METTLER TOLEDO Application M466A-2010

Aluminum Content in Aluminum Ore (Bauxite) – Bayer Liquor

Determination of free alkali and aluminum content in aluminum ore (Bauxite) by potentiometric titration
with hydrochloric acid according to the Bayer procedure. The titration is monitored with a pH glass
combined sensor.

Sample 5 mL alkaline digestion solution Preparation and Procedures

from original aluminum ore
(Bayer Liquor, 30.23 g/500 mL)
Compound Aluminum trihydroxide, Al(OH)3
M = 78.00 g/mol, z = 3
Sodium hydroxide, NaOH
M = 40.00 g/mol, z = 1
Chemicals 25% Na-gluconate, NaC6H11O7
30% Potassium fluoride, KF
Deionized water
(see Preparation and
Titrant Hydrochloric acid, HCl
c(HCl) = 1 mol/L
c(HCl) = 0.1 mol/L
Standard Tris(hydroxymethyl)-
aminomethane, THAM
Indication DGi115-SC
CAUTION:
Work in a fume hood and wear gloves and safety
goggles.
- Weight in about 30 gr into a 600 mL
Erlenmeyer flask.
- Add 350 mL 7 mol/L NaOH and cover it with a
watch glass.
- Heat the sample on a heating plate set at
200°C, and keep it boiling while continuously
stirring for at least 4 hours.
- The alumina is first converted into aluminum
hydroxide, Al(OH)3, and further to [Al(OH)4]-
which is dissolved in the hydroxide solution.
- Some components are not dissolved; these are
mainly insoluble iron hydroxide compounds.
- Let the solution cool down; prepare a 500 ml
volumetric flask with a glass funnel and a paper
filter to avoid the solid impurities.
- Filter the cooled solution into the 500 mL
volumetric flask.
- Wash the paper filter with 100 mL 7 M NaOH.

Chemistry OH- + H3O+ → 2 H2O
see “Comments” for more
detailed information
Calculation Free Caustic NaOH (g/L):
R1 = (Q-Q2)*C/m ; C=M/z
Free Carbonate CaCO3 (g/L):
R2 = Q2*C/m ; C=M/z
Aluminum hydroxide Al(OH)3 (g/L):
R3 = (Q[2]+QEX)*C/m ;
C = M/z, M = 78.00 , z = 3
(see “Comments”)
Waste After neutralization dispose the
disposal sample solution as heavy
metals.
Author, Cosimo De Caro
MSG Anachem, July 2010
Version
- Mix well and fill up to the mark with deionized
water, and mix again. Note: Temperature can
increase again; thus, filling with water may be
necessary again.
- 5 mL sample solution is added to a titration
beaker together with 35 mL deion. water.
Remarks
- Rinsing and conditioning of the pH sensor is
crucial to achieve accurate and precise results.
In fact, the pH sensor is titrating in a strong
alkaline solution (pH > 12).
- The parameters have been optimized for this
specific sample solution. It may be necessary
to adapt the method to your sample.
- The %-content Al2O3 is calculated from the
mg/g-content Al(OH)3 (see R4) by multiplying it
with a conversion factor from the ratio between
M(Al2O3) and M(Al(OH3)) (see R5).

METTLER TOLEDO Page 1 of 7 Titration Application M466A-2010

 Instruments - T70 / T90 Titration Excellence
- Analytical Balance, e.g. XP205
- Precision Balance, e.g. MS6002S
- Rondo 20 sample changer

Accessories - 3 additional dosing units

- 2 x 10 mL DV1010 burette, 2 x 20 ml DV1020 burette
- PP Titration beakers ME-101974
- LabX pro titration software

Results

No. Comment / ID Start time Sample size and results

1/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 08:30:39 R1 = 279.72 g/L Free Caustic NaOH
R2 = 83.60 g/L Free Carbonate CaCO3
R3 = 18.42 g/L Content Al(OH)3 (g/L)
R4 = 304.71 mg/g Content Al(OH)3 (mg/g)
R5 = 39.83 % Content Al2O3 (%)
2/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 08:47:48 R1 = 276.73 g/L Free Caustic NaOH
R2 = 85.45 g/L Free Carbonate CaCO3
R3 = 18.19 g/L Content Al(OH)3 (g/L)
R4 = 300.89 mg/g Content Al(OH)3 (mg/g)
R5 = 39.33 % Content Al2O3 (%)
3/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 09:04:36 R1 = 275.96 g/L Free Caustic NaOH
R2 = 82.50 g/L Free Carbonate CaCO3
R3 = 18.10 g/L Content Al(OH)3 (g/L)
R4 = 299.43 mg/g Content Al(OH)3 (mg/g)
R5 = 39.14 % Content Al2O3 (%)
4/6 +25 mKL HO / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 09:21:20 R1 = 275.76 g/L Free Caustic NaOH
R2 = 85.72 g/L Free Carbonate CaCO3
R3 = 18.18 g/L Content Al(OH)3 (g/L)
R4 = 300.74 mg/g Content Al(OH)3 (mg/g)
R5 = 39.31 % Content Al2O3 (%)
5/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 09:38:06 R1 = 274.60 g/L Free Caustic NaOH
R2 = 84.16 g/L Free Carbonate CaCO3
R3 = 18.21 g/L Content Al(OH)3 (g/L)
R4 = 301.19 mg/g Content Al(OH)3 (mg/g)
R5 = 39.37 % Content Al2O3 (%)
6/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3
-- 22.07.2010 09:54:50 R1 = 276.91 g/L Free Caustic NaOH
R2 = 85.52 g/L Free Carbonate CaCO3
R3 = 18.38 g/L Content Al(OH)3 (g/L)
R4 = 303.94 mg/g Content Al(OH)3 (mg/g)
R5 = 39.73 % Content Al2O3 (%)
Statistics

Rx Name n Mean value Unit s srel [%]

R1 Free Caustic NaOH 6 276.61 g/L 1.729829 0.625

R2 Free Carbonate CaCO3 6 84.49 g/L 1.292786 1.530
R3 Content Al(OH)3 (g/L) 6 18.25 g/L 0.125167 0.686
R4 Content Al(OH)3 (mg/g) 6 301.82 mg/g 2.048743 0.679
R5 Content Al2O3 (%) 6 39.45 % 0.267806 0.679

METTLER TOLEDO Page 2 of 7 Titration Application M466A-2010

 Titration curve (1st Titration: NaOH and carbonate)

Sample 1/6 22.07.2010 08:30

Table of measured values (1st Titration: NaOH and carbonate)

Volume Increment Signal Change 1st derive. Time Temperature
mL mL pH pH pH/mL s °C
------------------------------------------------------------------------------------------------------------------------------------------------------------------------
0.000 NaN 13.542 NaN NaN 0 25.0
17.143 17.143 13.295 -0.247 NaN 20 25.0
25.714 8.571 13.024 -0.271 NaN 57 25.0
30.000 4.286 12.842 -0.182 NaN 63 25.0
30.200 0.200 12.794 -0.048 NaN 82 25.0
30.400 0.200 12.781 -0.013 -0.06 85 25.0
... ... ... ... ... ... ...
39.011 0.088 11.242 -0.070 -0.86 220 25.0
39.151 0.140 11.114 -0.128 -0.92 224 25.0
EQP1 39.219895 11.049 NaN -0.93 NaN NaN
39.248 0.097 11.023 -0.091 -0.93 227 25.0
39.354 0.106 10.922 -0.101 -0.88 230 25.0
39.460 0.106 10.826 -0.096 -0.84 234 25.0
39.579 0.119 10.735 -0.091 -0.79 236 25.0
39.736 0.157 10.618 -0.117 -0.72 240 25.0
39.876 0.140 10.526 -0.092 -0.66 243 25.0
40.056 0.180 10.404 -0.122 -0.60 272 25.0
40.202 0.146 10.321 -0.083 -0.54 275 25.0
40.402 0.200 10.219 -0.102 -0.48 278 25.0
40.602 0.200 10.044 -0.081 -0.41 284 25.0
41.002 0.200 9.968 -0.076 -0.41 287 25.0
41.202 0.200 9.879 -0.089 -0.41 290 25.0
41.402 0.200 9.797 -0.082 -0.41 293 25.0
41.602 0.200 9.712 -0.085 -0.42 296 25.0
41.802 0.200 9.627 -0.085 -0.43 299 25.0
42.002 0.200 9.542 -0.085 -0.45 302 25.0
42.202 0.200 9.442 -0.100 -0.50 305 25.0
42.402 0.200 9.338 -0.104 -0.57 309 25.0
42.595 0.193 9.228 -0.110 -0.67 312 25.0
42.758 0.163 9.109 -0.119 -0.81 315 25.0
42.868 0.110 9.015 -0.094 -0.93 318 25.0
42.971 0.103 8.918 -0.097 -1.11 321 25.0
43.069 0.098 8.811 -0.107 -1.35 324 25.0
43.150 0.081 8.701 -0.110 -1.64 327 25.0
43.211 0.061 8.600 -0.101 -1.94 330 25.0
43.261 0.050 8.493 -0.107 -2.29 333 25.0
43.298 0.037 8.401 -0.092 -2.60 336 25.0
43.334 0.036 8.302 -0.099 -2.93 339 25.0
43.368 0.034 8.191 -0.111 -3.27 342 25.0
43.394 0.026 8.111 -0.080 -3.47 345 25.0
EQP2 43.404282 NaN 8.071 NaN -3.47 NaN NaN
43.429 0.035 7.975 -0.136 -3.43 348 25.0
43.450 0.021 7.895 -0.080 -3.22 352 25.0
43.477 0.027 7.813 -0.082 -2.91 356 25.0
43.520 0.043 7.691 -0.122 -2.54 360 25.0
43.559 0.039 7.606 -0.085 -2.25 365 25.0
43.620 0.061 7.484 -0.122 NaN 371 25.0
43.676 0.056 7.395 -0.089 NaN 376 25.0
43.756 0.080 7.284 -0.111 NaN 381 25.0
43.842 0.086 7.187 -0.097 NaN 387 25.0
43.952 0.110 7.085 -0.102 NaN 393 25.0

METTLER TOLEDO Page 3 of 7 Titration Application M466A-2010

 Titration curve (2nd Titration: Aluminum)

Sample 1/6 22.07.2010 08:30

Table of measured values (2nd Titration: Aluminum)

Volume Increment Signal Change 1st deriv. Time Temperature

mL mL mV mV mV/mL s oC
---------------------------------------------------------------------------------------------------------------------------------------------------------------------
0.000 NaN -191.9 NaN NaN 0 25.0
0.005 0.005 -191.7 0.2 NaN 3 25.0
0.010 0.005 -191.6 0.1 NaN 6 25.0
0.022 0.012 -191.3 0.3 NaN 9 25.0
0.052 0.030 -190.4 0.9 NaN 12 25.0
0.127 0.075 -188.4 2.0 26.57 15 25.0
0.315 0.188 -183.7 4.7 24.46 19 25.0
0.515 0.200 -178.8 4.9 23.88 23 25.0
0.715 0.200 -174.2 4.6 23.24 26 25.0
0.915 0.200 -169.8 4.4 23.22 31 25.0
1.115 0.200 -164.8 5.0 23.99 35 25.0
1.315 0.200 -159.6 5.2 24.70 38 25.0
1.515 0.200 -155.2 4.4 26.05 42 25.0
1.715 0.200 -149.3 5.9 27.88 46 25.0
1.915 0.200 -143.2 6.1 30.89 50 25.0
2.115 0.200 -137.1 6.1 36.57 54 25.0
2.315 0.200 -128.8 8.3 45.60 58 25.0
2.503 0.188 -119.9 8.9 59.88 61 25.0
2.650 0.147 -110.6 9.3 78.62 65 25.0
2.746 0.096 -102.7 7.9 96.22 68 25.0
2.819 0.073 -96.1 6.6 111.74 72 25.0
2.900 0.081 -85.7 10.4 130.48 76 25.0
2.944 0.044 -80.1 5.6 144.01 79 25.0
EQP1 3.002191 NaN -70.0 NaN 158.53 NaN NaN
3.006 0.062 -69.3 10.8 158.46 83 25.0
3.040 0.034 -62.2 7.1 154.14 86 25.0
3.072 0.032 -57.5 4.7 139.57 90 25.0
3.150 0.078 -46.9 10.6 121.06 95 25.0
3.213 0.063 -40.0 6.9 107.18 100 25.0
3.305 0.092 -31.7 8.3 NaN 106 25.0
3.413 0.108 -23.8 7.9 NaN 111 25.0
3.546 0.133 -14.9 8.9 NaN 116 25.0
3.679 0.133 -7.8 7.1 NaN 121 25.0
3.862 0.183 0.7 8.5 NaN 126 25.0

METTLER TOLEDO Page 4 of 7 Titration Application M466A-2010

 Comments
Principle:

 Bauxite contains approximately 30 – 54% alumina (Al2O3). The rest mainly consists of silica, iron
oxides, and titanium dioxide.

 During the Bayer process bauxite is digested by washing with a hot solution of sodium hydroxide,
NaOH, at 175°C. The alumina is first converted into aluminum hydroxide, Al(OH)3, which
subsequently dissolves in the hydroxide solution according to the chemical equation:

Al2O3 + 2 OH- + 3 H2O → 2 [Al(OH)4]-

The resulting, strong alkaline solution is called “Bayer liquor”.

Left: Bauxite powder Middle and right: Digested bauxite solution (Bayer liquor).
Note that the digested solution is turbid due to the presence of precipitated iron componds (iron hydroxide).

Titration of Bayer liquor with hydrochloric acid:

 Addition of excess sodium gluconate (NaGluc):
Al(OH)4- + NaGluc → Al(OH)3Gluc- + NaOH
 Titration with 1 mol/L hydrochloric acid, HCl:
1st Equivalence point:
OH- + H3O+ → 2 H2O
2- +
CO3 + H → HCO3-
2nd Equivalence point:
HCO3- + H3O+ → CO2 + 2 H2O
 Addition of excess potassium fluoride:
Al(OH)3Gluc- + 6KF → K3AlF6 + 3KOH + Gluc-
 The released KOH is titrated with 1 mol/L HCl:
OH- + H3O+ → 2 H2O

Digestion of bauxite:
Generally, a freshly prepared NaOH solution does not contain carbonate. Thus, only one equivalence
point can be detected in the first titration with HCl. Carbonate is formed in alkaline solution due to
intake of CO2 during a long exposition time to air. To reproduce two equivalence points, the synthetic
Bayer liquor was spiked with 10 mL sodium carbonate solution (approx. 3 g Na2CO3/60 mL).

METTLER TOLEDO Page 5 of 7 Titration Application M466A-2010

 Method
Concentration [mol/L] 30
001 Title Volume [mL] 10
Type General titration Dosing rate [ml/min] 60
Compatible with T70 / T90 Condition No
ID m466
Title Aluminum content in bauxite 008 Stir
Author Administrator Speed [%] 30
Date/Time 23.07.2010 16:23:20 Duration [s] 180
Modified at 23.07.2010 16:23:20 Condition No
Modified by Administrator
Protect No 009 Titration (EQP) [2]
SOP None Titrant
Titrant HCl
002 Sample Concentration [mol/L] 1
Number of IDs 1 Sensor
ID 1 -- Type pH
Entry type Fixed volume Sensor DG115-SC
Volume [ml] 5.0 Unit mV
Density 1.0 g/mL Temperature acquisition
Correction factor 1.0 Temperature acquisition No
Temperature 25.0°C Stir
Speed[&] 30
003 Titration stand (Rondo/Tower A) Predispense
Type Rondo/Tower A Mode None
Titration stand Rondo60/1A Waiting time [s] 0
Lid handling No Control
Control User
004 Dispense (normal) [1] Titrant addition Dynamic
Titrant Na-gluconate dE (set value)[mV] 8.0
Concentraition [mol/L] 25 dV (min)[ml] 0.005
Volume [mL] 10 dV (max)[ml] 0.2
Dosing rate [ml/min] 60 Mode Equilibrium controlled
Condition No dE[mV] 0.5
dt[s] 1
005 Stir t (min)[s] 3.0
Speed [%] 30 t (max)[s] 30.0
Duration [s] 120 Evaluation and recognition
Condition No Procedure Standard
Threshold[mV/ml] 5
006 Titration (EQP) [1] Tendency Positive
Titrant Ranges 0
Titrant HCl Add. EQP criteria Steepest jump
Concentration [mol/L] 1 Steepest jumps 1
Sensor Termination
Type pH At Vmax[ml] 5
Sensor DG115-SC At potential No
Unit pH At slope No
Temperature acquisition After number of
Temperature acquisition No recognized EQPs Yes
Stir Number of EQPs 1
Speed [%] 30 Combined termination
Predispense criteria No
Mode Volume Accompanying stating No
Volume [ml] 30 Condition No
Waiting time [s] 15
Control 010 Rinse
Control User Auxiliary reagent Water
Titrant addition Dynamic Rinse cycles 1
dE (set value)[mV] 6 Vol. per cycle[mL] 10
dV (min)[ml] 0.002 Position Current position
dV (max)[ml] 0.2 Drain No
Mode Equilibrium controlled Condition No
dE[mV] 0.5
dt[s] 1 011 Conditioning
t (min)[s] 3.0 Type Fix
t (max)[s] 30.0 Interval 1
Evaluation and recognition Position Conditioning beaker
Procedure Standard Time [s] 60
Threshold[pH/ml] 0.5 Speed [%] 30
Tendency Negative Condition No
Ranges 0
Add. EQP criteria No 012 Calculation R1
Termination Result Free Caustic NaOH
At Vmax [ml] 60 Result unit g/L
At potential Yes Formula R1=(Q-Q2)*C/m
Potential [pH] 6 Constant C= M/z
Termination tendency Negative M M[Sodium hydroxide]
At slope No z z[Sodium hydroxide]
After number of Decimal places 2
recognized EQPs Yes Result limits No
Number of EQPs 2 Record statistics Yes
Combined termination Extra statistical func. No
criteria No Send to buffer No
Accompanying stating No Condition No
Condition No
013 Calculation R2
007 Dispense (normal) [2] Result Free Carbonate CaCO3
Titrant KF Result unit g/L

METTLER TOLEDO Page 6 of 7 Titration Application M466A-2010

 Formula R2=Q2*C/m
Constant C= M/z
M M[Calcium carbonate]
z z[Calcium carbonate]
Decimal places 2
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

014 Calculation R3
Result Content Al(OH)3 (g/L)
Result unit g/L
Formula R3=(Q[2]+QEX)*C/m
Constant C= M/z
M M[Aluminum trihydroxide]
z z[Aluminum trihydroxide]
Decimal places 2
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

015 Calculation R4
Result Content Al(OH)3 (mg/g)
Result unit mg/g
Formula R4=((Q[2]+QEX)*C/30.23)*100
Constant C= M/z
M M[Aluminum trihydroxide]
z z[Aluminum trihydroxide]
Decimal places 2
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

016 Calculation R5
Result Content AL2O3 (%)
Result unit %
Formula R5=(R4/10)*C
Constant C= 1.30717
M M[None]
z z[None]
Decimal places 2
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

017 End of sample

018 Park
Titration stand Rondo60/1A
Position Conditioning beaker
Condition No

Calculation R4:
30.23 = sample size of bauxite powder
100 = dilution factor (5 mL -> 500 mL)

Calculation R5:

1.30717 = M(Al2O3)/M(Al(OH)3) = 101.96/78.00

METTLER TOLEDO Page 7 of 7 Titration Application M466A-2010