This document describes a method for determining caustic, carbonate, and alumina content in Bayer process liquors using thermometric titration. An aliquot of the liquor is first titrated with HCl to determine total caustic and carbonate content. Then, potassium fluoride is added to destroy aluminum complexes and release hydroxyl ions, which are titrated to determine alumina content. The method was tested on a digestion feed liquor and found to accurately measure caustic at 343.1±0.37 g/L Na2CO3, total soda at 409.1±0.65 g/L Na2CO3, and alumina at 125.3±0.13 g/L Al2O3
This document describes a method for determining caustic, carbonate, and alumina content in Bayer process liquors using thermometric titration. An aliquot of the liquor is first titrated with HCl to determine total caustic and carbonate content. Then, potassium fluoride is added to destroy aluminum complexes and release hydroxyl ions, which are titrated to determine alumina content. The method was tested on a digestion feed liquor and found to accurately measure caustic at 343.1±0.37 g/L Na2CO3, total soda at 409.1±0.65 g/L Na2CO3, and alumina at 125.3±0.13 g/L Al2O3
This document describes a method for determining caustic, carbonate, and alumina content in Bayer process liquors using thermometric titration. An aliquot of the liquor is first titrated with HCl to determine total caustic and carbonate content. Then, potassium fluoride is added to destroy aluminum complexes and release hydroxyl ions, which are titrated to determine alumina content. The method was tested on a digestion feed liquor and found to accurately measure caustic at 343.1±0.37 g/L Na2CO3, total soda at 409.1±0.65 g/L Na2CO3, and alumina at 125.3±0.13 g/L Al2O3
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
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