DESC:FIELD OF THE INVENTION
The present invention in general relates to the chemical analysis, the invention of aluminium chlorohydrate by the WD-XRF for quick chemical composition.
BACKGROUND OF THE INVENTION
The aluminumchlorohydrate (ACH) product is an inorganic compound. It is a white powder or colourless liquid and water-soluble compound. The product widely using in the chemical industries as an ingredient for the pharmaceutical applications such as antiperspirant, industrial waste water & drinking water treatment etc.
The ACH product quality control is a stringent for the measurement of chemical concentrations such as Aluminum (Al), Chloride (Cl) & other impurities etc.
Determination of Aluminum (Al) & Chloride (Cl) concentrations has performed by wet chemical techniques i.e. titration chemistry with Ethylenediaminetetraacetic acid (EDTA) for the aluminium concentration (Al as Al2O3), and chloride measured with silver nitrate titration. The wet chemical method is reliable at higher concentration level, but low concentration of Al & Cl measurements is very difficult and also lengthy process i.e. time-consuming process.
Solution based analytical techniques are available for easy and quick chemical measurements, the solution-based techniques such as Wavelength Dispersive X-ray Fluorescence (WD-XRF) inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) & atomic absorption spectroscopy (AAS) etc. The ICP-OES, ICP-MS & AAS these analytical techniques are useful for Aluminum (Al) measurement at the lower level of concentration only. And the chloride (Cl) measurement maybe difficult by the ICP-OES, ICP-MS & AAS.
The novel analytical method was developed by the WD-XRF for determination of Aluminum (Al) & Chloride (Cl) measurements from lower concentration to higher concentration level with a short time of run time i.e. 2minutes for both the compounds (Al & Cl), the two compounds measured with a single run time of measurement by the WD-XRF.The Aluminum (Al) & Chloride (Cl) measurements extensively studied with different concentrations in various reference samples such as process samples, vendor/supplier samples and plant (manufacturing) samples etc. in the form of liquids & solids by WD-XRF.
The XRF technique is a powerful for quick measurement of chemical concentrations in a various samples. And covered wide range of sample concentrations from ppm to % level in a single run of the sample with multiple elements.
OBJECT OF THE INVENTION
An object of the invention is to provide a simple and quick practical non-destructive method for the measurement of aluminium (Al) & Chloride (Cl) concentration in an ACH product samples.
Another object of the invention is to provide method to analyse chemical concentrations (Al & Cl), which is capable to minimize the time-consuming, labours, reduction of chemicals utilization & sample wastage (effluent) etc. and measured the compounds with high level of accuracy & precision.
SUMMARY OF THE INVENTION
An object of the invention is achieved by providing a simple and quick practical NON-DESTRUCTIVE method for the measurement of aluminum (Al) & Chloride (Cl) concentration in an ACH product samples.
Another object of the invention is achieved using a method to analyse chemical concentrations (Al & Cl), which is capable to minimize the time-consuming, labours, reduction of chemicals utilization & sample wastage (effluent) etc. and measured the compounds with high level of accuracy & precision.
In an aspect, the invention provides a method of analysing the Aluminum (Al) &Chloride (Cl) concentration in the aluminumchlorohydrate (ACH) product samples.
The object of the invention is achieved by a method for measuring aluminum and chlorine composition in a sample. Firstly, forming an aluminum chlorohydrate (ACH) liquid using a liquid sample. Secondly, transferring 10 ml of the ACH liquid into an XRF thin film polypropylene liquid cup andmeasuring a concentration by XRF for the determination of Aluminum and Chlorine contents in the sample.
The another embodiment of the invention is to add 20 ml of water into 0.5 gm of ACH solid sample, and dissolving the sample by shaking, and diluting the sample solution up to 50ml standard volumetric flaskby using a purified water to form a liquid sample.
The another embodiment of the present invention is to form ACH liquid using a sample includes diluting 4 ml to 10 ml of the liquid sample with up to 6 ml of water.
The another embodiment of the present invention is when 10ml of sample solution is taken no water is added, when 9ml of sample solution is taken, 1ml of water is added to it, when 8ml of sample solution is used 2ml water is added to it,when 6ml of sample solution is used 4ml water is added to it,when 5ml of sample solution is used 5ml water is added to it, andwhen 4ml of sample solution is used 6ml water is added to it.
The another embodiment of the present invention is wherein for liquid sampleswhen 10ml of sample solution is taken no water is added, the linearity standard for Aluminium is 13 % and for Chlorine is 8.6%,when 9ml of sample solution is taken, 1ml of water is added to it, the linearity standard for Aluminium is 11.7 % and for Chlorine is 7.74%,when 8ml of sample solution is used 2ml water is added to it, the linearity standard for Aluminium is 10.4 % and for Chlorine is 6.88%, when 6ml of sample solution is used 4ml water is added to it, the linearity standard for Aluminium is 7.8 % and for Chlorine is 5.16%, when 5ml of sample solution is used 5ml water is added to it, the linearity standard for Aluminium is 6.5 % and for Chlorine is 4.3%, andwhen 4ml of sample solution is used 6ml water is added to it, the linearity standard for Aluminium is 5.2 % and for Chlorine is 3.44%.
The another embodiment of the present invention is wherein for solid sampleswhen 10ml of sample solution is taken no water is added, the linearity standard for Aluminium is 0.133 gm and for Chlorine is 0.088 gm,when 9ml of sample solution is taken, 1ml of water is added to it, the linearity standard for Aluminium is 0.1197 gm and for Chlorine is 0.0792 gm,when 8ml of sample solution is used 2ml water is added to it, the linearity standard for Aluminium is 0.1064 gm and for Chlorine is 0.0704 gm,when 6ml of sample solution is used 4ml water is added to it, the linearity standard for Aluminium is 0.0798 gm and for Chlorine is 0.0528 gm,when 5ml of sample solution is used 5ml water is added to it, the linearity standard for Aluminium is 0.0665 gm and for Chlorine is 0.044 gm, andwhen 4ml of sample solution is used 6ml water is added to it, the linearity standard for Aluminium is 0.0532 gm and for Chlorine is 0.0352 gm.
The another embodiment of the present invention is for example take 10ml of ACH liquid sample and transfer into the XRF thin film polypropylene liquid cup and measure the concentration by XRF for the determination of Al & Cl content.

For Solid Samples:
0.5 gm of ACH solid sample transferred in to 250 ml beaker, added 20ml of water and dissolved the sample by shaking, the sample solution made up to 50ml standard volumetric flask with a purified water.Taken 10ml of above sample solution and transferred into the XRF thin film polypropylene liquid cup and measure the Al & Cl concentration by WD-XRF.
BRIEF DESCRIPTION OF DRAWINGS
The novel features and characteristics of the disclosure are set forth in the description. The disclosure itself, however, as well as a preferred mode of use, further objectives, and advantages thereof, will best be understood by reference to the following description of an illustrative embodiment when read in conjunction with the accompanying drawings. One or more embodiments are now described, by way of example only, with reference to the accompanying drawings wherein like reference numerals represent like elements and in which:
Figure 1 and 2 shows the calibration linearity standard’s curve for aluminium (Al) & Chloride (Cl).
Figure 3 and 4 provides ACH liquid sample comparation study with traditional method (Wet chemical) with concentration of Al & Cl.
Figure 5 and 6 provides ACH solid sample comparation study with traditional method (Wet chemical) with concentration of Al & Cl.
Figure 7 shows the repeatability & reproducibility study conducted with known concentration of the AluminumChlorohydrate samples by WD-XRF.
Figure 8 provides recovery study conducted, the recovery of aluminium and chlorine.
DESCRIPTION
For promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the figures and specific language will be used to describe them. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as would normally occur to those skilled in the art are to be construed as being within the scope of the present invention.
It will be understood by those skilled in the art that the foregoing general description and the following detailed description are exemplary and explanatory of the invention and are not intended to be restrictive thereof.
The terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such a process or method. Similarly, one or more sub-systems or elements or structures or components preceded by "comprises... a" does not, without more constraints, preclude the existence of other, sub-systems, elements, structures, components, additional sub-systems, additional elements, additional structures, or additional components. Appearances of the phrase "in an embodiment", "in another embodiment" and similar language throughout this specification may, but not necessarily do, all refer to the same embodiment.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The system, methods, and examples provided herein are only illustrative and not intended to be limiting.
Embodiments of the present disclosure will be described below in detail with reference to the accompanying figures.
As used herein, “WD-XRF” The X-ray fluorescence (XRF) is a technique which non-destructively analyses a material to identify the elements that make it up [1]. A material bombarded with high-energy X-rays absorbs it and emits characteristic secondary X-rays of lower energy, but higher energy X-rays can also be produced using an X-ray tube [2].
As used herein, “Inductively coupled plasma optical emission spectroscopy (ICP-OES)” as used herein refers to a technique, when plasma energy is given to sample, the atoms/ions can absorb energy and move electrons from the ground state to an excited state, those excited atoms emit electromagnetic radiation at wavelength of a particular element as they transition to lower energy level.
Figure 1 and 2 explains the method for measuring aluminum and chlorine composition in a sample. Firstly, forming an aluminum chlorohydrate (ACH) liquid using a liquid sample. Secondly, transferring 10 ml of the ACH liquid into an XRF thin film polypropylene liquid cup, and finally measuring a concentration by XRF for the determination of Aluminum and Chlorine contents in the sample.
Figure 3 and 4 provides ACH liquid sample comparation study with traditional method (Wet chemical) with concentrations of Al & Cl.
The In-house standards were developed with a concentrated reference sample i.e. Aluminium Chlorohydrate liquid and solid. Weighed accurately, about (2.5 gm of powder sampleand for Liquidabout 7 gm), of the test sample in a weighing bottle. Transferred it quantitatively to a 500 ml volumetric flask with the aid of about 150 ml water dissolve by shaking and make up to mark. Pipette out accurately 5 ml of this solution to a 250 ml conical flask add 2 ml of nitric acid, 1:12 (the pH value shall be between 1 to 2), boil for 1 min, allow to cool and add 20 ml of 0.05M of EDTA solution exactly by pipette.
Adjusted the pH 3 with 1ml of nitric acid (1:12) and Boiled for about 5 min.Cool and add approximately 10 ml sodium acetate buffer solution (pH of mixture should be between 5 and 6) add 2 to 5 drops of xylenol orange solution (0.1 percent w/v)
Titrate the solution with 0.02M with zinc solution, making the endpoint the time when the colour of the solution turns from pink colour to pale red.
In parallel, pipette out 20 ml 0.05M EDTA, add 2 ml of nitric acid (1:12) solution to a 250 ml conical flask, add about 5 ml distilled water and proceed the blank test. Followed the same procedure for the blank.
CALCULATION for Al2O3%
Percent aluminium as aluminium oxide (AI2O3), A = 1+(5.1 x M1 (d-a))/(5 S/500)
Where
A= percent aluminium as aluminium chloride (Al2O3)
M1= Molarity of standard Zinc solution
d= Titre of standard zinc solution used in blank determination, in ml
a= Titre of standard zinc solution used for sample solution, in ml
S= sample taken for test, in g.
Example:
Percent aluminium as aluminium oxide (AI2O3), A
5.1xM of Zn x (Blank-sample) x 500/ sample Vol. x sample wt.
DETERMINATION OF CHLORIDE
Weigh accurately about (for liquid 5g, solid 1.7g) of the sample in a 100 ml beaker and dissolve it in approximately 30 ml of water, transfer it to a 500 ml volumetric flask, and dilute with water and makeup to the mark. Shake well. Pipette out 25 ml of this solution into a 250 ml Erlenmeyer flask and dilutewith water to 50 ml. Add 5-10 drops of mixed indicator solution and shake the flask. If a blue-violet or red colour develops, add nitric acid (3: 997) drop-wise until the colour changes to yellow. Add 1 ml of excess acid. Titrate the solution against standard 0.1 N mercuric nitrate solution, until the colour of the solution turns to blue-violet. Record the volume.
Calculation for Chloride %
where
VxNx35.46x2 /M.
V = volume (ml) of mercuric nitrate solution used in titration.
N = normality of mercuric nitrate solution.
M = mass of the material taken for test, in gm.
Standard for Liquid:
The liquid sample Al concentration is 13.0% and Cl is 8.6%.(*Sample Solution)
Linearity standards for WD-XRF for liquid
10ml *sample solution 0ml water. (Al 13 % and Cl 8.6%)
9ml sample solution 1ml water. (Al 11.7 % and Cl 7.74%)
8ml sample solution 2ml water (Al 10.4 % and Cl 6.88%)
6ml sample solution 4ml water (Al 7.8 % and Cl 5.16%)
5ml sample solution 5ml water (Al 6.5 % and Cl 4.3%)
4ml sample solution 6ml water (Al 5.2 % and Cl 3.44%)
Standard for Solid:
The solid sample Al concentration is 26.6% and Cl is 17.6%.
The Al & Cl standard prepared with 0.5 gm of ACH powder sample (Reference sample) dilute to 50ml, this standard used for solid sample measurement.(*sample solution).
Linearity standards for WD-XRF for Solid:
10ml *sample solution 0ml water. (Al 0.133gm and Cl 0.088gm)
9ml sample solution 1ml water. (Al 0.1197gm and Cl 0.0792gm)
8ml sample solution 2ml water (Al 0.1064gm and Cl 0.0704gm)
6ml sample solution 4ml water (Al 0.0798gm and Cl 0.0528gm)
5ml sample solution 5ml water (Al 0.0665gm and Cl 0.044gm)
4ml sample solution 6ml water (Al 0.0532gm and Cl 0.0352gm)
Determination of Aluminium (Al) & Chloride (Cl) concentrations has performed by wet chemical techniques (traditional method) i.e. titration chemistry with Ethylenediaminetetraaceticacid (EDTA) for the aluminium concentration (Al as Al2O3), and chloride measured with Mercury/silver nitrate titration. The wet chemical method is reliable at higher concentration levels, but low concentration of Al & Cl measurements is a very difficult and also lengthy process i.e. time-consuming process.

Quick elemental analysis is always in high demand for not only regular production process but also in R&D for new process/ product development. In order to meet these requirement, quick analysis while handling huge sample load has always been challenging for quality laboratories. The conventional analytical methods are having some limitations to measure the elemental concentrations using wet chemical techniques, ICP & AAS etc. i.e. Concentration of the analyte, working range of linearity, high TDS, improper sample ionization, dilution errors & also consumes a lot of time. In this context, quick characterization method is developed using Wavelength Dispersive X-ray Fluorescence (WD-XRF) for the measurement of multiple elements in a wide range, from ppm to % level without any deviation of the sample concentrations in a single run with Two (2) minutes of run time. This method is great support to the research projects/ industries by processing huge number of samples with less manual intervention and more accuracy of results.
Figure 5 and 6 provides ACH solid sample comparation study with traditional method (Wet chemical) with concentrations of Al & Cl.
Figure 7 shows the repeatability & reproducibility study conducted with known concentrations of the AluminumChlorohydrate samples by WD-XRF.
Figure 8 provides recovery study conducted, the recovery of aluminium and chlorine.
In an embodiment, the said method is capable to extend the analysis of ACH samples of any concentration varying at low ‘Al’ concentrations such as 0.1-5% as well as higher ‘Al’ concentrations 15-20%. Correspondingly, wide variation of chloride concentrations is also measured accurately.
An embodiment, the said method is demonstrated using WD-XRF and is capable to extend similar analysis of ACH samples using other XRF techniques such as ED (energy dispersive) XRF.

In an embodiment, the method of analyzing the Al & Cl in ACH sample, comprising:
a) Contacting said ACH sample with a reagent water.
b) Analyzing the sample for Al & Cl content.
In an embodiment, analyzing of samples is performed by WD-XRF.
Details of the WD-XRF process parameters:
Instrument Name: Wavelength Dispersive X-ray Fluorescence Spectroscopy (WD-XRF)
Make & Model: Malvern Panalytical - Zetium
Instrument Conditions: (Operating parameters)
Measurement Conditioning
Analysis medium: Helium (He)
Collimator mask: 37mm
Helium Flush time: 6 (s)
Delay time: 2 (s)
Spinner: off
Measurement execution
Sample cup: Thin film polypropylene liquid sample cup
Priority: Normal
Condition optimization
Create channels of type: WD (Wavelength Dispersive)
Optimize gonio channels: Optimal sensitivity
Power settings
Maximum voltage (KV): 60
Maximum current (mA): 160
Maximum power (W): 4000
Compounds: Al & Cl
Measurement conditions:
Channels:
Elements Spectra Line Line type Energy
(KeV) Type Kv mA Crystal Collimator Detector 2 ? (Angle) PHD
Cl Ka1,2 Fluorescent 2.62 WD-G 25 160 Ge 300µm Flow 92.8394 LL32&UL76
Al Ka1,2 Fluorescent 1.49 WD-G 25 160 PE 300µm Flow 144.9194 LL21&UL78
Background correction: on
Linearity standards for Al: 5.2, 6.5,7.8,10.4,11.7 &13%
Linearity standards for Cl: 3.4, 4.3, 5.1, 6.8, 7.7 & 8.6%
Correlation Coefficient for Aluminium (Al) r2: 0.997
Correlation Coefficient for Chloride (Cl) r2: 0.991
WORKING EXAMPLES
EXAMPLE 1:
The calibration linearity standard’s curve for aluminium (Al) & Chloride (Cl) provided in figure 1 & figure 2. The obtained correlation-coefficient (R2) is 0.997 & 0.991.
Al & Cl calibration curves
EXAMPLE 2:
AluminumChlorohydrate Liquid reference sample determination by WD-XRF & Wet chemical technique.
10ml of liquid sample and transfer into the XRF liquid cups and measure the concentration by XRF for the determination of Al & Cl content in the range of 15-20% & 5-8% respectively.
Comparation study with traditional method (Wet chemical) with said concentration of Al & Cl is provided in figure 3& figure 4 respectively
The Standard deviation obtained for Al is 0.2% and Chloride standard deviation obtained 0.3%.
EXAMPLE 3:
AluminumChlorohydrate Solid reference sample determination by WD-XRF & Wet chemical technique.
0.5gm of ACH solid sample transfer in to the beaker and add 20ml of water, dissolve the sample by shaking and made up to the 50ml volumetric flask with purified water.
10ml of sample solution from 50ml (above solution) and transfer into the XRF liquid cup and measure the concentration by XRF for the determination of Al & Cl content.
Comparation study of solid reference samples for the determination of Al & Cl in the AluminumChlorohydrate samples with traditional method (Wet chemical) and WD-XRF.
The Standard deviation obtained for Al is 0.1% and Chloride standard deviation obtained 0.2%.
The Almunium results are shown in figure 5and Chloride results are shown in figure 6.
EXAMPLE 4:
Repeatability Study by WD-XRF with known aluminium chloride liquid sample with concentration of Al 13-13.5% and Cl 8-8.5%.
The repeatability study conducted with said concentration of the AluminumChlorohydrate samples by WD-XRF. The repeatability and reproducibility is provided in figure 7 and obtained RSD as 0.01% for Al and Chloride RSD is 1.0%.
The recovery of aluminium and chloride for the said concentration is obtained as 97-98% & 98-99% respectively and is provided figure 8
The major challenges of analytical method are quick and accurate measurements of elemental concentration in ppm & % level. The claimed method is accurate and reliable for measurement of Aluminium & Chloride concentration in AluminumChlorohydrate by using WD-XRF.
For futuristic use, a method of analyzing the Aluminium (Al) & Chloride (Cl) concentration in the range of 0.5 to 15% & 0.5 to 10% with respectively in AluminumChlorohydrate samples by the WD-XRF (wave length dispersive X-ray fluorescence spectrometry). The given sample measured 10ml of sample solution with liquid cup (Thin film polypropylene liquid cup) and Sample Measurement Conditions.
a) Analysis medium: Helium
b) Collimator mask: 37mm,
c) Helium Flush time: 6 (s)
d) Delay time: 2 (s)
The said analyzing of samples is performed by WD-XRF
a) Al & Cl lines i.e. Ka1,2 and 2 ? Angle i.e. 90 to 150.
b) Crystals are Ge & PE with 300µm Collimator.
The method involves the development of various standards for Al & Cl with concentrations ranging from 1-20% & 1-10% respectively.
a) standards for Al demonstrated: 5.2, 6.5, 7.8, 10.4, 11.7, 13 &15%
b) standards for Cl demonstrated: 3.4, 4.3, 5.1, 6.8, 7.7, 8.6 & 10%
This refer to the novelty of developed method with-out use of any additional chemicals thus avoiding generation of hazardous waste. There is recovery of aluminium up to 96-97% whereas Chlorine up to 98-99% is obtained for all the aluminium chloride feed samples for all the mentioned concentration range. This method extent to aluminium chloride powder samples with error of 0.5% for both aluminium & chloride concentrations measured.
Solution based analytical techniques are available for easy and quick chemical measurements, the solution-based techniques such as Wavelength Dispersive X-ray Fluorescence (WD-XRF).
Name of the Compound Traditional Method WD-XRF Method
Al 5 samples/day >10hrs. 5samples/10 minutes formeasurementof Al & Cl with single run.
Cl 5 samples/day >10hrs.
Manual Error Yes, Possibilities in the Reagents preparations No reagent/chemical preparation for the XRF.

,CLAIMS:1. A method for measuring aluminum and chlorine composition in a sample comprising:
- forming an aluminum chlorohydrate (ACH) liquid using a liquid sample;
- transferring 10 ml of the ACH liquid into an XRF thin film polypropylene liquid cup, and
- measuring a concentration by XRF for the determination of Aluminum and Chlorine contents in the sample.

2. The method of claim 1, wherein adding 20 ml of water into 0.5 gm of ACH solid sample, and dissolving the sample by shaking, and diluting the sample solution up to 50ml standard volumetric flaskby using a purified water to form a liquid sample.

3. The method as claimed in claims 1 or 2, wherein the method for forming ACH liquid using a sample includes diluting 4 ml to 10 ml of the liquid sample with up to 6 ml of water.

4. The method as claimed in claim 3, wherein:
- when 10ml of sample solution is taken no water is added,
- when 9ml of sample solution is taken, 1ml of water is added to it,
- when 8ml of sample solution is used 2ml water is added to it,
- when 6ml of sample solution is used 4ml water is added to it,
- when 5ml of sample solution is used 5ml water is added to it, and
- when 4ml of sample solution is used 6ml water is added to it.

5. The method as claimed in claim 4, wherein for liquid samples:
- when 10ml of sample solution is taken no water is added, the linearity standard for Aluminium is 13 % and for Chlorine is 8.6%,
- when 9ml of sample solution is taken, 1ml of water is added to it, the linearity standard for Aluminium is 11.7 % and for Chlorine is 7.74%,
- when 8ml of sample solution is used 2ml water is added to it, the linearity standard for Aluminium is 10.4 % and for Chlorine is 6.88%
- when 6ml of sample solution is used 4ml water is added to it, the linearity standard for Aluminium is 7.8 % and for Chlorine is 5.16%
- when 5ml of sample solution is used 5ml water is added to it, the linearity standard for Aluminium is 6.5 % and for Chlorine is 4.3%, and
- when 4ml of sample solution is used 6ml water is added to it, the linearity standard for Aluminium is 5.2 % and for Chlorine is 3.44%.

6. The method as claimed in claim 4, wherein for solid samples:
- when 10ml of sample solution is taken no water is added, the linearity standard for Aluminium is 0.133 gm and for Chlorine is 0.088 gm,
- when 9ml of sample solution is taken, 1ml of water is added to it, the linearity standard for Aluminium is 0.1197 gm and for Chlorine is 0.0792 gm,
- when 8ml of sample solution is used 2ml water is added to it, the linearity standard for Aluminium is 0.1064 gm and for Chlorine is 0.0704 gm,
- when 6ml of sample solution is used 4ml water is added to it, the linearity standard for Aluminium is 0.0798 gm and for Chlorine is 0.0528 gm,
- when 5ml of sample solution is used 5ml water is added to it, the linearity standard for Aluminium is 0.0665 gm and for Chlorine is 0.044 gm, and
- when 4ml of sample solution is used 6ml water is added to it, the linearity standard for Aluminium is 0.0532 gm and for Chlorine is 0.0352 gm.