Thermo. Titr. Application Note No.

H-026
Title:

Determination of caustic, carbonate and

alumina in Bayer Process liquors

Scope:

Determination of caustic, carbonate and alumina in Bayer

Process liquors using a method based on procedures
developed by Watts-Utley1 and VanDalen-Ward2
1. H. L. Watts and D. W. Utley, Anal. Chem. 28, 1731
(1956)
2. E. VanDalen and L. G. Ward, Anal. Chem. 45, 2248
(1973)

Principle:

An aliquot of alumina refinery sodium aluminate liquor is

treated with sodium potassium tartrate solution to complex
aluminate and release one mole hydroxyl for each mole
aluminate present. The total hydroxyl content of the liquor
(total caustic) and the carbonate content is determined
by titration with standard hydrochloric acid.
Al (OH ) 4 + n(C 4 H 4O6 ) 2 Al (OH ) 3 (C 4 H 4O6 ) 2n + OH
CO 32 + H + HCO 3
A second titration is carried out contiguously with the first
to determine the aluminate content (as alumina)
immediately thereafter. This second titration is preceded
by the addition of potassium fluoride solution, which
destroys the alumino-tartrate complex, forming an
insoluble potassium sodium aluminium fluoride and
releasing three moles of hydroxyl for each mole of
aluminate.
Al (OH )3 (C 4 H 4O6 ) 2n + 6F 3OH + n(C 4 H 4O6 )2 + AlF63
This hydroxyl content is determined again by the standard
hydrochloric acid titrant.
The entire two-titration sequence is carried out
automatically.

Reagents:

Standard 1.5 mol/L HCl solution

Potassium sodium tartrate solution, 450g/L
Potassium fluoride solution, 600g/L (neutralized with
NaOH to faint pink with phenolphthalein)

Method:

Basic Experimental Parameters:

Data rate (per second)

10

Titrant delivery rate (mL/min.)

2.5

No. of exothermic endpoints

2, 1

Data smoothing factor

45

Procedure: An aliquot of liquor is pipetted into a titration

vessel, and treated with 10mL potassium sodium tartrate
solution. The total liquid volume is made to approximately
25mL and the titration sequence commenced. The first
titration (caustic and carbonate) stops automatically
after the bicarbonate endpoint is detected. The second
titration sequence (alumina) begins automatically with
the addition of 10mL potassium fluoride solution. A brief
delay is programmed; to allow full reaction. The liberated
hydroxyl ions are then titrated.
Results:

Calculations:

Replicate analysis (n=10) of alumina refinery digestion

feed liquor
Total Caustic (C) as g/L Na2CO3

343.10.37

Total Soda (S) as g/L Na2CO3

409.10.65

Alumina (A) as g/L Al2O3

125.30.13

A/C

0.3650.0006

C/S

0.8390.013

(see Titration Plots below for an explanation of terms)

Total Caustic " C " Na2CO3 g / L =
Total Soda " S " Na2CO3 g / L =

Al 2O 3 " A" g / L =

((B A) M HCl 105.99)

Aliquot , mL 2

((C B ) M HCl 105.99 )

+ TC
Aliquot , mL

(((F E ) + (D B )) M HCl 101 .96 )

( Aliquot , mL 6 )

Thermometric Titration Plots:

A
B
C
D

Fig. 1. First titration in sequence

A = First titration blank volume, mL
B = Total caustic titre volume, mL
C = Total caustic + bicarbonate titre, mL
D = Total volume dispensed, mL
E
F

Fig. 2. Second titration in sequence

E = Second titration blank volume, mL
F = Alumina titre, mL
Legend:
Red = solution temperature curve
Green = first derivative curve
Black = second derivative curve