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August 2010

UMA-HPC Method of Analysis

UMA Number: UMA-6312
Old UMA Code: New Date of issue: August 2010
Status Current
Method owner: Analytical Science R&D LatAm
Source: Analytical Science R&D LatAm
Author (year): Paulo E. de Gusmão (2010)
Approved by (year): Adriana Aoki - Analytical Science R&D LatAm (2010)

Determination of zeolite in raw materials and detergent powders

as acid-soluble aluminium by complexometric titration

Printed Copy = Uncontrolled Copy

The information contained in this document is proprietary to Unilever. No further distribution is

permitted without prior consent of Unilever.

1. WARNING AND SAFETY PRECAUTIONS:

THE MAIN HAZARDS OF THE MATERIALS INVOLVED ARE INDICATED BELOW. USERS SHOULD REFER TO SUPPLIER
SAFETY INFORMATION FOR FURTHER DETAILS. AN ASSESSMENT OF THE RISK TO EMPLOYEES, AND SAFETY
PRECAUTIONS REQUIRED SHOULD BE CARRIED OUT LOCALLY BEFORE COMMENCEMENT OF WORK. IN SOME
COUNTRIES THERE IS A REQUIREMENT TO DOCUMENT THIS ASSESSMENT.

2. SCOPE:

The method is suitable for the determination of zeolite in detergents products. For other matrices the applicability of the
method has to be checked.

3. NORMATIVE REFERENCES:

Not available

4. DEFINITIONS:

Not available

5. PRINCIPLE:

Aluminium is determined indirectly by adding Ethylenediaminetetraacetic Acid (EDTA) solution and titrating the excess
with standard Zinc nitrate solution.
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6. REACTIONS:

Not available

7. REAGENTS AND MATERIALS:

7.1 Concentrated Hydrochloric Acid CAUTION: CORROSIVE

7.2 Xylenol Orange indicator – 0.5% solution in distilled water
7.3 Hexamine – AR grade
7.4 Standard EDTA solution (0.05M) AR grade (Primary Standard)
Weigh exact 18.162 g/L of ethylene diamine tetra acetic acid disodium salt (EDTA) (100 percent pure) or take
appropriate exact weight as per the purity
7.5 Standard Zinc Nitrate solution (0.05M) AR grade
Weigh exact 14.8745 g/L of Zinc nitrate (100 percent pure) or take appropriate exact weight as per the Purity

8. APPARATUS AND EQUIPMENT:

8.1 Standard laboratory apparatus

8.2 Burettes or motor burettes e.g. Metrohm or similar
8.3 Porcelain Crucibles (only for detergents products).

9. SAMPLING TECHNIQUE:

9.1 The minimal amounts of sample needed for the analysis are:
9.1.1 Powder: Weigh approximately 10.0g of splitted sample according to UMA-5861
9.1.2 Zeolite raw material: 0.5g

10. PROCEDURE:

10.1 Standardisation of Zinc nitrate solution:

10.1.1 Pipette out 25 ml std. EDTA solution by bulb pipette into three 250mL conical flask.
10.1.2 Add few drops Xylenol Orange indicator and 5 g of hexamine in each flask.
10.1.3 Titrate each EDTA solution with Zinc Nitrate solution until the solution becomes red.
10.1.4 Calculate the molarity and take the average of three.

Calculation:
M1 - Molarity of EDTA solution (0.05M)
V1 - Volume of EDTA taken in procedure 1.1
V2 - Volume of Zinc Nitrate solution (burette reading.)

M 1xV 1
Molarity of Zinc Nitrate solution 
V2
10.2 Sample preparation
10.2.1 Weigh representative sample (9) into 250 mL beaker or porcelain crucible (See note 14.2)
10.2.2 Add 50ml Conc. HCl and dissolve it by boiling till it completely dissolves into solution and if required add more
HCl, till the solution is clear.
10.2.3 Transfer to 1000 mL volumetric flask, wash the beaker thoroughly and add to the volumetric flask, make up
the volume.
10.2.4 Pipette out 25 mL of this solution into a 250mL beaker.
10.2.5 Add 25 ml EDTA solution with stirring by bulb pipette, 5 drops of Xylenol Orange indicator and 5g of hexamine
(pH 5-6).
10.2.6 Heat the solution to boiling, allow to stand for 10 minutes on a water bath.
10.2.7 Titrate with std. Zinc Nitrate solution. Add under magnetic stirring 1 mL of the titrant until 1 ml before the end
point (indicated by a red colour). Then add the titrant with steps of 0.1 mL until the solution becomes
orange/red. A red colouration indicates that the end point has been passed. Note the volume of Zinc Nitrate
used.
10.2.8 Carry out the blank without sample in same way.
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11. CALCULATION & EXPRESSION OF RESULTS:

Calculate the Aluminium content in the sample as follows:

Weight (g) sample = W

Volume (mL) Zinc Nitrate solution used (blank – 10.2.8) = V1
Volume (mL) Zinc Nitrate solution used (sample – 10.2.7) = V2
Molarity of Zinc nitrate solution = M

% Aluminium = (V1 – V2)xMx1000x100x26.98154

1000x25xW

= (V1 – V2) x M x 4 x 26.98154

W

% Zeolite = % Aluminium x 100 (14.5 is the % of Aluminium in Zeolite)

14.5

12. RAW AND PROCESSED DATA:

All weights and volumes must be recorded in a laboratory notebook

13. QUALITY ASSURANCE AND CONTROL:

13.1 Validation

A validation has been carried out by adding different levels of Zeolite to a powder base sample.

Sensitivity Limit of detection : 0.19 % Limit of quantification : 0.62 %

Accuracy
Dosing low intermediate high
Trueness no bias detected
Recovery (%) 112.61 96.07 97.71
Repeatability (r) 0.29 0.22 0.31
Reproducibility (R) 0.96 0.95 0.97
Pooled Repeatability (r) 0.27
Pooled within lab. Reprod. (R) 0.96

14. SPECIAL CASES AND NOTES:

14.1 All Aluminium compounds can be analysed by this method.

14.2 Weigh about 10.0 g with an accuracy of 0.1g of detergents products sample in porcelain crucible and burn off
in muffle furnace to ash at 600ºC for 30 min. Allow to cool and quantitatively transfer to 250 mL beaker. Follow
the procedure 10.2.2 to 10.2.8.
14.4 Appropriate factor to be used for calculation of Aluminium compounds and its derivatives. Aluminium in zeolite
raw materials should be in between 14.5 to 15.5 %
14.5 Acid is not required for water soluble compounds.
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15. REFERENCES:

15.1 Vooijs, C., and Dalen, G. van, Determination of the aluminium, silicon, sodium and zeolite content in detergent
raw materials and final products by X-ray fluorescence spectrometry, VD 98 0276.
15.2 Slikkerveer, F.J., and Dalen, G. van, Determination of the zeolite content in washliquors and final products by
Flame-Atomic Absorption Spectrometry, PVD 82 3099.
15.3 D. A. Skoog, D. M. West and F. J. Holler, Analytical Chemistry: An Introduction, 6th Edition , Saunders College
Publishing, Philadelphia, 1994.
15.4 Unilever Method of Analysis, Determination of Aluminium Oxide; UMA 5632.
15.5 Unilever Method of Analysis, Validating an analytical method, Bruggen, Peter van ; Zandbelt, Peter; UMA 1009
15.6 U.S. Environmental Protection Agency Method Detection Limit. EPA ref: 40 CFR 136, Appendix B, Revision
1.11
15.7 J.N. Miller, J.C. Miller, Statistics and chemometrics for analytical chemistry, 5th Edition, Pearson Education
Limited, 2005.

16. ANNEXES:

16.1 Xylenol Orange Indicator

The Xylenol Orange indicator (Figure 1) forms complexes with metal ions. It is yellow when not complexed and red
when complexed with a metal.

Figure 1 - Xylenol Orange indicator

16.2 Indicator Colour Changes

The endpoint of the titration, all the EDTA has been used and the Zinc starts to form a red complex with xylenol orange
indicator (Figure 2). A red colouration indicates that the end point has been passed.

Figure 2 - The EDTA is back titrated with standard Zinc nitrate solution to a sharp color change of xylenol orange
from yellow to red.