p a r a t i o n of S o l u t i o n s f o r H y d r o l y s i s

The aluminum s u l p h a t e s o l u t i o n was prepared by d i s s o l v i n g hydrated

aluminum s u l p h a t e Al^(SO^)^.I8H2O i n d i s t i l l e d water. A s o l u t i o n of

approximately 6.0 gr/£ o f aluminum was made h a v i n g 3 0 2 ^ 1 ^ 0 2 r a t i o

of about 3.0, and a pH of 3.10. The s o l u t i o n was f i l t e r e d b e f o r e i t

was used for hydrolysis. S o l u t i o n s of the lowest pH (pH = 0.70) used

i n t h i s work were prepared by d i s s o l v i n g A^C^SO^) ^. I8H2O i n dilute

sulphuric acid. Any s o l u t i o n between these two l i m i t s (pH = 0.70 and

pH = 3.10) was prepared by m i x i n g s e l e c t e d r a t i o s of the two.

S o l u t i o n s c o n t a i n i n g a l k a l i n e metal s u l p h a t e s and d i v a l e n t metal

s u l p h a t e s a l t s were prepared by m i x i n g the s o l u t i o n o f the c o r r e s p o n d i n g

s a l t w i t h aluminum s u l p h a t e s o l u t i o n .

S o l u t i o n s of normal aluminum s u l p h a t e were d i s c a r d e d a f t e r 7 days o f

 - 22 -

storage. Aluminum s u l p h a t e s o l u t i o n s c o n t a i n i n g excess sulphuric acid

were kept f o r a few weeks. Solutions containing alkaline metal

s u l p h a t e s were prepared j u s t b e f o r e u s i n g them.

3.4 Chemical Analysis

Initial and f i n a l s o l u t i o n s were a n a l y z e d f o r aluminum, s u l p h a t e ,

and added metal ions. The pH of the s o l u t i o n s was measured b e f o r e

and after hydrolysis.

The s u l p h a t e content was determined by p r e c i p i t a t i o n as BaSO^.

20 *
Aluminum was determined by complexing w i t h EDTA and then back

titrating the excess EDTA w i t h z i n c s u l p h a t e u s i n g d i t h i z o n e as

an i n d i c a t o r and 1 M CH C00H-l M CH C00NH. s o l u t i o n

o o as a b u f f e r .
3 3 4
Standard aluminum s u l p h a t e s o l u t i o n was made from " A n a l a r " aluminum

by d i s s o l v i n g i t i n s u l p h u r i c a c i d .
* disodium s a l t o f e t h y l e n e diamine

Na-OOCH„C CH C00H
o

H00CH C o
CH^COONa

diphenylthiocarbazone

.H H

II S II

H H
 D i v a l e n t i r o n i n the aluminum s u l p h a t e s o l u t i o n was a n a l y z e d by
I| | | i
titrating Fe w i t h CeCHSO^)^ to o x i d i z e i t to Fe using 1,10-

orthophenanthroline ferrous sulphate ( F e r r o i n ) as an i n d i c a t o r . In

t h i s case the aluminum content of the s o l u t i o n was determined from the

d i f f e r e n c e i n EDTA used to t i t r a t e both i r o n and aluminum.

Copper and aluminum sulphate s o l u t i o n was a n a l y z e d by titrating

l i b e r a t e d 1^ w i t h ^2820^ to determine the copper content. The

aluminum content was determined from t h e d i f f e r e n c e i n EDTA used t o

t i t r a t e both copper and aluminum.

The p r e c i p i t a t e d phase was a l s o a n a l y z e d f o r aluminum and

sulphate. The s o l i d phase i s s o l u b l e i n s t r o n g s u l p h u r i c a c i d and

s t r o n g sodium h y d r o x i d e , and t h e r e f o r e the same methods as f o r the

s o l u t i o n s were used for analysis. Water content was taken as the

d i f f e r e n c e between the t o t a l weight and the aluminum and s u l p h a t e

content. L i , Na and K content was determined by the "EEL" flame

photometer.

,c—c c — C.>
c// \ c — C// \C
\ / \ '
C=N N=C

[ F e ( C H N ) ] ++
1 2 g 2 3 c a t i o n ; red colour

41 + 2Cu
++
2CuI + I 2

I 21
2
 - 24 -

4. RESULTS AND DISCUSSION

The i n t e n t i o n of the work p r e s e n t e d i n t h i s t h e s i s was t o study

the change i n e q u i l i b r i u m h y d r o l y s i s o f aluminum s u l p h a t e solutions

w i t h temperature, s u l p h u r i c a c i d c o n c e n t r a t i o n and o t h e r c a t i o n s . It

is generally known t h a t the amount of p r e c i p i t a t e d phase i s determined

by the c o n c e n t r a t i o n o f aluminum and s u l p h a t e i n the i n i t i a l solution

3

for a given temperature. In the p r e s e n t work the c o n c e n t r a t i o n of

aluminum i n the i n i t i a l s o l u t i o n was not v a r i e d i n o r d e r to make i t

possible to e s t a b l i s h the e f f e c t o f other f a c t o r s . Results obtained

are d i s c u s s e d under the f o l l o w i n g classifications:

4.1 The e f f e c t of temperature on h y d r o l y s i s o f aluminum s u l p h a t e

solutions.

4.2 The e f f e c t o f s u l p h u r i c a c i d c o n c e n t r a t i o n on h y d r o l y s i s o f

aluminum s u l p h a t e s o l u t i o n s .

4.3 The e q u i l i b r i u m constants

4.4 T e r n a r y diagrams f o r the A^O^-SO^-f^O system.

4.5 Mechanism o f the h y d r o l y s i s of aluminum sulphate.

4.6 The e f f e c t of a l k a l i m e t a l s u l p h a t e s on h y d r o l y s i s o f

aluminum sulphate.

4.7 The e f f e c t of d i v a l e n t m e t a l s u l p h a t e s on h y d r o l y s i s o f

aluminum s u l p h a t e s o l u t i o n s .

4.8 A p p l i c a t i o n of the h y d r o l y s i s process.

 - 25 -

4.1 The E f f e c t o f Temperature on H y d r o l y s i s of Aluminum Sulphate

Solutions

At o r d i n a r y temperatures, c o n c e n t r a t e d s o l u t i o n s of aluminum

sulphate w i l l only c r y s t a l l i z e a b a s i c s a l t i f the S O ^ i A ^ O ^ ratio

in the i n i t i a l s o l u t i o n i s l e s s than 3.0.

14

S. B r e t s z n a j d e r has o b t a i n e d normal aluminum s u l p h a t e from clay

( c a l c i n e d at 770-820°C f o r 1 h r ) b y l e a c h i n g i t w i t h d i l u t e s u l p h u r i c

acid f o r 10-12 h r s at 80°C and c o o l i n g the f i l t r a t e to crystallize

3

the normal aluminum s u l p h a t e h y d r a t e . I t was r e p o r t e d by T.R. Scott

that at temperatures h i g h e r than 1 1 0 ° C h y d r o l y s i s of aluminum s u l p h a t e

solutions with i n i t i a l SO^A^O^ ratio l e s s than 3.0 precipitates

c r y s t a l l i n e m a t e r i a l " b a s i c aluminum s u l p h a t e " (B.A.S.). T h i s compound

is related to the m i n e r a l a l u n i t e , h a v i n g a f o r m u l a expressed as

3AI2O2.4SO2.9H2O w i t h a t h e o r e t i c a l c o m p o s i t i o n as f o l l o w s : ^ 2°3
L
~

38.8%; S 0 3 = 40.6%; HyO = 20.6%.

The temperature e f f e c t on h y d r o l y s i s was determined by h y d r o l y z i n g

d i l u t e s o l u t i o n s of aluminum s u l p h a t e w i t h i n i t i a l S02:Al202 ratio

of about 3.0 i n the temperature range 125-250°C. Retention time

in these experiments was as l o n g as 16 h r s . The equilibrium was

determined from the h y d r o l y s i s curves when t h e r e was no further change

in the aluminum c o n c e n t r a t i o n w i t h p r o l o n g e d time.

4.1.1 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s at 125°C

H y d r o l y s i s experiments at t h i s temperature were done w i t h

u n f i l t e r e d s o l u t i o n s of pH = 3 . 1 0 . R e s u l t s o b t a i n e d were not

reproducible. When the same s o l u t i o n s were f i l t e r e d , and then

h y d r o l y z e d , r e s u l t s were more u n i f o r m . Hydrolysis yields

at e q u a l time i n t e r v a l s were l e s s f o r
 - 26 -

filtered s o l u t i o n s , and, i n both c a s e s , n o t s u f f i c i e n t f o r chemical

analysis. F o r times which were l o n g enough t o e s t a b l i s h equilibrium,

h y d r o l y s i s y i e l d s were almost the same f o r both the f i l t e r e d and the

unfiltered s o l u t i o n s , thus s u g g e s t i n g t h a t a n u c l e a t i o n p r o c e s s p l a y s

an important r o l e i n -the k i n e t i c s o f the r e a c t i o n a t t h i s temperature.

R e s u l t s of the a n a l y s i s o f h y d r o l y z e d s o l u t i o n s a r e shown i n T a b l e 1

and F i g . 9.

'»
T a b l e 1. H y d r o l y s i s o f aluminum s u l p h a t e s o l u t i o n s a t 125 C.

Time a t Al i n s o l . SO. i n s o l . A l prec. SO^ p r e c . pH S0 /A1 0

3 2 3
4
125°C
hrs gr/Ji gr/i> gr/£ i n the pre-

1.00 6.09 - 0.01 . - 2.98 -

3.00 5.89 - 0.21 - 2.53 -

5.00 5.80 31.70 0.30 0.70 2.24 1.31

6.00 5.69 31.33 0.41 1.07 1.80 1.47

7.00 5.68 31.34 0.42 1.06 1.80 1.41

12.50 5.76 31.30 0.34 1.10 1.78 1.82

13.75 5.65 31.38 0.45 1.02 1.79 1.27

16.50 5.68 31.38 0.42 1.02 1.78 1.36

32.40 + 0.3 gr/£ S 0 .

=

Starting solution :
6.10 + 0.05 gr/£ A
pH = 3.10
 - 28 -

4.1.2 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s at 150°C

Filtered s o l u t i o n s of aluminum s u l p h a t e w i t h i n i t i a l SO^rA^O^

r a t i o of about 3.0 were h y d r o l y z e d a t 150°C f o r d i f f e r e n t times.

R e s u l t s o b t a i n e d are p r e s e n t e d i n T a b l e 2 and F i g . 10. From F i g . 10

e q u i l i b r i u m seems to be reached i n 6.0 h r s and the SO^tA^O^ r a t i o

of the p r e c i p i t a t e d compound remains unchanged w i t h p r o l o n g e d times.

The amount of p r e c i p i t a t e d compound was not s u f f i c i e n t f o r chemical

a n a l y s i s but the X-ray d i f f r a c t i o n pattern indicated that basic

aluminum s u l p h a t e e x i s t e d at t h i s temperature (see Appendix III-A).

Table 2. H y d r o l y s i s of aluminum s u l p h a t e s o l u t i o n s at 150°C*

Time at A l i n s o l . SO, i n s o l . A l p r e c . SO. p r e c . PH s o :A1 0

3 2 3

4 4
150°C

hrs gr/£ gr/£ gr/£ i n the p r e c .

1.00 5.28 30.44 0.82 1.96 1.67 1.34

2.00 5.07 29.96 1.03 2.44 1.55 1.33

3.00 4.84 - 1.26 - 1.45 -

4.00 4.76 - 1.34 - 1.45 -

6.00 4.64 28.65 1.46 3.75 1.40 1.44

10.00 4.64 28.60 1.46 3.80 1.38 1.46

16.00 4.65 28.64 1.45 3.46 1.44 1.34

Starting solution: 32.40 gr/2, SO

6.10 gr/£ Al

pH = 3.10
 - 30 -

4.1.3 Hydrolysis of Aluminum Sulphate Solutions at 175°C

F i l t e r e d solutions of aluminum sulphate with i n i t i a l SO^iA^O^

r a t i o of about 3.0 were hydrolyzed at 175°C and results obtained are

presented i n Table 3 and F i g . 11. The precipitated phase has a r a t i o

of SOyA^O^ of about 1.32 (calculated from F i g . 11) corresponding to

the r a t i o of basic aluminum sulphate. Analysis of the s o l i d phase

confirmed the presence of the basic aluminum sulphate (see Appendix

II, f o r Chem. Anal, and Appendix III-B f o r X-ray d i f f . patterns.).

Table 3. Hydrolysis of aluminum sulphate solutions at 175 C

Time at A l i n s o l . SO i n s o l . A l prec. SO prec. pH SO :A1 0»

9

175°C 4
*
hrs. gr/Jl gr/>! gr/£ gr/£ i n the prec.

1.00 4.45 28.53 1.54 3.87 1.30 1.32

2.00 3.96 27.26 2.14 5.14 1.27 1.35

4.00 3.68 26.76 2.42 5.64 1.18 1.31

6.00 3.56 26.39 2.54 6.01 1.15 1:33

10.00 3.55 26.40 2.55 6.00 1.15 1.32

16.30 3.50 26.40 2.60 6.00 1.15 1.30

*
Starting solution: 32.40 gr/£ S0 4

6.10 gr/£ A l
pH = 3.10
J
' " 1
-J 1 I > I ! * ' ' ' ' I L_
0 • 2 3 4 5 6 7 8 9 10 II 12 13 14 15 16
Fig II. HYDROLYSIS OFALUMINIUM SULPHATE AT 175 C° timeinhrs.
 - 32 -

4.1.4 Hydrolysis of Aluminum Sulphate S o l u t i o n s at 200°C

Solutions with i n t i a l SO^ikl^O^ ratio of about 3.0 were h y d r o l y z e d

at 200°C f o r as long as 18 h r s . Results o b t a i n e d are shown i n T a b l e

4 and F i g . 12. The e q u i l i b r i u m h y d r o l y s i s y i e l d i s h i g h e r than at 175°C. The

SO^iAl^O^ r a t i o of the p r e c i p i t a t e d compound c a l c u l a t e d from F i g . 12

i s about 1.31. Analysis of s o l i d phase shows t h a t the p r e c i p i t a t e d

compound i s the b a s i c aluminum s u l p h a t e (see Appendix I I f o r Chem. a n a l ,

and Appendix I I I - C f o r X-ray d i f f . pattern).

Table 4. Hydrolysis of aluminum s u l p h a t e s o l u t i o n s at 200°C

*

Time at Al i n s o l . SO, i n s o l . Al prec. SO, p r e c pH S0 :A1 0

4
3 2 3

200°C 4

hrs. gr/2, gr/£ gr/£ gr/£ i n the prec.

1.00 3.30 25.78 2.80 6.62 1.07 1.33

2.00 3.01 24.98 3.09 7.42 1.03 1.35

4.00 2.71 24.32 3.39 8.08 0.99 1.34

6.00 2.51 23.91 3.59 8.49 0.98 1.33

6.45 2.51 23.89 3.59 8.51 0.98 1.33

18.00 2.40 23.65 3.70 8.75 0.98 1.33

Starting solution: 32.40 gr/SL S0~

6.10 gr/£ Al

pH = 3.10
0 I 2 3 4 5 6 7 8 9 10 II 12 13 14 15 16
Fig.12. HYDROLYSIS OF ALUMINIUM SULPHATE AT 2 0 0 C ° timsinhrs.
 - 34 -

4.1.5 H y d r o l y s i s of Aluminum Sulphate S o l u t i o n s a t 225°C

Filtered s o l u t i o n s of aluminum sulphate with i n i t i a l SO^iA^O^

ratio of about 3.0 were h y d r o l y z e d at 225°C and r e s u l t s o b t a i n e d a r e

shown i n Table 5 and F i g . 13. H y d r o l y s i s y i e l d s are very high. The

p r e c i p i t a t e d phase has an S O ^ A l , ^ r a t i o 1.33 ( c a l c u l a t e d from F i g .

13). A n a l y s i s of the s o l i d phase showed the c o m p o s i t i o n of b a s i c

aluminum sulphate (see Appendix I I f o r Chem. a n a l , and Appendix I I I - D

f o r X-ray d i f f . p a t t e r n ) .

Table 5. H y d r o l y s i s of aluminum s u l p h a t e s o l u t i o n s at 225°C

Time at A l i n s o l . SO. i n s o l . A l prec. SO, p r e c . pH SO

4 4 3 : A 1
2°3
225°C
hrs. gr/l gr/H gr/n gr/X, i n the p r e c .

1.00 1.89 22.45 4.21 9.95 0.89 1.33

1.00 1.88 22.35 4.22 10.05 0.92 1.34

2.00 1.80 22.31 4.30 10.09 0.92 1.32

2.00 1.73 21.55 4.37 10.85 0.89 1.39

3.00 1.65 21.96 4.45 10.44 0.88 1.32

5.00 1.58 21.40 4.52 11.00 0.89 1.37

8.40 1.44 21.36 4.66 11.04 0.85 1.33

16.00 1.48 21.63 4.54 10.77 0.85 1.33

*
Starting solution: 32.40 gr/j> S0 4

6.10 gr/Z A l

pH = 3.10
Fig. 13- HYDROLYSIS OF ALUMINIUM SULPHATE AT 2 2 5 C* timemhrs
 - 36 -

4.1.6 H y d r o l y s i s o f Aluminum Sulphate S o l u t i o n s a t 250°C

Filtered s o l u t i o n s o f aluminum s u l p h a t e were h y d r o l y z e d a t 250°C

and i t was found t h a t t h e amount of p r e c i p i t a t e d b a s i c aluminum

s u l p h a t e on h e a t i n g the a u t o c l a v e t o t h i s temperature was comparable

to the amount o f b a s i c s a l t p r e c i p i t a t e d i n 16 h r s a t 225°C. This

suggests t h a t t h e r e a c t i o n r a t e above 225°C must be v e r y h i g h . Results

o b t a i n e d at t h i s temperature a r e shown i n T a b l e 6 and F i g . 14.

The S O ^ A ^ O ^ r a t i o of the p r e c i p i t a t e d compound i s 1.33. Analysis

of t h e s o l i d corresponds t o t h e b a s i c aluminum s u l p h a t e (see Appendix

I I f o r Chem. a n a l , and Appendix I I I - E f o r X-ray d i f f . p a t t e r n ) .

T a b l e 6. H y d r o l y s i s of aluminum s u l p h a t e at 250°C*

Time at A l i n s o l . SO, i n s o l . A l prec. SO^ prec. P H S0 :A1 0

3 2 3

250°C 4

hrs. gr/£ gr/£ gr/£ gr/£ in the p r e c .

0.00 1.52 21.57 4.58 10.83 0.85 1.33

1.00 0.97 20.27 5.13 12.13 0.80 1.33

3.30 0.88 20.27 5.22 12.13 0.80 1.31

6.30 0.91 20.13 5.19 12.27 0.79 1.33

*
Starting solution: 32.40 gr/2, SO

6.10 gr/£ A l

pH = 3.10
 o o
ca

0 PH
O Al o
< vI 3.0
6.0 J 1-30
o Q S0|
\
5.0 1 l V PH 2.0 4
-28

- 26

4.0 24
1.0 -I Co

22
3.0 H
h20

2.0 H
\
18
\
16
I.OJ

1 1
' 1
• 1 1 L 1 1 I I I • •
3 1 2
3 4 5 6 7 8 9 10 II 12 13 14 15 16
Fig. 14. HYDROLYSIS OF ALUMINIUM S U L P H A T E AT 2 5 0 C ° timeinhrs.
 - 38 -

4.2 The E f f e c t of S u l p h u r i c A c i d C o n c e n t r a t i o n on H y d r o l y s i s

of Aluminum Sulphate Solutions

Most of the work on h y d r o l y s i s of aluminum s u l p h a t e was done on

s o l u t i o n s having initial S O ^ A l ^ O ^ r a t i o l e s s than 3.0. The reason

for t h i s was to o b t a i n h i g h y i e l d s i n a s h o r t time and at low tempera-

tures. If hydrolysis i s to be used as a p u r i f i c a t i o n p r o c e s s f o r

l e a c h s o l u t i o n s h i g h e r c o n c e n t r a t i o n s of s u l p h u r i c a c i d would be

expected. In the work p r e s e n t e d i n t h i s t h e s i s a s e r i e s of experiments

w i t h s o l u t i o n s c o n t a i n i n g about 6.0 gr/£ aluminum and different

c o n c e n t r a t i o n s of s u l p h u r i c a c i d was done. H y d r o l y s i s curves i n the

p r e v i o u s p a r t were used to determine the r e t e n t i o n time f o r the two

temperatures 225°C and 250°C. These two temperatures were chosen because

of the h i g h y i e l d s at s h o r t times w i t h s o l u t i o n s h a v i n g an SO^rA^O^

r a t i o of about 3.0.

4.2.1 H y d r o l y s i s of Aluminum Sulphate Solutions with Initial

S0 :A1 0
3 2 3 Ratio > 3.0 a t 250°C

F i l t e r e d s o l u t i o n s w i t h excess s u l p h u r i c a c i d were h y d r o l y z e d at

250°C f o r 4 h r s . The h i g h e s t S 0 : A 1 0
3 2 3 r a t i o used i n t h i s s e t of

experiments was about 4.63. R e s u l t s o b t a i n e d are shown i n T a b l e 7 and

Fig. 15. As the c o n c e n t r a t i o n of excess a c i d i n the initial

s o l u t i o n was increased the amount of p r e c i p i t a t e d b a s i c aluminum

sulphate decreased.

!
 - 39 -
~~i r~ —T" n 1 1 1 1 r
22 24 26 28 30 32 34 36 38 SO^jn sol. gr/1.

O Al

0 S
°4

VPH

'0 o

o 0 v

IO 2.0 3.0 4.0 AI in sol. gr/1.

— L —
+
—r- 2.0 finalpH
Fig.15. HYDROLYSIS 1.OF
0 ACID ALUMINIUM
SULPHATE A T 2 5 0 C *
 - 40

Table.7. The e f f e c t of excess s u l p h u r i c a c i d on h y d r o l y s i s o f

aluminum s u l p h a t e a t 250°C.

pH SOT i n i t . Al insol. SO, i n s o l . Al p r e c . SO^ p r e c . pH

4 4
initial gr/£ gr/Jl gr/£ gr/£ gr/A final

0.70 50.08 3.31 43.43 2.79 6.65 0.56

1.00 44.26 2.17 34.97 3.93 9.29 0.60

1.50 37.05 1.25 25.45 4.85 11.60 0.70

2.00 34.08 1.00 22.05 5.10 12.03 0.76

2.50 33.21 0.98 21.13 5.12 12.08 0.78

3.10 32.40 0.91 20.13 5.19 12.27 0.80

4.2.2 H y d r o l y s i s o f Aluminum Sulphate Solutions with Initial

S0 :A1 0
3 3 R a t i o > 3.0 a t 225°C

F i l t e r e d s o l u t i o n s o f aluminum s u l p h a t e were h y d r o l y z e d a t 225°C

for 6 hrs. Initial s o l u t i o n s used i n this set 0 f experiments were the

same as s o l u t i o n s used a t 250°C. Hydrolysis yields increased

with i^preasing pH o f the i n i t i a l solution. Results obtained

from t h i s s e t o f experiments a r e p r e s e n t e d i n T a b l e 8 and F i g . 16.

 - 41 -

~i— I i p — r — i i
22 26 30 34 38 42 S O 4 in soLgr/l.

X
o.

3.0 H

1.0 20 3.0 4.0 A l i n sol.gr/1.

•
-4
f-
,-. .~ IX) 2 0 pH final
Fig. 16. HYDROLYSIS OF ACID ALUMINIUM
SULPHATE AT 2 25C°
 - 42 -

T a b l e 8. The e f f e c t of excess s u l p h u r i c a c i d on h y d r o l y s i s of

aluminum s u l p h a t e a t 225°C.

pH SO. i n i t . Al i n s o l . SO. i n s o l . A l p r e c . SO^ p r e c . pH

4 4
initial gr/£ gr/£ gr/a gr/A gr/£ final

0.70 50.08 4.94 47.04 1.16 3.04 0.65

1.00 44.26 3.62 38.35 2.48 5.91 0.70

1.50 37.05 2.33 28.37 3.77 8.68 0.78

2.00 34.08 1.87 24.10 4.23 9.98 0.83

2.50 33.21 1.63 22.60 4.47 10.61 0.84

3.10 32.40 1.50 21.52 4.60 10.88 0.85

4.3 The E q u i l i b r i u m Constants

Application of the phase r u l e to the system Al^O^-SO^-H^O requires

that a t constant temperature, a s o l u t i o n composition e x i s t s which i s

i n v a r i a n t when i n e q u i l i b r i u m w i t h two s o l i d phases, e.g. A ^ O ^ n R ^ O and

3A1 0 .4S0 .9H 0 (B.A.S. - the most b a s i c

2 3 3 salt).

If the s t a r t i n g s o l u t i o n has a c o m p o s i t i o n below t h i s point,

the f i r s t phase to p r e c i p i t a t e i s always the o x i d e , but the s o l u t i o n

composition w i l l change i n t h e d i r e c t i o n of the i n v a r i a n t p o i n t until

the b a s i c salt also p r e c i p i t a t e s . The l o c a t i o n o f the i n v a r i a n t

point P ( F i g . 17) w i l l change w i t h the temperature.

Fig.I 7 . PHASE DIAGRAM OF THE A I 2 O 3 - S O 3 - H 2 O SYSTEM
 - 44 -

If the solution composition i s below the invariant point P at the

temperature T and above the invariant point at any temperature higher

than T, then the oxide w i l l p r e c i p i t a t e i n the early stages of heating

and at l a t e r stages the basic s a l t w i l l p r e c i p i t a t e while the oxide

w i l l tend to redissolve. Eventually the oxide may completely disappear

i f the composition of the solution i s such that i t i s above the

invatiant point. In the work of T.R. Scott, a second phase (A^O^m^CO

was not observed because the hudrolysis was carried out at high

concentrations of aluminum i n solutions and i t can only be expected to

p r e c i p i t a t e from d i l u t e solutions of basic aluminum sulphate.

The X-ray d i f f r a c t i o n patterns did not show the presence of A^O^

i n the s o l i d phase and therefore i t can be concluded that the solution

composition i s above the invariant point where only one phase exists

i n equilibrium with the l i q u i d phase. The X-ray d i f f r a c t i o n pattern

of the p r e c i p i t a t e obtained at 125°C, was very poor so that no

conclusion about the presence of aluminum oxide could be made. I f

there i s only one s o l i d phase i n equilibrium with l i q u i d phase at a l l

temperatures from 125°C up to 250°C, then the same hydrolysis reaction

should occur. For such a reaction, the slope of a plot of log

[equilibrium constant] vs. 1/T°K should be l i n e a r .

21

R.G. Robins has reported values f o r the second d i s s o c i a t i o n

constant of sulphuric acid up to about 200°C which are i n good agreement

with the values calculated from the correspondence principle. Values of

these constants, are given i n Table 9. The presence of aluminum sulphate

w i l l s h i f t the equilibrium to the l e f t i n the reaction 4SC> " J H4

+
+ SO^".

Therefore only HSO^ ions w i l l exist i n solution. Assuming that aluminum

sulphate i s completely dissociated, and that only HSO, i o n can exist

 - 45 -

- -»• +
T a b l e 9. E q u i l i b r i u m c o n s t a n t s f o r the r e a c t i o n HSO, H + SO.
4 4

T°C 125 150 175 200 225 250

log K -3.53 -3.89 -4.40 -4.72 -5.95 -6.05

i n s o l u t i o n i n the temperature range .125-250°C the h y d r o l y s i s reaction

can be w r i t t e n a s :

6A1 444
" + 4HS0. + 14KL0 — — 3Al 0„.4S0 .9H 0
o o o + 14H +
(1)
4 2 — 2 3 3 2

The e q u i l i b r i u m c o n s t a n t f o r t h i s r e a c t i o n can be e x p r e s s e d a s :

K = ( 2 )
[A1 ] [HS0 "]^
W D
4

An e x p r e s s i o n f o r the v a r i a t i o n of the e q u i l i b r i u m c o n s t a n t K w i t h

temperature i s d e r i v e d by combining

-AG 0
= RT in K (3)

and

9T ^ T ; J
P T 2 K
'

Therefore

,9 in K. = d&n K = AH°_ ,,-\

9T P ;
dT 2 U J

Kl

assuming thatAH° is virtually independent of temperature. Equation

(5) can be a l s o w r i t t e n as
 - 46 -

din K AH° . .
dl/T =
R { b )

Thus, i f £n K i s p l o t t e d a g a i n s t 1/T the s l o p e of the curve at any

point i s equal to -AH°/R. From the e x p r e s s i o n f o r the equilibrium

constant (2) i t f o l l o w s that

- l o g K = 14pH + 6 log [Al + + +

] + 4 log [HS0 ~]
4 (7)

The pH of the h y d r o l y z e d s o l u t i o n s was measured at room temperature

and as such i t i s d i f f e r e n t from the pH at which the r e a c t i o n occurs.

The change i n the d i s s o c i a t i o n c o n s t a n t of water (Table 10) i s such

t h a t the pH of the s o l u t i o n should decrease w i t h i n c r e a s i n g temperature.

T a b l e 10. Hydrolysis c o n s t a n t of water

T C° 25 60 100 150 200 250 300 350

-log K 14.0 13.05 12.21 11.65 11.30 11.18 11.19 11.33

True pH value at any temperature can be defined thermodynamically

but i t cannot be e a s i l y measured. The pH change which o c c u r s i n heating

or c o o l i n g an e l e c t r o l y t e s o l u t i o n i s due to the h y d r o l y s i s and

change i n a c t i v i t y of a l l i o n s i n s o l u t i o n . Assuming t h a t the pH of

h y d r o l y z e d s o l u t i o n s remains unchanged w i t h temperature the equilibrium

constant f o r the h y d r o l y s i s r e a c t i o n can be c a l c u l a t e d at each

temperature.
 - 47 -

R e s u l t s of the e q u i l i b r i u m h y d r o l y s i s of normal aluminum s u l p h a t e

s o l u t i o n s i n the temperature range 125-250°C are p r e s e n t e d i n Table

11 and F i g . 18. R e s u l t s i n T a b l e 7 and T a b l e 8 were a l s o used to

c a l c u l a t e the e q u i l i b r i u m c o n s t a n t s f o r h y d r o l y s i s of aluminum

s u l p h a t e s o l u t i o n s w i t h excess sulphuric acid. Calculated v a l u e s of

log K are p r e s e n t e d i n Table 12.

Table 11. Equilibrium h y d r o l y s i s of normal aluminum s u l p h a t e i n the

temperature range 125-250°C.

Temp. Aluminum i n s o l . Sulphate i n s o l . pH

°C gr/a gr/Ji

125 5.68 31.35 1.78

150 4.65 28.65 1.42

175 3.50 26.40 1.15

200 2.45 23.80 0.98

225 1.46 21.60 0.85

250 0.90 20.20 0.79

Table 12. Values of l o g K f o r the h y d r o l y s i s of aluminum s u l p h a t e

solutions with excess s u l p h u r i c a c i d at 225°C and 250°C

Init. pH 0.70 1.00 1.50 2.00 2.50 3.10

log K 2 2 5 -3.43 -2.96 -2.42 -2.16 -1.93 -1.77

-1.00 0.00 0.513 0.503 0.374 0.35

l o g K
250
- 48 -
 - 49 -

Mean e q u i l i b r i u m c o n s t a n t s f o r 225°C and 250°C were c a l c u l a t e d from

T a b l e 12 and were found to be:

log K 2 2 5 < > c = -2.44 K = 3.62 x 10

log K 2 5 0 o c = 0.302 K = 2.0

T a b l e 13 p r e s e n t s the e q u i l i b r i u m c o n s t a n t s f o r h y d r o l y s i s reaction

of aluminum s u l p h a t e i n the temperature range 125-250°C.

T a b l e 13. E q u i l i b r i u m c o n s t a n t s f o r the h y d r o l y s i s r e a c t i o n of

aluminum s u l p h a t e

1/T x 1 0 4
log K 1/T°K T°C

25.10 -18.92 1.2 x 1 0 " 1 9

125

23.60 -13.20 6.3 x I O - 1 4

150

22.30 - 8.63 2.3 x 1 0 " 9

175

21.10 - 5.05 8.9 x I O - 6

200

20.05 - 2.44 3.6 x 1 0 ~ 3

225

19.10 +• 0.302 2.0 . 250

S i n c e the p l o t of l o g K a g a i n s t 1/T g i v e s a s t r a i g h t line ( F i g . 19)

it i s most p r o b a b l e t h a t t h e r e i s o n l y one s o l i d phase i n e q u i l i b r i u m

w i t h t h e l i q u i d phase. T h e r e f o r e t h e s o l u t i o n composition i s above

the i n v a r i a n t p o i n t P ( F i g . 17) at a l l temperatures.

,9 ~^~0 3 Zi ?i 24 . ^ 5
Fig. 19.THE CHANGE OF EQUILIBRIUM
CONSTANT WITH TEMPERATURE
 - 51 -

4.4 T e r n a r y Diagrams f o r the System Al^O^-SOy-H^O

Some d a t a i s a v a i l a b l e on the h y d r o l y s i s o f b a s i c aluminum s u l p h a t e

3

at temperatures up to 220°C, but no u s e f u l d a t a i s a v a i l a b l e on

h y d r o l y s i s of a c i d aluminum s u l p h a t e s o l u t i o n s . Experimental data

from S e c t i o n 4.2 was used t o c a l c u l a t e the e q u i l i b r i u m l i q u i d composi-

t i o n i n a c i d aluminum s u l p h a t e s o l u t i o n s a t 225 and 250°C. Ternary

diagrams were c o n s t r u c t e d f o r the water c o r n e r of the A 1 0 " S 0 - H 0 2 3 3 2

system at 225 and 250°C. T a b l e s 14 and 15 show the c o m p o s i t i o n o f

the i n i t i a l and f i n a l s o l u t i o n s a t 250 and 225°C.

T a b l e 14. S o l u t i o n c o m p o s i t i o n a t 250°C

Starting l i q . comp. wt % Equil. l i q . comp. wt %

A1 0 2 3 so 3
H 02 A1 0 2 3
so 3 H 0 .
2

1 1.12 4.10 94.78 0.51 3.52 95.98

2 1.12 3.59 95.29 0.40 2.84 96.76

3 1.12 3.00 95.88 0.23 2.07 97.70

4 1.12 2.77 96.11 0.184 1.79 98.03

5 1.12 2.69 96.20 0.18 1.72 98.10

6 1.12 2.64 96.24 0.168 1.63 98.20

 - 52 -

T a b l e 15. S o l u t i o n c o m p o s i t i o n a t 225°C

Starting l i q . comp. wt % Equil. liq. comp. wt %

A1 0 2 3 so 3 H 0
2 A1 0
2 3 so 3 HgO

1 1.12 4.10 94.78 0.91 3.81 95.28

2 1.12 3.59 95.29 0.66 3.11 96.23

3 1.12 3.00 95.88 0.43 2.31 97.26

4 1.12 2.77 96.11 0.345 1.96 97.69

5 1.12 2.69 96.20 0.30 1.84 97.86

6 1.12 2.64 96.24 0.276 1.75 97.97

The d a t a from T a b l e s 14 and 15 a r e p r e s e n t e d g r a p h i c a l l y i n F i g . 20

and 21. The i n t e r s e c t i o n o f the i n i t i a l and f i n a l l i q u i d composition

l i n e s suggests the p o s s i b i l i t y o f the presence o f a second phase i n

the system a t 250 and 225°C. The second phase i s p r o b a b l y a normal

aluminum s u l p h a t e but i t c o u l d n o t be d e t e c t e d i n any o f the experiments

from the X-ray d i f f r a c t i o n p a t t e r n s o f the s o l i d . Although a number o f

experiments w i t h s o l u t i o n s o f the composition c o r r e s p o n d i n g t o the p o i n t s

A^ and A 2 i n F i g . 20 and 21 were done, the presence of a second phase

c o u l d not be unambiguously proven.

A c i d aluminum s u l p h a t e s o l u t i o n s (compositions A^ and A 2 - Figs.

20 and 21) were h y d r o l y s e d f o r predetermined times, and s o l u t i o n samples

were taken. The a u t o c l a v e and the remaining m a t e r i a l was c o o l e d t o room

temperature, and the r e s u l t i n g s o l u t i o n was a n a l y z e d . From the d i f f e r e n c e

i n s o l u t i o n compositions, the S 0 : A 1 0
3 2 3 r a t i o o f the r e - d i s s o l v e d

p r e c i p i t a t e was c a l c u l a t e d . I t was
- 53 -
- 54 -
 - 55 -

found to be s l i g h t l y increased but i t was f a r from the SO^.-AJ^O^

r a t i o of a normal s a l t .

4.5 Mechanism of the Hydrolysis of Aluminum Sulphate

In aqueous solutions aluminum sulphate i s at least p a r t i a l l y

dissociated into i t s constituents.

Al (S0 ) (aq)
2 4 3 ^ 2A1 + 3S0 4 (8)

The A l i o n i n solution w i l l react with ^ 0 to give:

Al" " " "

1 1 1
+ H0
2 * AKOH)" ^ 1
+ H +
(9)

The concentration of A1(0H) i n solution w i l l depend on the concentra-

-H-
tion of A l and H i n the i n t i a l solution. A1(0H) cation i n

solution reacts with HS0 4 ion to give the basic aluminum sulphate:

eAKOH)""" + 4HS0 " + 8H 0 —»-

1 1
4 2 3A1 0 .4S0 .9H 0 + 8H
2 3 3 2
+
(10)

22
The equilibrium.constant for reaction (9) was reported by Helgeson
-4. 75

and i t i s 10 * f o r d i l u t e solutions. Because of the change i n the

d i s s o c i a t i o n constant of water with temperature this constant w i l l

change, and become more and more p o s i t i v e as the temperature i s

increased. Helgeson gives the equilibrium constant values f o r the

reaction: i
A1(0H) >- Al + OH (11)
 - 56 -

Reaction (9) i s simply a combination of r e a c t i o n (11) and

H 0
2 - — v H +
+ 0H~ (12)

Knowing the e q u i l i b r i u m c o n s t a n t s a t temperatures up t o 300°C

for r e a c t i o n s (11) and (12) the e q u i l i b r i u m c o n s t a n t f o r r e a c t i o n (9)

can be c a l c u l a t e d from the r e l a t i o n :

log K 9 = log K 1 2 - log K n

Calculated values f o r a r e g i v e n i n T a b l e 16.

I | |

T a b l e 16. E q u i l i b r i u m constants f o r r e a c t i o n A l + R^O «-

A1(0H) + +
+ H +

Temp °C 25 50 60 100 150 200 . 250 300

log K -4.75 -3.87 -3.53 -2.26 -0.84 +0.63 +1.97 +3.31

Precipitation r e a c t i o n (10) i s a f a s t r e a c t i o n as can be seen from the

precipitation curves a t h i g h temperatures where i t reaches e q u i l i b r i u m

d u r i n g the h e a t i n g p e r i o d .

4.6 The E f f e c t o f A l k a l i M e t a l Sulphates on H y d r o l y s i s o f

Aluminum Sulphate a t 225°C

When s u l p h a t e s o f L i , Na o r K a r e p r e s e n t i n aluminum s u l p h a t e

s o l u t i o n s during h y d r o l y s i s , corresponding a l u n i t e s of the g e n e r a l form

 - 57 -

M2O.3Al2O2.4sO3.6H2O are p r e c i p i t a t e d instead of basic aluminum

sulphate. Since the s o l u b i l i t y of these compounds i s less than the

s o l u b i l i t y of basic aluminum sulphate ("Hydrogen Alunite") the

hydrolysis y i e l d s are higher and very close to 100%.

3

P.T. Davey and T.R. Scott have reported complete p r e c i p i t a t i o n

of aluminum i n 30 min.at 220°C from solutions with i n i t i a l SO^iA^O^

r a t i o of. 2.87. The r a t i o of I^SO^:Al (SO^)3

2 calculated on the basis

of aluminum present i n s t a r t i n g solution was 2.16. The precipitated

compound was of a composition corresponding to K 2 O . 3 A l 2 O 3 . 4 S O 3 . 6 H 2 O .

13

V.S. Sazhin, A.K. Zapolskii and N.N. Zakharova have studied

hydrolysis of aluminum sulphate solutions having an i n i t i a l molar

r a t i o of I^SO^iA^CSO^^ of 0.33. Concentration of aluminum sulphate

i n solution was 308 gr/& (0.9 M), having S 0 : A 1 03 2 3 r a t i o of 3.0.

Such solutions were hydrolyzed for 1 hr i n the temperature range

175-250°C. Maximum hydrolysis y i e l d at 250°C was about 82%. Their

results show the presence of two s o l i d phases. In the temperature

range 175-190°C, basic potassium-aluminum sulphates of the form

K^SO^.3AI2O3.4SO3.9H2O are precipitated. At temperatures higher

than 230°C, alunites are formed with the formula K^O .3AI2O3.4SO3.6H2O.

In the temperature range 190-230°C they have reported a mixture of the

two. In order to see the effect of a l k a l i metal sulphates on

hydrolysis of d i l u t e solutions of aluminum sulphate, solutions with

M2S0 :Al2(30^)3
4 r a t i o of about 0.5 containing 6.10 gr/£ aluminum with

S0 :A1 03
3 2 r a t i o of about 3.0 were hydrolyzed at 225°C u n t i l

equilibrium was established. ^SO^ corresponds to I^SO^, N a 2 S 0 ^ and

K S0 .
2 4
 - 58 -

4.6.1 The E f f e c t of Lithium Sulphate on Hydrolysis of Aluminum

Sulphate at 225°C

Aluminum sulphate-lithium sulphate solution containing 6.12 gr/£

aluminum, 38.30 gr/£ SO^ and 0.815 gr/£ lithium was hydrolyzed at

225°C u n t i l equilibrium was reached. The results obtained are

presented i n Table 17 and F i g . 22.

Table 17. Hydrolysis of aluminum sulphate-lithium sulphate solution

at 225°C*

I || = —
Time at A l i n s o l SO, i n s o l L i i n s o l A l prec SO, prec L i prec pH
225°C
hrs gr/£ gr/£ gr/£ gr/£ gr/£ ,gr/£

0 1.74 27.87 0.44 4.38 10.43 0.375 0.82

1 1.29 26.71 0.40 4.83 11.59 0.415 0.78

2 1.16 26.48 0.39 4.96 11.82 0.425 0.75

3 1.07 26.36 0.39 5.05 11.94 0.425 0.71

3 1.11 26.36 0.39 5.01 11.94 0.425 0.73

5 1.05 26.37 0.39 5.07 11.93 0.425 0.72

8 1.05 26.36 0.39 5.07 11.94 0.425 0.72

Starting solution: 38.30 gr/£ SO

6.12 gr/£ A l
0.815 gr/£ L i
pH = 3.05
 o
o o c
c
O Al (0 » .
x
a. •
_"
—
]o
c: o^
to
<
6.0 -I ?\
D L i
-1.0 36
0 S O 4
34
S.O'-
V PH _ 0 8 32

40 _| ;i\ V v V — _ 3 0 ^|
VO

-0.6 2 8
3.0-
26

20-j V • n n n n - 0 . 4 24 -

O O - 22 -
1.0 -
-0.2 20 •

0 1 2 3 4 5 6 7 8 9 10 II 12 13 time in hrs.
Fig. 2 2. HYDROLYSIS OF LITHIUM-ALUMINIUM SULPHATE
SOLUTION AT 2 2 5 C °
 - 60 -

The p r e c i p i t a t e d compound was analyzed (see App. I I ) and i t s composition

was found t o be L i 2 O . 3 A l 2 O 2 . 4 S O 2 . 6 H 2 O . In a f o u r component system

such as t h i s , i t i s normal to have at l e a s t two s o l i d phases i n

e q u i l i b r i u m w i t h the l i q u i d phase, but s i n c e the c o n c e n t r a t i o n o f L i +

i o n s i n s o l u t i o n i s h i g h enough to p r e c i p i t a t e a l l the aluminum p r e s e n t

i n the s t a r t i n g s o l u t i o n as l i t h i u m a l u n i t e , o n l y one s o l i d phase i s

precipitated. The X-ray d i f f r a c t i o n p a t t e r n f o r both b a s i c aluminum

s u l p h a t e and b a s i c lithium-aluminum s u l p h a t e i s almost the same, so

it is difficult to d i s t i n g u i s h between the two (see App. III-K and

III-E).

4.6.2 The E f f e c t of Sodium Sulphate on H y d r o l y s i s of Aluminum

Sulphate at 225°C.

Aluminum sulphate-sodium s u l p h a t e s o l u t i o n c o n t a i n i n g 6.12 gr/£

A l " " , 2.625 gr/£ N a

4-1 4 +
and 38.14 gr/£ S0 4
=
was h y d r o l y z e d at 225°C.

About 5.0 gr/£ of aluminum was p r e c i p i t a t e d w h i l e h e a t i n g the system

to 225°C. When the e q u i l i b r i u m was reached about 98% of the aluminum

p r e s e n t i n the i n i t i a l s o l u t i o n was precipitated as a b a s i c s a l t .

The r e s u l t s o b t a i n e d i n t h i s s e t of experiments are p r e s e n t e d i n

T a b l e 18 and F i g . 23. A n a l y s i s of p r e c i p i t a t e d s o l i d phase shows the

composition corresponding to N a 2 O . 3 A l 2 O 2 . 4 S O 2 . 6 H 2 O (see App. II). The

X-ray d i f f r a c t i o n p a t t e r n of t h i s compound i s the same as f o r b a s i c

aluminum s u l p h a t e and lithium alunite (see App. III-H).

 - 61 -

Table 18. H y d r o l y s i s of aluminum sulphate-sodium sulphate s o l u t i o n

at 225°C*

Time at A l i n s o l SO. i n s o l N a +
i n s o l A l prec SO^ prec Na prec pH
4
225°C
hrs gr/a gr/il gr/il gr/il gr/il gr/il

0 1.05 26.06 1.44 5.07 12.08 1.185 0.77

1 0.41 24.58 1.00 5.71 13.56 1.625 0.70

2 0.24 24.19 0.925 5.88 13.95 1.70 0.69

2 0.32 24.06 0.925 5.80 14.08 1.70 0.69

4 0.17 24.04 0.925 5.95 14.10 1.70 0.63

8 0.13 23.84 0.925 5.99 14.20 ' 1.70 0.63

* =
Starting solution: 38.14 gr/Jl SO^
6.12 gr/Jl A l

2.625 gr/il Na
pH = 3.09

4.6.3. The E f f e c t of Potassium Sulphate on H y d r o l y s i s of Aluminum

Sulphate at 225°C

Potassium sulphate-aluminum sulphate s o l u t i o n containing 6.12 gr/il

aluminum, 4.465 gr/£ potassium and 38.14 gr/£ SO^ was hydrolyzed at

225°C. About 97% p r e c i p i t a t i o n occurs i n heating the system to 225°C.

100% p r e c i p i t a t i o n occurs i n only a few minutes at 225°C. Results

obtained are presented i n Table 19 and F i g . 24. Thev.precipitated

compound was analyzed and i t was found to correspond to the formula

K 0.3A1 0 .4S0 .6H 0 (see App. I I ) .

2 2 3 3 2
0 I 2 3 4 5 6 7 8 9 10 II 12 13 timeinhrs.
Fig. 2 3. HYDROLYSIS OF SODIUM-ALUMINIUM SULPHATE
SOLUTION A T 2 2 5 C °
 - 63 -

T a b l e 19. H y d r o l y s i s o f aluminum s u l p h a t e - p o t a s s i u m sulphate solution

at 225°C*

Time at A l i n s o l SO, i nsol K i n sol Al p r e c SO, p r e c K prec pH

4
225°C 4
hrs gr/£ gr/£ gr/Jt gr/£ gr/£ gr/£

0 0.21 .24.06 1.61 5.91 14.08 2.855 0.69

1 o.oo • 23.54 1.51 6.12 14.60 2.955 0.67

2 0.00 23.56 1.51 6.12 14.58 2.955 0.66

3 0.00 23.54 1.51 6.12 14.60 2.955 0.66

Starting solution: 38.14 gr/£ SO^"

6.12 g r / i l A l

4.465 gr/£ K

pH = 3.09

When a l k a l i metal sulphate-aluminum s u l p h a t e s o l u t i o n s a r e

h y d r o l y z e d a t 225°C o n l y one s o l i d phase i s found t o be i n e q u i l i b r i u m

w i t h the l i q u i d phase. The s o l i d phase corresponds t o the formula

13

M 0.3A1 0 .4S0 6H 0.
2 2 3 3< 2 T h i s i s c o n t r a r y to the r e s u l t s o f V.S. S a z h i n .

I f t h e r e i s any temperature limit i n f o r m a t i o n o f M 0. 3 A 1 0 « 4S0.J. 6H 0

2 2 3 2

it should be below 225°C and not 230°C. The most probable.second phase

in such mixed s o l u t i o n s would be the b a s i c aluminum s u l p h a t e under

the c o n d i t i o n t h a t t h e r e i s Insufficient M +
p r e s e n t i n the i n i t i a l

s o l u t i o n to p r e c i p i t a t e a l l aluminum i n the form of a l u n i t e .

The reaction f o r • the hydrbthermal p r e c i p i t a t i o n of alunites

can be w r i t t e n as

ekl^ + 4HS0 " + 2M +

+ 12H.0 *• M 0.3A1.0 .4S0„.6H 0 + 16
o o H
(13) o
+

4 2 -< 2 2 3 3 2
 _: o
v •»
o c
0 - n"t~:
o
« - 6 o
« pH
O
(A
^
o
c

k
O Al
x - 36
<
5.0 A
D K
3.0 -0.8 34

0 S 0
4 - 32 -
4.0 -
V PH
2.0 -0.6 30 -

3.0 - *• • • — 28 • ON
4>-

1.0 -0.4 26 "•

2.0 -
V - 24
\ ^o—o—o
1.0 -
\ OJO -0.2 2 2 •

\ 20
O v
0.0- ^•—o—o—o-
0 I 2 3 4 5 6 7 8 9 10 11 12 time in hrs.
Fig. 24. HYDROLYSIS OF POTASSIUM—ALUMINIUM SULPHATE
SOLUTION AT 225 C°
 - 65 -

The e f f e c t of a l k a l i , metal s u l p h a t e s a l t s i s such t h a t the h y d r o l y s i s

y i e l d s are i n c r e a s e d i n the f o l l o w i n g s e r i e s K > Na > L i . This

s e r i e s i s the same i f the i o n i c r a d i i of the L i , Na, and K are compared.

Table 20 shows the i o n i c r a d i i of the i o n s i n v o l v e d i n t h i s system.

Fig. 25 shows the s t r a i g h t l i n e r e l a t i o n between the i o n i c r a d i i and

p r e c i p i t a t e d amount of aluminum i n h e a t i n g the system to 225°C.

Table 20. Ionic r a d i i of the i o n s i n v o l v e d i n the system

Element Type of Ionic radius Al prec.

Radius A° %

H 1 +
0.00 48.00

Al 3 +
0.57

Fe 3 +
0.67

Li 1 +
0.68 71.80

Fe 2 +
0.80 60.50

Cu 2 +
0.80 61.40

Na 1 +
0.98 83.00

K 1 +
1.33 96.80

4.7 The E f f e c t of D i v a l e n t M e t a l Sulphates on H y d r o l y s i s of

Aluminum Sulphate S o l u t i o n s at 225°C

As a general r u l e , i o n s of d i v a l e n t metals do not p r e c i p i t a t e

with b a s i c aluminum s u l p h a t e . Many t r i v a l e n t or q u a d r i v a l e n t metals

p r e c i p i t a t e as o x i d e s , h y d r o x i d e s or b a s i c s a l t s under the same

- 66 -
 - 67 -

c o n d i t i o n s as f o r h y d r o l y s i s of aluminum s u l p h a t e . The effect of

copper and i r o n was i n v e s t i g a t e d a t 225°C m o s t l y because of their

presence i n many l e a c h s o l u t i o n s .

4.7.1 The E f f e c t of Copper S u l p h a t e on H y d r o l y s i s of Aluminum

Sulphate S o l u t i o n s at 225°C

A copper- sulphate-aluminum s u l p h a t e s o l u t i o n c o n t a i n i n g

6.10 gr/£ aluminum, 3.58 gr/£ copper and 37.92 gr/£ SO^ was

h y d r o l y z e d at 225°C. There was p r a c t i c a l l y no copper precipitation

d e t e c t e d i n these experiments. R e s u l t s o b t a i n e d are p r e s e n t e d i n

T a b l e 21 and F i g . 26.

T a b l e 21. H y d r o l y s i s of aluminum s u l p h a t e - c o p p e r sulphate s o l u t i o n

at 225°C*

Time a t Al in sol Cu i n s o l SO. i n s o l Al prec Cu prec SO^ prec pH

4
225°C

hrs. gr/il gr/Jl gr/£ gr/jl gr/£ gr/£

0 2.35 3.56 29.02 3.75 0.02 8.90 0.94

1 1.48 3.58 26.92 4.62 0.00 11.00 0.85

2 1.23 3.57 26.32 4.87 0.01 11.60 0.82

4 1.12 3.56 26.06 4.98 0.02 11.86 0.82

6 1.10 3.58 26.06 5.00 0.00 11.86 0.82

Starting solution: 6.10 gr/£ Al

3.58 gr/£ Cu

37.92 gr/£ S0 4

pH = 3.0
 ON
00
I

0 I 2 3 4 5 6 7 8 9 10 I I 12 time in hrs.
Fig.26. HYDROLYSIS OF COPPER-ALUMINIUM SULPHATE
SOLUTION AT 2 2 5 C°
 - 69 -

4.7.2 The Effect of Ferrous Sulphate on Hydrolysis of Aluminum

Sulphate Solutions at 225°C

A ferrous sulphate-aluminum sulphate solution containing

6.12 gr/£ aluminum, 3-26 gr/SL iron and about 38.29 gr/£ SO^ -
was

hydrolyzed at 225°C. Some iron was precipitated i n the form of ¥e^0^

due to atmospheric oxidation of ferrous i r o n . Results

obtained i n this set of experiments are presented i n Table 22 and F i g .

27. The increased p r e c i p i t a t i o n of aluminum can be attributed to the

common ion e f f e c t . The bivalent ions are not compatible with the

alunite l a t t i c e and do not tend to replace the hydrogen ions i n basic

3

aluminum sulphate.. T.R. Scott has reported that no contamination

of basic aluminum sulphate occurs i n the presence of Mg, Cd, Zn and Ni

even at high concentrations.

Table 22. Hydrolysis of aluminum sulphate-ferrous sulphate solution

at 225°C*

Time at A l i n s o l Fe i n s o l SO. i n s o l A l prec Fe prec SO, prec pH

hrs gr/£ gr/£ gr/Jl . gr/£ gr/Jl gr/Jl

0 2.42 2.69 29.44 3.70 0.57 8.85 0.97

1 1.57 2.68 27.48 4.55 0.58 10.81 0.82

2 1.40 2.69 27.04 4.72 0.57 11.25 0.80

4 1.15 2.66 26.42 4.97 0.60 11.87 0.82

6 1.12 2.69 26.40 5.00 0.57 11.89 0.80

Starting solution: 6.12 gr/£ A l ; 3.26 gr/l Fe; 38.29 gr/£ SO

pH = 3.0
 I8 -

-i 1 i — J 1 i ' « » ' • ' • ' ' '

0 I 2 3 4 5 6 7 8 9 10 II 12 time in hrs.

Fig. 27 HYDROLYSIS OF IRON-ALUMINIUM SULPHATE

SOLUTION AT 22 5C°
 - 71 -

4.8 A p p l i c a t i o n of the H y d r o l y s i s P r o c e s s

B a s i c aluminum s u l p h a t e of the form 3 A 1 0 . 4 S 0 . 9 H 0 i s the

2 3 3 2

product o f h i g h temperature h y d r o l y s i s o f aluminum s u l p h a t e s o l u t i o n s

w i t h a wide range of i n i t i a l S O ^ A l ^ ratios. A b a s i c s a l t of the

form M2O.3Al2O2.4sO2.6H2O i s a h i g h temperature h y d r o l y s i s p r o d u c t of

aluminum s u l p h a t e s o l u t i o n s c o n t a i n i n g a l k a l i metals ( L i , Na or K ) .

Thermal decomposition o f such b a s i c s a l t s y i e l d s alumina as a f i n a l

product which can be used f o r aluminum p r o d u c t i o n . Thermal decomposi-

t i o n of a few samples of b a s i c aluminum s u l p h a t e was f o l l o w e d by

D.T.A. A t y p i c a l D.T.A. c u r v e i s shown i n F i g . 28. The first

endothermic peak i n the temperature range 200-400°C corresponds to the

l o s s of i n t e r s t i t i a l l a t t i c e w a t e r . 9
The peak a t about 450°C c o r r e s p o n d s

to the d e h y d r o x y l a t i o n p r o c e s s . T h i s p r o c e s s i s completed at

temperatures around 600°C where anhydrous b a s i c aluminum s u l p h a t e

exists. At temperatures above 600°C, SO^, SO2 and O2 are e v o l v e d

y i e l d i n g amorphous alumina which subsequently c r y s t a l l i z e s to y-alumina

at h i g h e r temperatures. Y Alumina
-
i s t r a n s f o r m e d to a-alumina a t

temperatures of 1000°C and h i g h e r . A few samples of K2O.3Al2O2.4SO2-

6H2O were c a l c i n e d at about 1000°C f o r 2 h r s . The decomposition of

these samples was f o l l o w e d by the weight l o s s . R e s u l t s of one of the

decomposition experiments i s shown below.

1.0811 gr K 0 . 3 A 1 0 . 4 S 0 . 6 H 0
2 2 3 3 2 > 0.5857 gr K S 0 2 4 + Al 0 +

, sulphurous
t
gases

0.5857 gr K 2 S 0 4 4- A 1 0 2 3 iffg^ 0.365 gr A 1 0 2 3

o

200 400 600

Fig. 2 8 . D . T . A . OF 3AI2O34SO39H2O
 - 73 -

In leaching processes at high temperatures where aluminum i s

present i n solution i t p r e c i p i t a t e s as a basic s a l t i n autoclaves and

pipelines"'"''" which necessitates "forced" shutdowns of the process i n

order to clean autoclaves and/or p i p e l i n e s . With increasing sulphuric

acid concentration and decreasing temperature the s o l u b i l i t y of basic

aluminum sulphate was found to increase. Therefore running concentrated

solutions of sulphuric acid through the system at low temperatures

should dissolve the p r e c i p i t a t e .

In dump leaching solutions aluminum i s present as aluminum

sulphate. I f aluminum i s not recovered the v i s c o s i t y of the solution

w i l l increase. To remove the, aluminum from solution, a part of the

liquor after cementation can be treated i n an autoclave to p r e c i p i t a t e

basic aluminum sulphate. Liberated acid from the hydrolysis can be

recycled to the heap.

 - 74 -

5. CONCLUSIONS

1. D i l u t e s o l u t i o n s of normal and a c i d aluminum s u l p h a t e h y d r o l y z e

when heated above 125°C to y i e l d a basic salt of the nominal c o m p o s i t i o n

3A1 0 ,4S0 .9H 0.

2 3 3 2

2. Hydrolysis yield i s a f u n c t i o n of the temperature and initial

concentration of s u l p h u r i c a c i d i n s o l u t i o n .

3. Only one s o l i d phase was found to be i n e q u i l i b r i u m w i t h the

l i q u i d phase i n the temperature r e g i o n 125-250°C, but t h e r e are

some i n d i c a t i o n s t h a t a l e s s b a s i c s a l t may e x i s t i n the system.

4. When L i , Na or K i o n s are p r e s e n t i n s o l u t i o n s of aluminum

s u l p h a t e a b a s i c s a l t of the form M 0 . 3 A 1 0 « 4 S 0 . 6 H 0
2 2 3 3 2 is precipitated.

5. The h y d r o l y s i s y i e l d s are i n c r e a s e d i n the p r e s e n c e of a l k a l i

m e t a l s u l p h a t e s i n the f o l l o w i n g s e r i e s : K > Na > L i .

I|

6. Aluminum can be s e l e c t i v e l y p r e c i p i t a t e d i n the presence of Cu

and Fe" " " as 3 A 1 0

1 1
2 3 > 4S0 -9H 0.
3 2

7. Both b a s i c aluminum s u l p h a t e and a l u n i t e s can be c a l c i n e d a t

temperatures above 1000°C to y i e l d alumina.

 - 75 -

APPENDIX I

SOLUBILITY OF ALUMINUM SULPHATE

I-A S o l u b i l i t y o f A l ( S O . K i n water

Temp. °C 20 30 40 50 60 70 80 90 100

gr A 1 ( S 0 )
2 4 3

26.7 28.8 31.4 34.3 37.2 39.8 42.2 44.7 47.1

100 gr s a t .
sol.

I-B Solubility o f aluminum s u l p h a t e i n aqueous s o l u t i o n s of

sulpuric a c i d a t 25°C.

gr A1 (S0 )
2 4 3

27.82 29. 21 26.2 19.5 11.6 4. 8 1. 5 1.0 2.3 4.0

100 g r s a t . s o l .

gr H S 0
2 4

0.0 5. 73 10.0 20.0 30.0 40. 0 50. 0 60.0 70.0 75.0

100 g r s a t . sol.

I-C Solubility o f aluminum s u l p h a t e i n aqueous 10% H SO

Temp. ° C 30 42 50

gr A1 (S0 )
2 4 3

14.52 16.45 18.77

100 g r s a t . sol.
 - 76 -

APPENDIX I I

ANALYSIS OF THE SOLID PHASES

Time a t Temp. % Al 0 % SO % M0 0 % HO Starting

hrs. C pH

6.00 175 38.7 37.2 - 24.1 3.10

10.00 175 38.5 39.6 - 21.9 3.10
16.30 175 38.7 39.7 - 21.6 3.10
4.0 200 38.6 39.5 - 21.9 3.10
6.0 200 38.8 39.9 - 21.3 3.10
18.00 200 38.7 40.1 - 21.2 3.10
1.00 225 38.8 40.2 - 21.0 3.10
5.00 225 38.9 40.8 - 20.3 3.10
16.00 225 39.1 41.6 - 19.3 3.10
0.00 250 38.8 40.3 - 20.9 3.10
1.00 250 38.7 40.2 - 21.1 3.10
3.30 250 39.0 40.5 - 20.05 3.10
6.30 250 39.2 40.9 - 19.9 3.10
6.00 225 39.0 . 40.6 - 20.4 2.5
6.00 225 38.7 40.6 - 20.7 2.0
6.00 225 38.9 40.8 - 20.3 1.5
6.00 225 . 38.9 40.2 - 20.9 1.0
6.00 225 39.2 41.7 - 19.1 0.70
4.00 250 38.9 40.6 - 20.5 2.5
4.00 250 38.8 40.7 - 20.5 2.0
4.00 250 38.9 41.2 - 19.9 1.5
4.00 250 39.2 41.6 - 19.20 1.0
4.00 250 38.9 40.8 - 20.3 0.70
Li 0 2

3.00 225 39.90 42.00 4.00 14.10 3.05

Na 0 2

2.00 225 38.40 40.10 7.70 13.80 3.09

8.00 225 38.50 40.20 7.80 13.50 3.09

K 0
2

0.00 225 37.05 38.39 11.36 13.20 3.09

0.00 225 36.91 38.91 11.38 12.80 3.09
1.00 225 37.12 38.48 11.30 13.10 3.09
 - 77 -

APPENDIX I I I

X-RAY DIFFRACTION PATTERNS

III-A D i f f r a c t i o n pattern of the p r e c i p i t a t e obtained at 150°C

Prec. obtained i n 10 hrs. Prec. obtained i n 16 hrs

o o
d A° I/x d A° I/T

5.71 7 5.71 7
5.03 2 5.03 2
3.55 5 3.57 5
3.01 1 3.01 1
2.27 4 2.27 4
1.909 3 1.908 3
1.76 5 1.755 5
1.654 7 1.659 7
1.566 7 1.570 7
1.496 5 1.500 5
1.325 7 1.329 7
1.290 6 1.299 6
1.220 7 1.217 7
1.171 7 1.171 7
1.150 7 1.147 7

III-B X-ray d i f f r a c t i o n patterns of the p r e c i p i t a t e obtained at 175

Prec. obtained i n 2 hrs. Prec. obtained i n 16.5 hrs

d A° I/I d A°
0 1 / T
o

5.71 7 5.75 1
5.034 2 5.12 2
3.56 5 3.56 5
3.01 :
1 3.04 1
2.87 7
2.486 8
2.27 4 2.30 4
2.22 8
1.908 3 1.920 3
1.757 5 1.770 5
1.654 7 1.654 7
1.566 7 1.570 7
1.495 5 1.500 5
1.380 8
1.325 7 1.330 7
1.293 6 .1.290 6
1.219 7 1.217 7
1.174 7 1.172 7
1.150 7 1.150 7
 - 78 -

III-C X-ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained at 200°C.

Prec. obtained i n 18 hrs.

d A° . I/I

5.72 7
5.03 2
3.56 5
3.04 1
2.87 7
2.27 4
2.22 8
1.910 3
1.756 •5
1.654 7
1.565 7
1.490 5
1.387 8
1.290 6
1.217 7
1.171 7
1.151 7

III-D X-ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained at 225°C

Prec. obtained i n 3 hrs at 225°G

d A° I 7 I
0
d A° I/I

5.61 8 1.736 6
5.02 2 1.666 8
4.80 2 1.641 8
3.43 6 1.550 8
3.03 1 1.546 8
2.932 1 1.479 4
2.806 4 1.4227 8
2.440 8 1.362 8
2.304 4 1.316 8
2.241 3 1.281 4
2.191 8 1.205 8
1.925 8 1.195 8
1.880 3 1.161 8
1.767 8 1.132 8
1.758 6
 - 79 -

III-E X-ray d i f f r a c t i o n p a t t e r n of the p r e c i p i t a t e obtained at 250°C

Prec. obtained i n 0.0 h r s . Prec. obtained i n 3.5 h r s .

d A° d A° d A° d A°
^ 0 I / T
o I / x
o l / 1
o
5.61 8 1.765 8 5.61 8
4.02 2 1.736 6 5.01 2 1.742 6
4.80 2 1.665 8 4.85 2 1.646 8
4.27 8 1.557 8 - 1.555
3.40 6 1.479 4 3.46 6 1.483 4
3.01 1 1.424 8 3.01 1 -
2.91 1 1.367 8 2.95 1 1.369 8
2.79 4 1.317 8 2.81 4 1.317 8
2.45 8 1.286 4 2.46 8 1.286 4
2.296 4 1.208 8 - 1.208 8
2.24 3 1.200 8 2.24 3 -
2.187 8 1.167 8 1.895 8 1.167 8
1.929 8 . 1.138 8 1.139 8
1.879 3

III-F X-ray d i f f r a c t i o n pattern of the p r e c i p i t a t e obtained from

from FeSO -Al„(SO s o l u t i o n at 225°C

4 2

Prec. obtained i n 4 . 0 h r s at 250°C

d A° d A° I/I
1 / T
o
5.08 2 1.558 4
4.80 2 1.501 5
3.03 1 1.481 2
2.915 1 1.423 5
2.294 5 1.371 3
2.234 1 1.314 4
1.918 4 1.209 3
1.888 2 1.1969 5
1.768 - 5 1.1867 5
1.737 2 1.1364 5
1.637 4 1.1054 5
 - 80 -

III-G X-ray d i f f r a c t i o n pattern of potassium alunite obtained at

225°C

Prec. obtained inO.Ohrs. at 225°C

d A° I/I d A° I/I r

5.71 5 1.560 8
5.01 2 1.546 8
3.49 3 1.489 3
3.01 1 1.422 8
2.90 8 1.380 8
2.47 8 1.316 8
2.29 3 1.281 5
2.20 5 1.205 5
1.888 2 1.161 6
1.736 2 1.132 6
1.641 8

III-H. X-ray d i f f r a c t i o n pattern of sodium alunite obtained at 225°C

Prec. obtained i n 2.0 hrs. at 225°C

d A° d A°
X / I
0

5.70 5 1.746 2
5.01 2 1.644 8
3.496 3 1.554 8
3.01 1 1.538 8
2.91 8 1.505 3
2.45 8 1.281 5
2.212 3 1.205 5
1.896 2 1.161 6

III-K X-ray d i f f r a c t i o n pattern of lithium alunite obtained at 225°C

Prec. obtained i n 3.0 hrs. at 225°C

d A° :
Wo d A° w„
5.68 :
5 1.736 2
5.01 2 1.641 8
3.491 3 1.554 8
3.01 1 1.535 8
2.90 8 1.489 3
2.44 8 1.281 5
2.20 3 1.205 5
1.887 2 1.161 6
 - 81 -

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866-868.
 - 82 -

16. V.S. Sazhin, A.K. Z a p o l s k i i , N.N. Zakharova and A.I. Volkovska,

Ukr. Khim. Zh. 1966, 32 (1), 95-100.

17. A.K. Z a p o l s k i i , Ukr. Khim. Zh. 33 (8), 805-809 (1967).

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Ukr. Khim. Zh. 32 (11), 1222-7 (1966).

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Vol. 12 (1955), 308-318.

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