St.

Pauls Convent School

Iron sucks!
By Zoe Chu () Karen Lau () Cherry Liu () Cherie Wong () Stephanie Yeung () Teacher Advisor: Mrs. T. Tam () Submitted for participation in the Fifteen Hong Kong Chemistry Olympiad for Secondary Schools From St. Pauls Convent School March 2010

Presentation materials: 1 CD-R disc (1 video clip and several digital photographs incorporated in a PowerPoint Presentation)

Abstract
Our research paper involves using a common household waste - used hand warmer powder to treat water pollutants. As the chemical composition of used hand warmer powder might resemble another frequently used industrial adsorbent - hydrous ferric oxide, we hypothesised that used hand warmer powder might exhibit similar effects on heavy metal ions, phosphate and dichromate. We synthesized hydrous ferric oxide to test our hypothesis. We have also investigated the adsorption abilities of materials isolated in the hand warmer powder, treated hand warmer powder and powder of different brands in order to derive a method which optimizes adsorption effects. After experimentation, we found that for adsorbing PO43 and Ni2+ ions, the used hand warmer powder should be treated with dilute hydrochloric acid; for adsorbing Cr2O72, Zn2+, Cu2+ and Pb2+ ions, no treatment is needed; and the longer the adsorbents are allowed to stand in the solutions, the more pollutants will be adsorbed. We also packed burettes and a compartmentalized filtration device with the most effective adsorbent among untreated hand warmer powders and passed solutions of heavy metal ions, phosphate and dichromate into it to simulate real life situation, it was found that the burette is a much more effective device.

Contents
Page Introduction Part I IA IB Part II - Preparation of various adsorbents - Preparation of hydrous ferric oxide (HFO) - Preparation of Processed Hand Warmer Powder (HWP) 1-2 3 - 15

- Investigating the effectiveness of anion adsorption on various adsorbents IIA - Determination of PO43- adsorption IIB - Determination of Cr2O72- adsorption - Investigating the effectiveness of cation adsorption on various adsorbents - Determination of Zn2+ adsorption by EDTA titration - Determination of Cu2+ and Ni 2+ adsorption by colorimetric measurement - Determination of Pb2+ adsorption by gravimetric analysis through precipitation Determination of hardness adsorption by EDTA titration Investigating the effectiveness of filtration device and the regeneration of HFO in the device

16 - 37

Part III IIIA IIIB IIIC IIID Part IV

38 - 77

78 - 89

Sources of Error and Suggestions for Improvements Conclusion References

90 - 93 94 - 97 98

P. 1

Introduction
Water pollution has been a serious problem worldwide. The clean water sources round the globe have become very limited and waste water such as factory effluents contains many pollutants like heavy metals ions, harming the wildlife and human environment when discharged. Many people have been making an effort in finding new and better ways of water treatment in order to reuse water. But so far most water treatment programs involve a huge amount of resources and are very expensive even for both commercial and domestic use. After reading a number of academic papers as reference, we found that iron compounds were claimed to be effective in adsorbing anions like phosphate as well as various heavy metal ions such as copper(II) and nickel(II) ions, the major pollutants found in waste water. Thus in this project, our group will try to explore a cheaper and more recyclable way to treat water, using iron compounds. We will also make an attempt in using used hand warmer powder with iron oxides as its main ingredient to treat waste water. Hand warmer powder can be commonly found in households and so it would be a good domestic adsorbent source. In part I, we will first prepare hydrous ferric oxide (HFO) of different structures by mixing iron(III) chloride solution and aqueous sodium hydroxide or ammonia and varying the pH of the supernatant liquid. Since the chemical composition of used hand warmer powder might be similar to that of HFO, we will identify substances present in the powder, possibly unused iron, hydrous iron(III) oxide, activated carbon and vermiculite, and try to isolate them. HFO prepared under different pH, hand warmer powder of different brands, hand warmer powder treated with hydrochloric acid under different conditions, iron filings, iron(III) oxide and activated carbon will later be tested as adsorbents. Vermiculite + Activated carbon

P. 2

In part II, we will focus on the effectiveness of anion adsorption. For part IIA, we will investigate the effectiveness of the adsorbents mentioned above on phosphate adsorption by colorimetric measurement with the addition of ammonium molybdate followed by tin(II) chloride to the treated water samples. The phosphate content of each treated water sample can be obtained by comparing the absorbance with a calibration curve. For part IIB, we will investigate the effectiveness of dichromate adsorption on the adsorbents mentioned above by colorimetric measurement as the colour intensity of dichromate solution changes with its concentration. We will also investigate the effect of time on dichromate solution adsorption of a particular adsorbent by varying the duration of the adsorbent in contact with dichromate solution. In part III, we will investigate the effectiveness of the adsorbents on heavy metal ions (e.g. Cu2+, Zn2+, Pb2+, Ni2+) and hardness (i.e. Ca2+, Mg2+) adsorption. For part IIIA, the effect of Zn2+ adsorption will be determined by carrying out titration against EDTA. For part IIIB, the effect of Cu2+, Ni2+ adsorption will be investigated by colorimetric measurement, with the addition of ethane-1,2-diamine to the water samples containing Cu2+ and Ni2+. For part IIIC, the effect of Pb2+ adsorption will be investigated. Yellow precipitate will be formed by adding excess KI solution to the treated water samples with Pb 2+. The precipitate will then be allowed to dry and the Pb2+ content can then be determined indirectly by measuring the dry mass of the precipitate of each sample. For part IIID, the effect of Ca2+, Mg2+ and hardness of mineral water adsorption will be determined by carrying out titration against EDTA. We will also investigate the effect of time on Cu2+ solution adsorption of a particular adsorbent by varying the duration of the adsorbent in contact with dichromate solution. Our ultimate aim is to find out a way of treating hand warmer powder so that its effectiveness in removing harmful substances in water is at its highest. In part VI, we will determine the effectiveness of toxic ions removal by hand warmer powder-packed columns. Known volumes of phosphate, dichromate, copper(II), zinc, lead(II) and nickel(II) ion solutions will be allowed to pass through the Warmergotchi-packed columns. The amount of the remaining anions / metal cations in the resulting solutions will be determined by gravimetric measurement. Moreover, we will also investigate the effectiveness of the regeneration of hydrous ferric oxide, by adding dilute sulphuric acid to the adsorbents to reverse the reaction.

P. 3

Part IA Preparation of hydrous ferrous oxide (HFO)

Objective:
To prepare samples of hydrous ferrous oxide under different pH conditions

Principle:
Hydrous ferric oxide are obtained from reacting FeCl3(aq) with NaOH(aq) until the pH of the supernatant liquid reached pH 5, pH 7 and pH 9. This is to investigate under which pH would produce a hydrous ferric oxide of a high level of activity. To attain the desired pH, the pH of the supernatant liquid is determined by using a pH paper, if the pH is too low, dilute aqueous sodium hydroxide is added and when the pH is too high, dilute hydrochloric acid is added as needed. HFO can also be produced by reacting FeCl3(aq) with alkaline NH3(aq). Fe3+(aq) + 3OH(aq) Fe(OH)3(s) The brown Fe(OH)3 precipitate is aged with the mother liquor for 5 days. Then, the supernatant liquid is filtered under suction and the while being washed with water until acid free. The aging of the reactant mixture and the washing steps as described are important to develop the physical properties such as high surface area and abrasion resistance of the final product. After filtering the precipitate under suction until shrinkage of the precipitate is complete, it is dried at 60 in an air oven for sufficient duration to reduce the water content of the product. If the drying step is initiated before sufficient water has been removed by filtering under suction, the product will be too soft. The product is then prepared for use by grinding. Fe(OH)3(s) FeO(OH)(s) + H2O(l) hydrous ferric oxide (HFO)

Chemicals used:
Anhydrous iron(III) chloride 1M sodium hydroxide solution

P. 4

1M ammonia solution 1M hydrochloric acid

Apparatus used:
Electronic balance Glassware Suction filter Oven

Procedures:
1. 7.60g of anhydrous iron(III) chloride was weighed accurately and was transferred to a large beaker. 2. 1M sodium hydroxide solution was added to the anhydrous iron(III) chloride until the pH value of the supernatant liquid has reached pH 5. 3. The above procedures were repeated and the pH values of the supernatants were adjusted to pH 7, 9 and 11 respectively, in which suitable volumes of 1M hydrochloric acid were added in order to adjust the pH.

pH 5 (NaOH)

pH 5 (NaOH)

pH 7 (NaOH)

pH 9 (NaOH)

pH 11 (NaOH)

pH 7 (NH3)

4. 1M ammonia solution was used instead of 1M sodium hydroxide solution in one condition under pH 7. The mixtures were allowed to stand for 5 days.

P. 5

5. The mixtures were filtered under suction and the residues were washed and collected.

6. The residues were dried in the oven at 60C for about 12 hours, which were then ground and weighed.

Results:
Mass of HFO obtained under different experimental conditions: Batch Mass of anhydrous FeCl3 (g) 7.60 6.08 7.60 7.60 7.60 3.04 1M NaOH (cm3) 118 (NaOH) 89.5 (NaOH) 140.5 (NaOH) 285 (NH3) 130 (NaOH) 123.5 (NaOH) 1M HCl (cm3) 1.25 65 pH value 5 5 7 7 9 11 Mass of HFO made (g) 3.30 2.75 5.18 4.40 3.80 1.31

1 2 3 4 5 6

P. 6

Discussion:

Results show that the yield of HFOs was the highest under the pH condition of pH 7. The thickness and fineness of the solids were after the five-day period was observed to be different for different pH conditions. The mass of solid after filtration and drying was found to be the greatest for the condition under pH7. Thus, we found that pH 7 is a favourable condition for the formation of HFO.

P. 7

The filtration procedure for the condition of pH 5 was most time-consuming and repetitive. Not only did the mixture filter slowly, but the residues of the condition pH 5 often passed through the filter paper and entered the filtrate. It can be deduced that the particle size of the HFO formed under pH 5 was the smallest, leading to easier blocking and passing through of filter paper pores. This may have an effect on the adsorption ability of HFO due to an increased surface area.

As seen from the above photo, the supernatant liquid of the second left beaker (Batch 2) appears to be quite reddish-brown. We deduced that it may be due to experimental errors during the adjustment of pH value. The actual pH of the supernatant liquid may be below pH 5, or that the mixture was stirred excessively, which results in a lot of iron(III) ions (reddish-brown in colour) still in aqueous form without being precipitated out, thus giving the supernatant liquid a reddish-brown colour. It can be deduced that minimizing the mixing of the precipitate and supernatant liquid was important to obtaining a higher yield of HFO. By comparing the yields of batches 3 and 4, the HFO yield of batch 3 which used sodium hydroxide was higher than that of batch 4 which used ammonia solution. Although 1.25 cm3 of 1M hydrochloric acid was added to the mixture in batch 3, this volume was considered insignificant compared to the 140.5 cm3 of 1M sodium hydroxide present. Therefore, we found that sodium hydroxide solution was a better alkali to be used in the preparation of HFO than ammonia solution. Batch 3 pH 7 (NaOH) Batch 4 pH 7 (NH3)

P. 8

Part IB

Preparation of Processed Hand Warmer Powder (HWP)

Objective:
To identify and isolate materials remained in used hand warmer powder by different treatments.

Principle:
The materials remained in used hand warmers were isolated and investigated individually for their adsorption effects. Used hand warmers usually consist of unused iron, hydrous iron(III) oxide, NaCl, activated carbon, and vermiculite. Different treatments would be used to find out which one would produce hand warmer packs with the best adsorption effect. Treatments: Changes in the amount of the following substances: Fe Hydrous Fe2O3 Vermiculite ferric oxide Unchanged Unchanged Dilute HCl Reduced Reduced (2 hrs, 4 hrs, 6 * * hrs) Implications: Activated carbon Unchanged Fe2O3 takes up a much larger proportion than Fe in the known mass of the treated hand warmer Fe2O3 takes up a similar proportion as Fe in the known mass of the treated hand warmer The treated hand warmer contains mostly vermiculite and carbon, with very little Fe and Fe2O3.
The treated hand warmer contains pure vermiculite and carbon.

Dilute HCl + Reduced Heat * (2 hrs, 4 hrs, 6 hrs) Conc HCl Almost (2 hrs, 4 hrs, 6 completely hrs) removed *
Conc HCl (48 hrs) Completely removed

Reduced *

Reduced *

Unchanged

Unchanged

Almost completely removed * Completely removed

Almost completely removed * Completely removed

Unchanged

Unchanged

Unchanged

Unchanged

* The amount removed increases with time.

P. 9

The adsorption effects of iron powder, iron(III) oxide, and activated carbon available in the laboratory would also be investigated to see which component in the hand warmer powder with the best adsorption effect is mainly responsible for adsorbing the ions, and to see with what treatment can the adsorption effect of used hand warmer powder be optimized.

Chemical used:
2M hydrochloric acid 11M hydrochloric acid Hand warmer powder ()

Apparatus used:
Hotplate magnetic stirrer Suction filter Oven Electronic balance Glassware

Procedures:
Treatment A 1. 300 cm3 of 2M hydrochloric acid was added to 20.0g of used hand warmer powder. 2. The mixture was allowed to stand for 2 hours. 3. The mixture was filtered under suction and the residue was washed and dried in an oven. 4. The above procedures were repeated twice, where the mixtures stood for 4 hours and 6 hours respectively.

P. 10

Treatment B 1. 300 cm3 of 2M hydrochloric acid was added to 20.0g of used hand warmer powder. 2. The mixture was heated at 60 C for 2 hours. 3. The mixture was filtered under suction and the residue was washed and dried in an oven. 4. The above procedures were repeated twice, where the mixtures were heated for 4 hours and 6 hours respectively. Treatment C 1. 300 cm3 of 2M hydrochloric acid was added to 20.0g of used hand warmer powder. 2. The mixture was allowed to stand for 2 hours. 3. The mixture was filtered under suction and the residue was washed and dried in an oven. 4. The above procedures were repeated twice, where the mixtures stood for 4 hours and 6 hours respectively. Treatment D 1. 200 cm3 of 11M hydrochloric acid was added to 20.0 g of used hand warmer powder. 2. The mixture was allowed to stand for 2 days in a fume cupboard till the remaining powder was no longer magnetic. 3. The mixture was filtered under suction and the residue was washed and dried in an oven.

P. 11

Results:
Mass of hand warmer powder (HWP) obtained after treatments Batch of HWP (20.0g each) A1 A2 A3 B1 B2 B3 C1 C2 C3 D HCl added Volume Molarity (cm3) 300 300 300 300 300 300 100 100 100 200 200 2M 2M 2M 2M 2M 2M 11M 11M 11M 11M 2M Time (hours) Heated? (Y/N) Mass of Processed HWP made (g) % yield (%) 63.52

2 4 6 2 4 6 2 4 6 48 48

N N N Y(60 C) Y(60 C) Y(60 C) N N N N N

13.04 13.48 11.59 6.46 6.26 7.69 6.06 5.59 4.33 3.22 2.86

Average 12.70 Average 6.803 Average 5.33 Average 3.04

34.02

26.63

15.20

A1

B1

C1

A2

B2

C2

A3

B3

C3

P. 12

Observations and inferences made on the HWP remained Batch of HWP Treatment Used hand -warmer powder A add dil HCl B C D heat with dil HCl add conc HCl add conc HCl (48 hrs) Observation a mixture of black powder, brown powder and shiny solids solution turned green, colourless gas bubbles evolved solution turned greenish yellow, colourless gas bubbles evolved solution turned brown, colourless gas bubbles evolved solution turned brown, colourless gas bubbles evolved Magnetic Yes

Yes Yes slightly No

Used Hand Warmer Powder

P. 13

Discussion:
The hand warmer powder manufacturer claimed that the hand warmer powder contained iron, activated carbon, vermiculite, and sodium chloride (assuming negligible mass). Thus we deduced that the used hand warmer powder contained unreacted iron, iron(III) oxide, vermiculite, activated carbon and sodium chloride. The series of treatments we conducted allowed us to prepare samples of used hand warmer powder which underwent different treatments and enabled us to confirm the constituents present in each of them.

Based on the above results and observations, we made some deductions. If the resulting powder is magnetic, it can be deduced that iron and iron(III) oxide may be present. The presence of black powder may be due to the activated carbon. The appearances of shiny solids may be due to the mineral vermiculite. Any sodium chloride would have dissolved in the mixture and thus would not be present in the processed HWP. As for the original HWP, sodium chloride would also dissolve in the aqueous solution in which the powder is to be placed into for adsorption. Therefore, the presence of sodium chloride can be negligible.

Deduced composition in processed HWP under different treatments Batch of HWP original A B C D Treatment -add dil. HCl heat with dil. HCl add conc. HCl add conc. HCl for 2 days Composition in remaining powder Fe + Fe2O3 + vermiculite + activated C traces of iron + mainly Fe2O3 + vermiculite + activated C traces of Fe + traces of Fe2O3 + vermiculite + activated C traces of Fe2O3 vermiculite + activated C vermiculite + activated C

P. 14

A1

B1

C1

A2

B2

C2

A3

B3

C3

Processed HWP

Together with the investigation of adsorption effects of independent materials from the HWP, the adsorption effect of used HWP under different treatments can be compared. By taking these results into account when we are going to investigate the adsorption effects on different ions, we can adjust our treatment for the HWP to produce HWP with the most adsorption effects.

From the results of treatment A, it was observed that the solution turned green and colourless gas bubbles evolved. We deduced that most iron has dissolved in the acid to form Fe(II) ions, producing colourless gas bubbles giving the solution a green colour. Since treatment A mainly removed iron, what remained in the residue were traces of iron, mainly iron(III) oxide, vermiculite and activated carbon. In our further investigations to be followed, if the adsorption effect of untreated used HWP is higher than that of treatment A, then it can be deduced that iron has the ability to adsorb. This could be confirmed by comparing the adsorption effect of iron powder alone.

P. 15

From the results of treatment B, the solution was observed to be greenish-yellow. This shows that the amount of iron(III) oxide that dissolved in acid to give yellowish Fe(III) ions was greater than that in treatment A. Thus in the processed HWP in treatment B, the proportion of iron and iron(III) oxide would be similarly low. In our following investigations, if the adsorption effect of processed HWP in treatment A was much better than that in treatment B, it can be deduced that iron(III) oxide was effective in adsorption.

For the processed HWP in treatments C and D, the composition in the remaining powder should be similar, in which there only remains mainly vermiculite and activated carbon. Since the treatment time for treatment C is shorter than that of D, there would probably be more iron(III) oxide traces in C than in D. If our hypothesis, iron(III) oxide possesses adsorption ability, is correct, then the adsorption effect of processed HWP from treatment C would be better than that of D.

C1

P. 16

Part IIA PO43- adsorption

Objective:
To investigate the effectiveness of PO43- adsorption on various adsorbents by colorimetric measurement

Principle:
Phosphate binds to hydrous ferric oxide through a direct ionic interaction between one or two negatively charged oxygen ions on the phosphate with the ferric ions (Fe3+) in the solid. The figure below shows phosphate in solution bound via two ionic bonds, with the displacement of hydroxide.

Fe O

OH

OH

O P

Fe H+

O P

+
Fe OH O-

+
O-

O Fe O

+ 2H2O
OH

Since phosphate binging takes place at the surface of the HFO instead of deep below the surface, the larger the surface area, the more phosphate the adsorbent can bind. To investigate the effectiveness of adsorbing phosphates by adsorbents, the Molybdenum Method is used. Phosphate in water combines with heptamolybdate to form a yellow complex. When SnCl2(aq) is added, the yellow complex turns blue as the oxidation state of molybdenum changes +6 to +5. 7H3PO4 + 12(NH4)6Mo7O24 + 51H+ 7(NH4)3PO412MoO3 + 51NH4+ + 36H2O Mo(VI)-yellow complex + Sn2+ Mo(V)-blue complex + Sn4+ The intensity of the blue colour produced is proportional to the amount of phosphate ions present, and the absorbance can be measure using a colorimeter. A calibration curve

P. 17

would be first made with the colorimeter readings of PO43- solutions with various concentrations. By comparing the absorbance of the water samples treated with various adsorbents with the calibration curve, the phosphate concentration in the solutions can be obtained. The types of adsorbents used include the different forms of HFO prepared previously so as to compare which method would create the best adsorbent for PO43-.

Chemicals used:
Ammonium Molybdate ( (NH4)6Mo7O24H2O) Tin(II) chloride (SnCl22H2O) Sodium phosphate (Na3PO4) 2M Hydrochloric acid (HCl) 11M Hydrochloric acid (HCl) HFO 1 (prepared with NaOH at pH 5) HFO 2 (prepared with NaOH at pH 5) HFO 3 (prepared with NaOH at pH 7) HFO 4 (prepared with NH3 at pH 7) HFO 5 (prepared with NaOH at pH 9) HFO 6 (prepared with NaOH at pH 11) Iron filings (Fe) Iron(III) oxide powder (Fe2O3) Activated carbon Vermiculite + activated carbon A1 Processed Hand warmer powder (treated with dilute HCl for 2 hours) A2 Processed Hand warmer powder (treated with dilute HCl for 4 hours) A3 Processed Hand warmer powder (treated with dilute HCl for 6 hours) B1 Processed Hand warmer powder (treated with dilute HCl with heat for 2 hours) B2 Processed Hand warmer powder (treated with dilute HCl with heat for 4 hours) B3 Processed Hand warmer powder (treated with dilute HCl with heat for 6 hours) C1 Processed Hand warmer powder (treated with concentrated HCl for 2 hours) C2 Processed Hand warmer powder (treated with concentrated HCl for 2 hours) Sodium phosphate Tin(II) chloride Ammonium Molybdate

P. 18

C3 Processed Hand warmer powder (treated with concentrated HCl for 2 hours) Hand warmer powder () Hand warmer powder () Hand warmer powder ( Warmergotchi) Hand warmer powder ( Pocket Sun) Hand warmer powder ()

Various adsorbents

Apparatus used:
Electronic balance Colorimeter Glassware

P. 19

Procedures:
Preparation of ammonium molybdate solution 2.4g of (NH4)6Mo7O24 H2O (molar mass: 1235.86 g)was added to 100 cm3 1M H2SO4(aq). The result solution has a concentration of 0.0194 M.

Preparation of Tin(II) chloride solution 1.0g of SnCl2(molar mass:325.63 g) was added to 100 cm3 1M HCl(aq). The result solution has a concentration of 0.0307 M.

Colorimetric measurements of phosphate solutions 1. 0.5g of Na3PO412H2O was added to 250.0 cm3 of deionised water. Then the standard solution of PO43-(aq) was diluted in different ways listed as follows: A. B. C. D. E. F. G. 5.0 cm3 of standard solution in 250.0 cm3 of deionised water 10.0 cm3 of standard solution in 250.0 cm3 of deionised water 15.0 cm3 of standard. solution in 250.0 cm3 of deionised water 20.0 cm3 of standard solution in 250.0 cm3 of deionised water 25.0 cm3 of standard solution in 250.0 cm3 of deionised water 35.0 cm3 of standard solution in 250.0 cm3 of deionised water 45.0 cm3 of standard solution in 250.0 cm3 of deionised water

2. 25.0 cm3 of each solution was pipetted into a 100 cm3 beaker.

P. 20

3. 2.0 cm3 of 0.0194 M ammonium molybdate solution was added to each beaker.
A B C D E F G

4. 12.0 cm3 of 0.0307 M tin(II) chloride solution and 25.0 cm3 of deionised water were pipetted to each beaker.

5. The solutions were then transferred to the test tubes. 6. The colour intensities of the solutions were compared with a colorimeter.

Colorimetric measurements of phosphate solutions with various adsorbents 1. 20.0 cm3 of solution G was pipetted into each beaker containing 0.5 g of an adsorbent.

P. 21

2. The mixtures were allowed to stand for 9 hours.

3.

The mixtures were filtered and the collected filtrate was made up to 30 cm3 with deionised water.

5. 5.0 cm3 of filtrate was pipetted into a 100 cm3 beaker. 6. 2.0 cm3 of 0.0194 M ammonium molybdate, 12.0 cm3 of 0.0307 M SnCl2 and 25.0 cm3 of deionised water were added into each beaker. 7. The mixtures were transferred into test tubes. 8. The colour intensities of the mixtures were tested with a colorimeter.

P. 22

Results:
Absorbance values of phosphate solutions A to G Solutions Absorbance A 0.18 B 0.34 C 0.50 D 0.65 E 0.85 F 0.95 G 1.40

Calibration Graph for Standard Phosphate Solution

P. 23

Absorbance of Various Phosphate Solutions after Adsorption Adsorbent (20.0 cm3 diluted to 30.0 cm3) Absorbance of phosphate solution (Absorbance x 1.5) 0.05 (0.075) 0.02 (0.03) 0.06 (0.09) 0.015 (0.0225) 0.33 (0.495) 0.31 (0.465) 0.54 (0.81) 0.98 (1.47) 0.90 (1.35) 0.30 (0.450) 0.30 (0.45) 0.045 (0.0675) 0.15 (0.225) 0.03 (0.045) 0.20 (0.30) 0.75 (1.125) 0.55 (0.825) 0.295 (0.4425) 0.26 (0.39) 0.30 (0.45) 0.22 (0.33) 0.20 (0.3) 0.70 (1.05) 0.34 (0.51) / (1.8) % change in absorbance (#) Concentration of phosphate solution ( 10-4 mol dm-3) 0.37 0.2888 0.8664 0.2166 3.1962 2.99 5.4236 10.44 9.50 9.40 2.888 0.321 1.363 0.173 1.87 7.749 5.532 2.836 2.48 2.888 2.07 1.866 7.187 3.302 13.165

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25.

HFO 1 (NaOH, pH 5) HFO 2 (NaOH, pH 5) HFO 3 (NaOH, pH 7) HFO 4 (NH3, pH 7) HFO 5 (NaOH, pH 9) HFO 6 (NaOH, pH 11) Hand warmer powder () Iron filings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon
A1 Processed HWP (dil. HCl + 2 hr) A2 Processed HWP (dil. HCl + 4 hr) A3 Processed HWP (dil. HCl + 6 hr) B1 Processed HWP (dil. HCl + 2 hr + heat) B2 Processed HWP (dil. HCl + 4 hr + heat) B3 Processed HWP (dil. HCl + 6 hr + heat) C1 Processed HWP (conc. HCl + 2 hr) C2 Processed HWP (conc. HCl + 4 hr) C3 Processed HWP (conc. HCl + 6 hr)

HWP () HWP ( Warmergotchi) HWP ( Pocket Sun) HWP () Control

# =

-99.58% -98.33% -95.00% -98.75% -72.50% -74.17% -55.00% -18.33% -25.00% -28.57% -75.00% -96.25% -87.50% -97.50% -83.33% -37.50% -54.17% -75.42% -78.33% -75.00% -81.67% -83.33% -41.67% -71.67% /

absorbance of phosphate solution after treatment absorbance of control 100% absorbance of control

P. 24

Concentration of Phosphate Solutions after Adsorption by Different Adsorbents

(From left to right) HFO pH5 (x2), pH7 (x2),pH 9, pH 11,

(From left to right) Iron(III)oxide, iron filings, A1-3, B1-3, control

P. 25

Discussion:
From the graphs above, we can see that HFO 4 is most effective in the removal of phosphate while activated carbon is least effective. The absorbance values of HFO were the lowest in average, while those of processed hand warmer powder varied.

Among the HFO samples, we found that the absorbance of HFO treated in acidic or neutral mediums (samples 1 to 4) were higher than that of HFO treated in an alkaline medium (samples 5 to 6). But the general adsorption performance of HFO samples was very satisfactory.

(From left to right) HFO pH5 HFO pH5 HFO pH7 HFO pH7 HFO pH9 HFO pH11 Control

P. 26

The adsorption power of the original hand warmer powder sample (sample 7) was found to be higher than those of iron filings, iron(III) oxide and activated carbon alone. But since suspension was observed in the samples of iron filing and iron(III) oxide powder, the absorbance values above could not accurately reflect their effectiveness in the removal of phosphate alone. The effectiveness in the removal of phosphate is higher when a mixture of the above ingredients is used.

(From left to right) HWP () Iron fillings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon Control

P. 27

Most of the treated hand warmer powder samples were found to be more effective phosphate adsorbents than the original hand warmer powder. Among the processed hand warmer powder samples (A1 to C3), the absorbance values of samples with the addition of dilute HCl(A samples) were lower than those of samples with addition of concentrated HCl or heating with dilute HCI. Referring to part I about the preparation of processed hand warmer powder, samples C1 to C3 are mainly composed of vermiculite and activated carbon. The experimental absorbance values of C samples matched with that of the mixture of vermiculite and activated carbon. It is likely that C samples have similar compositions. As for samples A1 to B3, A samples mainly comprises iron(III) oxide, while B samples contains more iron atoms and less iron(III) oxide in composition. As the absorbance values of A samples were significantly lower than those of B samples, it can be deduced that iron(III) oxide is more effective than iron in the removal of phosphate ions.

(From left to right) A1, A2, A3 B1, B2, B3 control

P. 28

Among all hand warmer powder brands, Warmergotchi hand warmer powder was found to be the most effective phosphate adsorbent while the lowest effectiveness was observe for Pocket Sun hand warmer powder. From the above data, we can see that some used hand warmer powder samples, like sample 21 ( ) and sample 22 (Warmergotchi), can also serve as effective phosphate adsorbents, as compared to the percentage change in absorbance of HFO samples. To maximise the effectiveness of the hand warmer powder, the powder can be first treated with dilute hydrochloric acid and allowed to stand for above 2 to 6 hours, since the adsorption power of such treated samples have similar or even higher phosphate removal power than HFO samples.

(From left to right) HWP () HWP ( Pocket Sun) HWP ( Warmergotchi) HWP () HWP () Control

P. 29

Part IIB Cr2O72- adsorption

Objective:
To investigate the effectiveness of Cr2O72- adsorption on various adsorbents by colorimetric measurement and the time effect on adsorption abilities.

Principle:
Dichromate ions are stable only in acidic medium and will be converted to chromate ions at high pH: Cr2O72- + H2O 2CrO42- + 2H+ When dichromate ions in the solution are in contact with the basic surface of HFO, the chromate ions formed would then be absorbed by HFO according to the following equation due to the high surface positive charge density of HFO. The an electrostatic attractive force between the solid adsorbent and adsorbate causes the chromate ions to bind to HFO.

Fe O

OH

OH

O Cr

Fe H+

O Cr

+
Fe OH O-

+
O

O Fe O

+ 2H2O
O

To investigate the effectiveness of chromium(VI) adsorption of various adsorbents, the colorimeter is used to measure the absorbance of the water samples, the lower the absorbance, the more effective is the adsorbent used. To investigate the effect of time on chromium(VI) adsorption of a particular adsorbent, the time period for the adsorbent being in contact with dichromate solution is varied and the absorbance values are compared.

P. 30

Chemicals used:
0.01M Potassium dichromate (K2Cr2O7) Various adsorbents

Apparatus used:
Electronic balance Colorimeter Glassware

Procedures:
1. 25.0 cm3 of 0.01M K2Cr2O7 was added to 0.5g of different adsorbents in a beaker. The mixtures were allowed to stand for 9 hours. Solution samples containing HFO at pH 7 and hand warmer powder were allowed to stand for 1, 3, 5 and 7 hours respectively. The mixtures were filtered and the filtrate collected was transferred into its respective test tube.

2.

3.

4.

The colour intensities of the mixtures were determined with a colorimeter.

P. 31

Results:
Dichromate adsorption: Adsorbent 1. HFO (NaOH, pH 5) 2. HFO (NaOH, pH 7) 3. HFO (NaOH, pH 9) 4. Hand warmer powder () 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Iron filings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon A2 - Processed HWP (dil. HCl + 4 hr)
B2 - Processed HWP (dil. HCl + 4 hr + heat) C2 - Processed HWP (conc. HCl + 4 hr)

absorbance 1.0 0.85 0.925 1.50 2.0 1.80 1.30 1.70 1.75 1.80 1.70 1.50 1.45 1.30 1.20 2.0

% change in absorbance -50.00% -57.50% -53.75% -25.00% 0.00% -10.00% -35.00% -15.00% -12.50% -10.00% -15.00% -25.00% -27.50% -35.00% -40.00% /

HWP (original, Pocket Sun) HWP (original, Warmergotchi) HWP (original, )

15. HWP (original, ) 16. Control

# =

absorbance of dichromate solution after treatment absorbance of control 100% absorbance of control

P. 32

Time effect on dichromate adsorption:

Duration Control 1 hr 3 hr 5 hr 7 hr Cr2O72+ HFO (pH 7) 1.7 1.4 1.2 1.1 0.9

% change in absorbance
/ -17.6% -29.4% -35.3% -47.1%

Cr2O72+ HWP () 1. 1.7 1.6 1.5 1.5

% change in absorbance
/ 0% -5.9% -11.8% -11.8%

Control

HFO pH7 (1 hr3hrs5hrs7hrs)

HWP (1 hr3hrs5hrs7hrs)

P. 33

Discussion:
Dichromate absorption: From the data above, HFO treated in a neutral medium (sample 2) was found to be most effective in the removal of dichromate while iron filings (sample 5) were shown to be the least effective adsorbents.

The average adsorption power of HFO was the highest among all absorbents. HFO treated in neutral and alkaline mediums (samples 2 and 3) were found to have better adsorption effects than that treated in an acidic medium (sample 1). It is likely that neutral and alkaline mediums favour dichromate adsorption of HFO. Moreover, dichromate ions are likely to be converted to chromate ions at high pH and therefore absorbed by HFO.

(From left to right) HFO (NaOH, pH 5) HFO (NaOH, pH 7) HFO (NaOH, pH 9) Control

P. 34

According to the data above, the adsorption power to adsorb dichromate was found to be higher for hand warmer powder than that of each ingredient. However, as suspension was observed in the samples of iron filings and iron(III) oxide powder, the absorbance values above could not accurately reflect their effectiveness in the removal of dichromate alone. Compared with the sample with activated carbon alone, the effectiveness in the removal of dichromate was found to be lower for the mixture of activated carbon and vermiculite. It can be deduced that vermiculite is not effective or even hinders the removal of dichromate.

(From left to right) HWP () Iron filings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon Control

P. 35

Among the treated hand warmer powder samples, the one treated with concentrated hydrochloric acid (sample 11) had a slight higher dichromate adsorption power than the other treated samples. However, the original hand warmer powder was found to be more effective than all treated samples.

(From left to right)

HWP () A2 B2 C2 HWP (Pocket Sun) HWP (Warmergotchi) HWP () HWP () Control

P. 36

Among all the brands, hand warmer powder of brand was shown to be the most effective dichromate adsorbent. Although the average dichromate adsorption power of HFO is the highest, some used hand warmer powder samples, like sample 14 () and sample 15 ()are also very effective in the removal of dichromate. Thus they are also desirable dichromate adsorbents because they are easily available for domestic use. They also save much time and cost spent on the preparation of HFO.

For both and PO43- and Cr2O72- adsorption, HFO samples were found to be the most effective adsorbents. Moreover, the hand warmer powder mixture works better than the separate pure components do. However, different treatments of hand warmer powder did not show a big discrepancy in the effectiveness of dichromate removal, unlike the case in phosphate adsorption. In dichromate adsorption case, the original hand warmer powder was found to be even more effective than the treated samples. Thus we recommend used hand warmer powder of the mentioned brands for phosphate and dichromate removal. As for phosphate removal, an even more effective way will be treating the powder with dilute acid for 2 to 6 hours before use.

P. 37

Time effect on dichromate absorption: Regarding the optimum amount of time for the immersion of adsorbents in dichromate ion solution, with HFO at pH7 as the adsorbent, the absorbance of the solution was found to decrease with time. As for being the adsorbent, adsorption was generally more effective when the mixture was allowed to stand for a longer period of time. However, the percentage decrease in absorbance remained unchanged after 5 hours.

P. 38

Part III Investigating the effectiveness of metal ions adsorption on various adsorbents
The adsorption abilities of HFO on different metal ions is investigated. At an oxide surface such as HFO, a surface functional group is typically represented as an amphoteric hydroxyl group (e.g. =FeOH, =FeO-, =FeOH2+). An electrostatic attraction arises from the development of surface charge. Zinc ions can be removed by HFO adsorption according to this equation. >FeOH + Zn2+(aq) FeOZn+ + H+(aq)

Copper(II) ions, nickel(II) ions and lead(II) ions are removed by HFO adsorption according to this equation, similar to zinc ions reaction with HFO. >FeOH + Cu2+(aq) >FeOH + Ni2+(aq) >FeOH +Pb2+(aq) FeOCu+ + H+(aq) FeONi+ + H+(aq) FeOPb+ + H+(aq)

These ions can also be removed by displacement reaction when reacting with iron: Fe + Cu2+ Fe+ Ni2+ Fe+ Pb2+ Fe2+ + Cu Fe2+ + Ni Fe2+ + Pb

Activated carbon can also adsorb some of the metal ions since activated carbon has high surface area. Individual particles are convoluted and display various kinds of porosity. These micropores allow adsorption to occur, since adsorbing material can interact with many surfaces simultaneously.

P. 39

Part IIIA Determination of Zn2+ adsorption by complexometric titration

Objective:
To determine the effectiveness of Zn2+ adsorption on various adsorbents by complexometric titration.

Principle:
Complexometric titration can be carried out to determine any change in the concentration of Zn2+ in a given solution. Any decrease in the volume of burette solution (ethylenediaminetetraacetic acid, also known as EDTA solution) used to reach the end point would indicate that some Zn2+ has been adsorbed by the adsorbents. To find out the adsorption effect of various adsorbents on Zn2+, equal mass of each adsorbent is allowed to stand for several hours in standard zinc sulphate solution. The mixtures are then filtered to remove the adsorbents. Eriochrome Black T, which acts as an indicator for the end point of the reaction, and buffer solution (pH 10), which regulates the pH of the solution in the conical flask during the titration, is added to the diluted filtrate in the conical flask. The standard ZnSO4 is treated similarly and is titrated against EDTA along with the filtrate solutions, such that the volume of EDTA required for complete reaction with the other solutions can be compared with it to determine whether adsorption of zinc ions by the adsorbents have taken place. The reaction taking place was: Zn2+ + EDTA4- ZnEDTA2wine red blue

Colour changes from wine red to light blue at the end point.

Chemicals used:
Various Adsorbents 0.01M ZnSO4 (aq) 0.01M EDTA solution

P. 40

pH10 NH3/ NH4Cl buffer solution Eriochrome Black T Deionized water

Apparatus used:
Glassware Electronic balance

Procedures:
1. 25.0 cm3 of 0.01M ZnSO4 (aq) was added to a 250 cm3 volumetric flask with a pipette. Deionized water was added up to the graduation mark. 250.0 cm3 of 0.001M ZnSO4 (aq) was obtained. 2. 50.0 cm3 of 0.01M EDTA solution was added to a 250 cm3 volumetric flask with a pipette. Deionized water was added up to the graduation mark. 250.0 cm3 of 0.002M EDTA solution was obtained. 3. 25.0 cm3 of 0.01M ZnSO4 (aq) was added to 0.5 g of each adsorbent and the mixture was allowed to stand for 9 hours. 4. The mixture was filtered. The obtained filtrate was made up to 250.0 cm3 in a 250 cm3 volumetric flask. 5. 25.0 cm3 of the diluted filtrate was added to a clean conical flask with a pipette. 6. 4.0 cm3 of pH10 NH3/NH4Cl buffer solution was added to the conical flask, followed by the addition of 0.1g Eriochrome Black T.

P. 41

7. The diluted filtrate was titrated against 0.002M EDTA solution. The end point was reached when the colour of the filtrate changed from wine red to light blue.

8. 0.001M ZnSO4 (control) was also titrated against 0.002M EDTA solution.

Results:
1. HFO (NaOH, pH5) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 31.80 31.40 27.70 3 Initial reading (cm ) 4.90 4.30 0.90 Titre (cm3) 26.90 27.10 26.80 Mean titre (cm3) 26.93

2.

HFO (NaOH, pH7) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 21.20 22.80 20.70 Initial reading (cm3) 2.80 4.30 2.20 3 Titre (cm ) 18.40 18.50 18.50 3 Mean titre (cm ) 18.47 3. HFO (NaOH, pH9) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 19.90 21.70 18.70 Initial reading (cm3) 3.70 5.50 2.60 3 Titre (cm ) 16.20 16.20 16.10 3 Mean titre (cm ) 16.17

P. 42

4.

HWP ()
3

Titration 1 Titration 2 Titration 3 Final Reading (cm ) 25.10 25.10 47.90 3 Initial reading (cm ) 3.10 3.00 25.80 Titre (cm3) 22.00 22.10 22.10 3 Mean titre (cm ) 22.07 5. Iron fillings
3

Titration 1 Titration 2 Titration 3 Final Reading (cm ) 22.50 21.40 25.70 Initial reading (cm3) 1.80 0.75 5.00 3 Titre (cm ) 20.70 20.65 20.70 3 Mean titre (cm ) 20.68 6. Iron(III) oxide
3

Titration 1 Titration 2 Titration 3 Final Reading (cm ) 33.00 29.60 32.70 Initial reading (cm3) 6.40 3.00 6.20 3 Titre (cm ) 26.60 26.60 26.50 3 Mean titre (cm ) 26.56 7. Activated carbon Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 28.00 28.90 27.80 Initial reading (cm3) 1.40 2.40 1.30 3 Titre (cm ) 26.60 26.50 26.50 Mean titre (cm3) 26.53 Vermiculite + activated carbon Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 30.50 35.00 29.00 Initial reading (cm3) 5.10 9.50 3.40 3 Titre (cm ) 25.40 25.50 25.60 Mean titre (cm3) 25.53 A2 Processed HWP (dil. HCl + 4hr) Titration 1 Titration 2 Titration 3 Final Reading (cm3) 28.80 27.10 39.70 3 Initial reading (cm ) 3.80 2.00 14.50 3 Titre (cm ) 25.00 25.10 25.20 Mean titre (cm3) 25.10

8.

9.

P. 43

10. B2 Processed HWP (dil. HCl + 4hr + heat) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 28.60 26.80 31.05 Initial reading (cm3) 2.40 0.60 4.75 3 Titre (cm ) 26.20 26.20 26.30 Mean titre (cm3) 26.23 11. C2 Processed HWP (conc. HCl + 4hr) Titration 1 Titration 2 Titration 3 Final Reading (cm3) 27.10 32.90 37.30 3 Initial reading (cm ) 1.10 6.90 11.40 3 Titre (cm ) 26.00 26.00 25.90 Mean titre (cm3) 25.96 12. HWP () Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 20.25 38.00 20.70 Initial reading (cm3) 2.65 20.30 2.90 3 Titre (cm ) 17.60 17.70 17.80 3 Mean titre (cm ) 17.70 13. HWP (Warmergotchi) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 38.25 19.15 36.75 Initial reading (cm3) 20.75 1.50 19.15 3 Titre (cm ) 17.50 17.65 17.60 Mean titre (cm3) 17.58 14. HWP (Pocket Sun) Titration 1 Titration 2 Titration 3 3 Final Reading (cm ) 17.10 32.85 18.55 Initial reading (cm3) 1.40 17.10 2.80 3 Titre (cm ) 15.70 15.75 15.75 Mean titre (cm3) 15.73 15. HWP () Titration 1 Titration 2 Titration 3 Final Reading (cm3) 41.00 24.20 23.95 3 Initial reading (cm ) 18.60 1.80 1.50 3 Titre (cm ) 22.4 22.4 22.45 Mean titre (cm3) 22.42

P. 44

12. Control Titration 1 Titration 2 Titration 3 Final Reading (cm ) 29.20 28.00 30.60 Initial reading (cm3) 2.10 1.00 3.55 3 Titre (cm ) 27.10 27.00 27.05 Mean titre (cm3) 27.05
3

Discussion:
Combining the experimental results, we made the following ranking on the effectiveness of Zn2+ adsorption on various adsorbents. Rank No. Adsorbent Mean Titre (cm3) 15.74 16.167 17.58 17.69 18.467 20.68 22.07 22.42 25.10 25.53 25.96 26.23 26.53 26.56 26.93 27.05 % Change in Mean Titre (#) -41.8% -40.2% -35.0% -34.6% -31.7% -23.5% -18.4% -17.1% -7.21% -5.62% -4.03% -3.03% -1.92% -1.81% -0.44% /

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.

14. 1. 13. 12. 2. 3. 4. 15. 5. 6. 7. 8. 9. 10. 11. 16.

HWP ( Pocket Sun) HFO (NaOH, pH 9) HWP ( Warmergotchi) HWP () HFO (NaOH, pH 7) Iron filings Hand warmer powder () HWP () A2 - Processed HWP (dil. HCl + 4 hr) Vermiculite + activated carbon C2 - Processed HWP (conc. HCl + 4 hr) B2 - Processed HWP (dil. HCl + 4 hr + heat) Activated carbon Iron(III) oxide powder HFO (NaOH, pH 5) Control

(#) =

mean titre of zinc solution after treatment mean titre of control mean titre of control

x 100%

P. 45

From the above table and graph, we can see that the untreated hand warmer powder (Pocket Sun) gave the best result in adsorbing Zn2+ ions among all adsorbents, which was even better than the results of the HFOs. Two other hand warmer powders were also relatively effective in adsorbing Zn2+ ions as they reduced the amount of ions by around 35%, while HFO at pH9 reduced it by around 40%. Among the HFOs produced, HFO (NaOH, pH 9) and HFO (NaOH, pH 7) had the best two effects in adsorbing Zn2+ ions. Conversely, the HFO produced in acidic medium had extremely poor adsorption effects. It was also found that the untreated hand warmer powder had better adsorption effects than the treated ones. As for the components of the hand warmer powders, they had worse adsorption effects than most of the original hand warmer powders, showing that the original hand warmer powders which contain different components were more suitable for adsorbing Zn2+ ions.

The best adsorbent for Zn2+

P. 46

Part IIIB Determination of Cu2+ and Ni2+ adsorption by colorimetric measurement

Objective:
To determine the effectiveness of Cu2+ and Ni2+ adsorption on various adsorbents by colorimetric measurement and the time effect on the adsorption abilities.

Principle:
To find out the reduction on copper(II) ions or nickel(II) ions by the various adsorbents, a known volume of standard copper(II) sulphate solution or nickel(II) chloride solution is added to the adsorbents and filtered. The filtrate is then treated with an excess of ethane-1, 2-diamine so that all the Cu2+(aq) or Ni2+(aq) can be converted to their corresponding purple complex ions. Cu2+(aq) + 2H2NCH2CH2NH2 pale blue Ni2+(aq) + 3H2NCH2CH2NH2 green [Cu(H2NCH2CH2NH2)2]2+(aq) purple

[Ni(H2NCH2CH2NH2)3]2+(aq) violet

The intensity of the purple colour produced is proportional to the amount of copper(II) ions or nickel(II) ions present, and the absorbance can be measured using a colorimeter. The colorimeter readings are compared with that of the original solutions treated with ethane-1, 2-diamine, which act as the control, to see if any copper(II) ions or nickel(II) ions have been adsorbed. To investigate the effect of time on Cu2+ adsorption of a particular adsorbent, the time period for the adsorbent being in contact with dichromate solution is varied and the absorbance values are compared.

Chemicals used:
0.1M ethane-1,2-diamine 0.01M CuSO4 (aq)

P. 47

0.01M NiSO4 Various adsorbents

Apparatus used:
Glassware Electronic balance Colorimeter

Procedures:
1. 25.0 cm3 of 0.01M CuSO4 (aq) was added to 0.5 g of each adsorbent and the mixtures were allowed to stand for 9 hours. In addition to this, solution samples containing HFO at pH 9 and hand warmer powder were allowed to stand for 1, 3, 5 and 7 hours respectively. 2. The mixtures were filtered. 5.0 cm3 of each obtained filtrate was mixed with 5.0 cm3 of 0.1M ethane-1,2-diamine. The mixtures were poured into test tubes respectively to obtain their absorbance in a colorimeter. 3. Steps 1-3 were repeated with 0.01M NiSO4 and all mixtures were allowed to stand for 9 hours only.

P. 48

Results:
Copper adsorption: Colorimetric measurement 0.01M Cu2+ 0.01M Ni2+ absorbance absorbance 0.37 0.05 0.15 0.005 0.07 0.035 0.32 0.045 0.28 0.38 0.22 0.35 0.38 0.37 0.36 0.39 0.34 0.20 0.23 0.425 0.05 0.037 0.04 0.035 0.04 0.044 0.05 0.055 0.048 0.044 0.023 0.06

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.

Adsorbent HFO (NaOH, pH 5) HFO (NaOH, pH 7) HFO (NaOH, pH 9) Hand warmer powder () Iron filings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon A2 - Processed HWP (dil HCl + 4 hr) B2 - Processed HWP (dil HCl + 4 hr + heat) C2 - Processed HWP (conc HCl + 4 hr) Hand warmer powder () Hand warmer powder (Warmergotchi) Hand warmer powder (Pocket Sun) Hand warmer powder () Control

(From left to right) Nickel solutions after adsorption HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), HWP ( ), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control

P. 49

Time effect on copper adsorption:

Duration Control 1 hr 3 hr 5 hr 7 hr Cu2+ + HFO (pH 9) 0.38 0.24 0.19 0.16 0.14

% Change in Absorbance
/ -36.8 -50.0 -57.9 -63.2

Cu2+ + HWP () 0.38 0.34 0.20 0.17 0.14

% Change in Absorbance
/ -10.5 -47.4 -55.3 -63.2

Control

HFO pH7 (1 hr3hrs5hrs7hrs)

HWP (1 hr3hrs5hrs7hrs)

P. 50

Discussion:
Copper adsorption: Based on the experimental results, we made the following ranking on the effectiveness of Cu2+ adsorption on various adsorbents. Colorimetric Measurement 0.01M Cu2+ Absorbance % Change in Absorbance (#) 0.07 -83.5 0.15 -64.7 0.2 -52.9 0.22 -48.2 0.23 -45.9 0.28 0.32 0.34 0.35 0.36 0.37 0.37 0.38 0.38 0.39 0.425 -34.1 -24.7 -20 -17.6 -15.3 -12.9 -12.9 -10.6 -10.6 -8.2 /

Rank

No.

Adsorbent

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.

2. 3. 14. 7. 15. 5. 4. 13. 8. 11. 10. 1. 6. 9. 12. 16.

HFO (NaOH, pH 9) HFO (NaOH, pH 7) Hand warmer powder (Pocket Sun) Activated carbon Hand warmer powder () Iron filings Hand warmer powder () Hand warmer powder (Warmergotchi) Vermiculite + activated carbon C2 - Processed HWP (conc HCl + 4 hr) B2 - Processed HWP (dil HCl + 4 hr + heat) HFO (NaOH, pH 5) Iron(III) oxide powder A2 - Processed HWP (dil HCl + 4 hr) Hand warmer powder () Control

12.

13. 16.

x 100% (#) = absorbance of copper solution after treatment absorbance of control absorbance of control (From left to right) HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), Hand warmer powder ( ), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control

P. 51

HFO at pH9 and HFO at pH7 were the best two adsorbents of Cu2+ ions among all adsorbents while the effectiveness of HFO at pH5 was still far lower than that of HFO at pH9 and HFO at pH7. As for the untreated hand warmer powders, although they were not as effective as HFO at pH9 and HFO at pH7, two of them led to reduction in absorbance by over 45%, showing that they can also be used to adsorb Cu2+ ions. Most of the untreated hand warmer powder had better adsorption effects than the treated ones. Also, the hand warmer powder named Pocket Sun had better adsorption effects than the separate components of hand warmer powder.

(From left to right) HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), Hand warmer powder ( ), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control

HWP , HWP Pocket Sun, HWP Warmergotchi, HWP

P. 52

Time effect on copper adsorption:

Concerning the optimum length of time for the immersion of absorbents in Cu2+ solution, with HFO at pH9 as the adsorbent, the percentage decrease in absorbance was found to increase with time. As for being the adsorbent, adsorption was more effective when the mixture was allowed to stand for a longer period of time. In short, the percentage decrease in absorbance was found to increase with time for both adsorbents, HFO at pH9 and .

P. 53

For the effectiveness of Ni2+ adsorption on various adsorbents, the ranking is as follows: Colorimetric Measurement 0.01M Ni2+ Absorbance % Change in Absorbance (#) 0.005 -91.7 0.023 -61.7 0.035 -41.7 0.035 -41.7 0.037 -38.3 0.04 -33.3 0.04 -33.3
0.044 0.045 0.045 0.048 0.05 0.05 0.05 0.055

Rank 1. 2. 3. 4. 5.

No. 2. 15. 3. 8. 6. 7. 9. 10. 14. 4. 13. 1. 5. 11. 12. 16.

Adsorbent
HFO (NaOH, pH 7) Hand warmer powder () HFO (NaOH, pH 9) Vermiculite + activated carbon Iron(III) oxide powder Activated carbon A2 - Processed HWP (dil HCl + 4 hr) B2 - Processed HWP (dil HCl + 4 hr + heat) Hand warmer powder (Pocket Sun) Hand warmer powder () Hand warmer powder (Warmergotchi) HFO (NaOH, pH 5) Iron filings C2 - Processed HWP (conc HCl + 4 hr) Hand warmer powder ()

6. 7. 8. 9.

-26.7 -25.0 -25.0 -20 -16.7 -16.7 -16.7 -8.33 /

10. 11.

Control

0.13

(#) =

absorbance of nickel solution after treatment absorbance of control x 100% absorbance of control (From left to right) HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), Hand warmer powder ( ), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control

P. 54

The experimental results showed HFO at pH7 was the best adsorbent in adsorbing Ni2+ ions, followed by the untreated hand warmer powder being the second best adsorbent. The untreated hand warmer powder led to a reduction of 61.7% in absorbance, showing that it had better adsorption effects than HFO at pH9, components of hand warmer powders and the treated hand warmer powders. In adsorbing Ni2+ ions, two of the treated hand warmer powders (treated with dilute hydrochloric acid for 4 hours, with and without heat) and three of the separate components of hand warmer powders (vermiculite, activated carbon and iron(III) oxide powder) performed better than some of the untreated hand warmer powder. Nevertheless, it is important to note that the untreated hand warmer is still quite effective in adsorbing Ni2+ ions and can therefore be used to adsorb Ni2+ ions.

(From left to right) HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), Hand warmer powder ( ), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control, HWP , HWP Pocket Sun, HWP Warmergotchi, HWP

P. 55

Part IIIC
Objective:

Determination of Pb2+ adsorption by gravimetric analysis through precipitation

To determine the effectiveness of Pb2+ adsorption on various adsorbents by gravimetric analysis through precipitation.

Principle:
To find out the reduction of Pb2+ by the various adsorbents, a known volume of Pb2+ solution is added to the adsorbents and filtered, same volume of an excess of potassium iodide is added to the filtrate and yellow precipitates is formed. Pb2+(aq) + 2I(aq) colourless PbI2(s) bright yellow ppt

The mixture is then filtered again to obtain the precipitates. The precipitates are washed, dried and weighed. The mass of the precipitates is proportional to the number of moles of Pb2+ present, lead(II) ions have been successfully adsorbed by the adsorbents if the mass of the lead(II) iodide of a particular sample is lower than that of the control.

P. 56

Chemicals used:
Various adsorbents 0.01M Pb(NO3)2 0.2M KI

Apparatus used:
Glassware Electronic balance Stopwatches

Procedures:
1. 0.5 g of various adsorbents were added to 25.0 cm3 of 0.01 M Pb(NO3)2 and were allowed to stand for 9 hours. 10 cm3 of 0.2M KI (in excess) was added to the filtrate to precipitate out all the PbI2(s). The mass of each dry filter paper was measured. The mixture was filtered and the total mass of the filter paper and the precipitate was measured after the filter paper was dried. 4. The mass of precipitate was calculated. Mass of precipitate (g) = Total mass of filter paper and precipitate Mass of each dry filter paper

2.

3.

P. 57

Results:
Gravimetric analysis 0.01M Pb2+ Mass of precipitate (g) 0.10 0.12(*) 0.10 0.09 0.03 0.11 0.10 0.10 0.10 0.11 0.10 0.12 (*) 0.10 0.11 0.10 0.12

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.

Adsorbent HFO (NaOH, pH 5) HFO (NaOH, pH 7) HFO (NaOH, pH 9) Hand warmer powder () Iron filings Iron(III) oxide powder Activated carbon Vermiculite + activated carbon A2 - Processed HWP (dil HCl + 4 hr) B2 - Processed HWP (dil HCl + 4 hr + heat) C2 - Processed HWP (conc HCl + 4 hr) Hand warmer powder () Hand warmer powder (Warmergotchi) Hand warmer powder (Pocket Sun) Hand warmer powder () Control

(*) The colour of the precipitate was not bright yellow, implying that the precipitate may contain other compounds and so the mass of precipitate was greater than the control.

(From left to right) Control, HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9) Hand warmer powder (),A2, B2, C2 Activated carbon, Vermiculite + activated carbon, Iron filings, Iron(III) oxide powder HWP , HWP Pocket Sun, HWP , HWP Warmergotchi

P. 58

Discussion:
The effectiveness of Pb2+ adsorption on various adsorbents were compared and the ranking is as follows: Gravimetric Analysis 0.01M Pb2+ Rank No. Adsorbent Mass of % Change in Mass Precipitate (g) of Precipitate (#) 0.03 1. 5. Iron filings -75 0.09 2. 4. Hand warmer powder () -25 0.10 3. 1. HFO (NaOH, pH 5) - 16.7 0.10 3. HFO (NaOH, pH 9) - 16.7 0.10 7. Vermiculite + activated carbon - 16.7 0.10 8. Activated carbon - 16.7 0.10 9. A2 - Processed HWP (dil HCl + 4 hr) - 16.7 0.10 11. C2 - Processed HWP (conc HCl + 4 hr) - 16.7 0.10 13. Hand warmer powder (Warmergotchi) - 16.7 0.10 15. Hand warmer powder () - 16.7 0.109 4. 14. Hand warmer powder (Pocket Sun) -9.2 Iron(III) oxide powder 0.11 5. 6. -8.3 B2 Processed HWP (dil HCl + 4 hr + 0.11 10. -8.3 6. 7. 12. 2. 16.
heat) Hand warmer powder () HFO (NaOH, pH 7) 0.12 0.12(*)

Control

0.12

0 0 /

(*) The colour of the precipitate was not bright yellow, implying that the precipitate may contain other compounds and so the mass of precipitate was greater than the control.

(#) =

mass of precipitate from lead(II) solution after treatment mass of precipitate from control mass of precipitate from control
adsorbance of control

x 100%

(From left to right) HFO (NaOH, pH 5), HFO (NaOH, pH 7), HFO (NaOH, pH 9), Hand warmer powder (), Iron filings, Iron(III) oxide powder, Activated carbon, Vermiculite + activated carbon, A2, B2, C2, Control

P. 59

In the case of adsorption of Pb2+ ions, iron filings was the best adsorbent since iron metal effectively precipitates Pb2+ ions from its aqueous solution. The second best adsorbent, untreated hand warmer powder () had better adsorption effects than the HFOs and the treated hand warmer powders. Some other used hand warmer powders like Warmergotchi and had similar adsorption effects as HFO at pH 5 and 9 and components of used hand warmer powders like vermiculite and activated carbon. In short, to adsorb Pb2+ ions, iron filings and the hand warmer powder () are preferred to be used.

P. 60

Combining results from part IIIA, IIIB and IIIC, we can see that among the HFOs prepared, HFO(NaOH, pH 7) and HFO(NaOH, pH 9) were the two adsorbents with the best effects in adsorbing Zn2+, Cu2+ and Ni2+ ions. However, we noticed that another type of HFO HFO(NaOH, pH 5) had relatively poor effectiveness in adsorbing Zn2+ and Cu2+ ions as compared to the other two HFOs. It was especially poor in adsorbing Zn2+ ions and could only reduce the amount of Zn2+ ions by 0.444%. This implies that the pH value of HFO affects its effectiveness in adsorbing metal ions. For instance, HFO produced in a neutral or alkaline medium better adsorbs Zn2+, Cu2+ and Ni2+ ions.

Nevertheless, the effectiveness of Pb2+ adsorption on different HFOs was quite different from that of Zn2+, Cu2+ and Ni2+ adsorption. The effectiveness of Pb2+ adsorption on HFO(NaOH, pH 7) and HFO(NaOH, pH 9) was significantly lower than that of Zn2+, Cu2+ and Ni2+ ions adsorption on them while the effectiveness of Pb2+ adsorption on HFO(NaOH, pH 5) was still quite low.

In short, among the three types of HFOs, HFO(NaOH, pH 9) was found to be the most suitable in adsorbing Zn2+ and Cu2+ ions while HFO(NaOH, pH 7) was found to be the most suitable in adsorbing Ni2+ ions. As for the adsorption of Pb2+ ions, considering the fact that the amount of yield of HFO(NaOH, pH 9) during production was greater than that of HFO(NaOH, pH 5), it was found to be the most appropriate in adsorbing Pb2+ ions.

The effectiveness of metal ions adsorption on hand warmer powders was another main focus of this part. It was found that some used hand warmer powder had similar or even better adsorption effects than the HFOs in

P. 61

adsorbing metal ions. For example, in adsorbing Zn2+ ions, the hand warmer powder (Pocket Sun) reduced the amount of ions by 41.8%, which was greater then the percentage reduced by the HFOs. Therefore, the hand warmer powders are also effective in adsorbing metal ions and may even have better adsorption effects than the HFOs.

Having known that hand warmer powders are effective in adsorbing metal ions, we looked into whether treated or untreated hand warmer powders had better adsorption effects. It was found that untreated hand warmer powders were generally more effective in adsorbing Zn2+ and Cu2+ ions. For the adsorption of Ni2+ ions, the hand warmer powder reduced the amount of ions by 61.7% while the treated hand warmer powders reduced the amount of ions by 25% on average only. While for the adsorption of Pb2+ ions, the hand warmer powder () performed better than the treated ones while other hand warmer powders had similar adsorption effects as the treated ones. Therefore, as most untreated hand warmer powders were more effective than the treated ones or had similar adsorption effects as the treated ones, the untreated hand warmer powders are more suitable for adsorbing metal ions so as to save resources for treating them.

P. 62

As the hand warmer powder is composed of different substances, the adsorption effects of these substances were investigated too to see whether these separate pure components of hand warmer powder adsorb better than the original hand warmer powder. From the experimental results, we noticed that for the five brands of hand warmer powders investigated, most of them had better or similar adsorption effects than their components. For instance, 3 brands of hand warmer powders investigated performed better than their components in adsorbing Zn2+ ions. This showed that the adsorption of metal ions with the original hand warmer powders is preferred to with the components of hand warmer powders. Hence, costs and resources of separating the components of used hand warmer powders can be saved when preparing adsorbents for metal ions adsorption.

P. 63

From all the results above, it was shown that some of the used untreated hand warmer powders were even more effective in adsorbing metal ions than the HFOs. Thus, it is a good idea to make use of used hand warmer powders to remove pollutants from industrial wastewater in order to conserve our environment. This is because there is no cost in using the used hand warmer powders which are considered as waste and the used hand warmer powders are not difficult to obtain. Also, by using used hand warmer powders to remove pollutants in wastewater, the volume of solid waste can be reduced which in turn reduce the pressure on the already over-burdened landfills.

In order to put this environmentally-friendly idea into practice, collection bins of used hand warmer powders can be set up in various places, for instance, MTR stations and lobbies of residential buildings so the collected powders can be transported to different sewage treatment station to remove pollutants from wastewater.

P. 64

Part IIID Determination of hardness adsorption by EDTA titration

Objective:
To investigate the adsorption ability of used hand warmer powder to remove hardness of water.

Principle:
Natural mineral water contains calcium and magnesium ions, resulting in hardness of water which brings about inconvenience in domestic water usage as well as environmental problems. In this part, we investigated the ability of used hand warmer powder to adsorb calcium and magnesium ions in both laboratory solutions and in commercial mineral water. In order to determine the amount of calcium and magnesium ions present, titration of the solution against a standard solution of ethylenediaminetetraacetic acid (EDTA) can be carried out in alkaline medium based on complexation reactions. Calcium and magnesium ions can be removed by adsorption according to these equations. >FeOH + Ca2+(aq) >FeOH + Mg2+(aq) FeOCa+ + H+(aq) FeOMg+ + H+(aq)

In experiment A, the Ca2+ and Mg2+ adsorption ability of various adsorbents will be investigated using laboratory reagents. Various adsorbents will be stood for several hours in standard calcium and magnesium solutions respectively. Titration against EDTA solution will be carried out to determine the concentration of calcium and magnesium ions after treatment. Control experiments will be carried out for comparison of results. As calcium ions, magnesium ions, calcium-EDTA complex and magnesium-EDTA complex are colourless, a suitable indicator that will change colour at the equivalence point has to be used. Eriochrome Black T. is chosen as the indicator, in which end point is reached when the wine red colour changes into a blue colour in high pH. A buffer of ammonium-ammonia at pH 10 will be added to maintain a steady pH value. Ca2+ + EDTA4- CaEDTA2wine red blue Mg2+ + EDTA4- MgEDTA2wine red blue

P. 65

In experiment B, the Ca2+ and Mg2+ adsorption ability of different brands of used hand warmer powder will be investigated using a commercial brand of mineral water. Same masses of used hand warmer powder will be stood in a fixed volume of mineral water for several hours. Titration against EDTA solution will then be carried out as in experiment A to determine the metal concentrations after the treatment. Mineral water contains other metal ions apart from calcium and magnesium. Since EDTA solution reacts directly with many metal ions, the presence of other metal ions in mineral water may interfere with the result. The metal cations present in the commercial brands of mineral water which are in relatively significant amounts are Ca2+, Mg2+, Na+ and K+. The alkali metals, sodium and potassium, do not react with EDTA solution thus their presence can be ignored. Other metal ions would be precipitated out under high pH and are not complexed by EDTA, thus their presence can also be ignored. A control of unadsorbed mineral water will be titrated as well for comparison. A smaller volume of EDTA solution used for titration of filtrates than the control would mean that there is a reduction in calcium and magnesium ions after adsorption, thereby indicating that used hand warmer powder is effective in removing hardness of water.

Chemicals used:
Various Adsorbents 0.01M CaCl2 (aq) 0.01M Mg(NO3)2 (aq) 0.01M EDTA solution No Frills bottled mineral water pH10 NH3/ NH4Cl buffer solution Eriochrome Black T Deionized water

P. 66

Apparatus used:
Glassware Electronic balance

Procedures:
Experiment A 1. 25.0 cm3 of 0.01M CaCl2 (aq) was added to a 250 cm3 volumetric flask with a pipette. Deionized water was added up to the graduation mark. 250.0 cm3 of 0.001M CaCl2 (aq) was obtained. 2. 50.0 cm3 of 0.01M EDTA solution was added to a 250 cm3 volumetric flask with a pipette. Deionized water was added up to the graduation mark. 250.0 cm3 of 0.002M EDTA solution was obtained. 3. 25.0 cm3 of 0.01M CaCl2 (aq) was added to 0.5 g of each adsorbent and the mixture was allowed to stand for 9 hours. 4. The mixture was filtered. The obtained filtrate was made up to 250.0 cm3 in a 250 cm3 volumetric flask.

5. 25.0 cm3 of the diluted filtrate was added to a clean conical flask with a pipette. 6. 4.0 cm3 of pH10 NH3/NH4Cl buffer solution was added to the conical flask, followed by the addition of 0.1g Eriochrome Black T.

P. 67

7. The diluted filtrate was titrated against 0.002M EDTA solution. The end point was reached when the colour of the filtrate changed from wine red to blue. 8. 0.001M CaCl2 (aq) (control) was also titrated against 0.002M EDTA solution. 9. The above procedures were repeated using Mg(NO3)2 (aq) instead of CaCl2 (aq) Experiment B 1. 1.0 g of each brand of used hand warmer powder was weighed separately. 2. 50.0cm3 of No Frills mineral water was pipetted into each sample of used hand warmer powder. 3. The mixture was left to stand for three and a half hours. 4. The mixture was filtered. The obtained filtrate was made up to 250.00 cm3 in a 250 cm3 volumetric flask. 5. 25.0 cm3 of the diluted filtrate was added to a clean conical flask with a pipette. 6. 4.0 cm3 of pH10 NH3/NH4Cl buffer solution was added to the conical flask, followed by the addition of 0.1g Eriochrome Black T. 7. The diluted filtrate was titrated against 0.002M EDTA solution. The end point was reached when the colour of the filtrate changed from wine red to blue.

8. 50.0 cm3 of No Frills mineral water was pipetted into a 250cm3 volumetric flask and made up to 250.0cm3 as the control. 9. 25.0 cm3 of the control solution was also titrated against 0.002M EDTA solution.

P. 68

Results:
Calcium ion adsorption titrations: 1. HFO pH 5 Titration 1 24.10 3.80 20.30 20.20 Titration 2 44.20 24.10 20.10 Titration 3 26.50 6.30 20.20

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 2. HFO pH 7
3

Titration 1 Final reading (cm ) 27.10 Initial reading (cm3) 6.50 Titre (cm3) 20.60 3 Mean titre (cm ) 20.60 3. HFO pH9
3

Titration 2 24.60 4.10 20.50

Titration 3 28.20 7.50 20.70

Titration 1 Final reading (cm ) 33.10 Initial reading (cm3) 19.00 Titre (cm3) 14.10 3 Mean titre (cm ) 14.20 4. HWP () Titration 1 25.40 7.10 18.30 18.35

Titration 2 17.00 2.70 14.30

Titration 3 31.20 17.00 14.20

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 5. Iron filings

Titration 2 23.15 4.70 18.45

Titration 3 23.60 5.30 18.30

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3)

Titration 1 21.60 2.40 19.20 19.12

Titration 2 25.65 6.60 19.05

Titration 3 35.10 16.00 19.10

P. 69

6.

Iron(III) oxide
3

Titration 1 Final reading (cm ) 25.50 Initial reading (cm3) 5.70 Titre (cm3) 19.80 Mean titre (cm3) 19.93 7. Activated carbon Titration 1 Final reading (cm3) 24.40 Initial reading (cm3) 4.50 Titre (cm3) 19.90 Mean titre (cm3) 19.97 8.

Titration 2 23.90 3.90 20.00

Titration 3 21.75 1.75 20.00

Titration 2 25.60 5.60 20.00

Titration 3 21.10 1.10 20.00

Vermiculite + Activated carbon Titration 1 Titration 2 Final reading (cm3) 20.20 20.80 3 Initial reading (cm ) 1.20 1.70 3 Titre (cm ) 19.00 19.10 Mean titre (cm3) 19.00 9. A2 Titration 1 25.40 6.35 19.05 19.02 Titration 2 44.50 25.40 19.10

Titration 3 39.70 20.80 18.90

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 10. B2 Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 11. C2

Titration 3 19.40 0.70 18.90

Titration 1 44.30 25.90 18.40 18.50

Titration 2 26.00 7.50 18.50

Titration 3 27.70 9.10 18.60

Titration 1 Final reading (cm ) 25.40 Initial reading (cm3) 6.10 Titre (cm3) 19.30 3 Mean titre (cm ) 19.37
3

Titration 2 44.90 25.40 19.50

Titration 3 25.40 6.10 19.30

P. 70

12. HWP () Titration 1 3 Final reading (cm ) 22.40 Initial reading (cm3) 2.60 Titre (cm3) 19.80 3 Mean titre (cm ) 19.67 13. HWP (WarmerGotchi) Titration 1 3 Final reading (cm ) 21.40 Initial reading (cm3) 3.30 Titre (cm3) 18.10 3 Mean titre (cm ) 18.00 14. HWP (Pocket Sun) Titration 1 3 Final reading (cm ) 18.60 Initial reading (cm3) 1.70 Titre (cm3) 16.90 3 Mean titre (cm ) 16.90 15. HWP () Titration 1 Final reading (cm3) 25.90 Initial reading (cm3) 7.30 Titre (cm3) 18.60 3 Mean titre (cm ) 18.67 16. Control Titration 1 Final reading (cm ) 23.00 Initial reading (cm3) 3.20 Titre (cm3) 19.80 3 Mean titre (cm ) 19.70
3

Titration 2 23.00 3.40 19.60

Titration 3 23.80 4.20 19.60

Titration 2 19.70 1.70 18.00

Titration 3 37.60 19.70 17.90

Titration 2 35.40 18.60 16.80

Titration 3 20.80 3.80 17.00

Titration 2 28.70 10.00 18.70

Titration 3 39.40 20.70 18.70

Titration 3 22.30 2.60 19.70

Titration 3 41.90 22.30 19.60

P. 71

Magnesium adsorption titrations: 1. HFO pH5

3

Titration 1 Final reading (cm ) 28.50 Initial reading (cm3) 5.10 Titre (cm3) 23.40 Mean titre (cm3) 23.33 2. HFO pH7 Titration 1 26.50 2.30 24.20 24.15

Titration 2 25.20 2.00 23.20

Titration 3 36.30 12.90 23.40

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 3. HFO pH9

Titration 2 24.70 0.65 24.05

Titration 3 24.70 0.50 24.20

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 4. Iron(III) oxide

Titration 1 26.00 1.00 25.00 24.90

Titration 2 49.60 24.70 24.90

Titration 3 26.40 1.60 24.80

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 5.

Titration 1 24.40 0.20 24.20 24.20

Titration 2 25.60 1.50 24.10

Titration 3 47.00 22.70 24.30

Activated carbon Titration 1 Final reading (cm3) 39.30 Initial reading (cm3) 4.30 Titre (cm3) 35.00 3 Mean titre (cm ) 34.90

Titration 2 35.50 0.60 34.90

Titration 3 35.90 1.10 34.80

P. 72

6.

Vermiculite + activated carbon Titration 1 Titration 2 3 Final reading (cm ) 24.30 26.40 Initial reading (cm3) 0.60 2.90 3 Titre (cm ) 23.70 23.50 Mean titre (cm3) 23.60 7. A2 Titration 1 23.30 1.20 22.10 22.08 Titration 2 25.10 3.05 22.05

Titration 3 25.40 1.80 23.60

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 8. B2

Titration 3 23.90 1.80 22.10

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 9. C2

Titration 1 23.00 0.85 22.15 22.08

Titration 2 26.10 3.90 22.20

Titration 3 40.20 18.30 21.90

Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3) 10. Control Final reading (cm3) Initial reading (cm3) Titre (cm3) Mean titre (cm3)

Titration 1 25.20 1.35 23.85 23.93

Titration 2 25.45 1.40 24.05

Titration 3 25.70 1.80 23.90

Titration 1 26.00 0.70 25.30 25.13

Titration 2 25.80 0.70 25.10

Titration 3 49.20 24.20 25.00

P. 73

Mineral water hardness adsorption titrations: 1. HWP () 1 Final burette reading (cm3) 13.70 Initial burette reading (cm3) 5.10 3 Titre (cm ) 8.60 Mean titre (cm3) 8.57 2. HWP () 1 Final burette reading (cm3) 12.15 Initial burette reading (cm3) 4.55 Titre (cm3) 7.60 Mean titre (cm3) 7.35 3. HWP (Warmergotchi) 1 Final burette reading (cm ) 14.50 Initial burette reading (cm3) 7.85 3 Titre (cm ) 6.65 Mean titre (cm3) 6.55
3

2 22.90 14.40 8.50

3 31.70 23.10 8.60

2 19.60 12.25 7.35

3 26.90 19.60 7.30

4 24.40 27.00 7.40

2 21.05 14.50 6.55

3 27.50 21.05 6.45

4. HWP (Pocket Sun) 1 Final burette reading (cm ) 7.45 Initial burette reading (cm3) 2.20 Titre (cm3) 5.25 Mean titre (cm3) 4.38
3

2 11.90 7.40 4.50

3 16.50 12.20 4.30

4 20.90 16.55 4.35

5. HWP () 1 Final burette reading (cm ) 10.80 3 Initial burette reading (cm ) 2.20 Titre (cm3) 8.60 3 Mean titre (cm ) 8.53
3

2 19.30 10.80 8.50

3 27.80 19.30 8.50

6. HWP (Control) 1 Final burette reading (cm ) 14.60 Initial burette reading (cm3) 4.10 3 Titre (cm ) 10.50 3 Mean titre (cm ) 10.47
3

2 25.40 14.90 10.50

3 35.80 25.40 10.40

P. 74

Discussion:
Effectiveness of Ca2+ adsorption: Mean Titre of Calcium Solutions after Treatment Mean titre (cm3)
25 20 15 10 5 0

Adsorbents
From the above graph, it can be seen that most the mean titre for most adsorbents were lower than that of control, indicating that there was a decrease in calcium content. Among the different brands of used hand warmer powder, Pocket Sun has the best adsorption effect while has the poorest adsorption effect. Rank 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. (#) = No. 3 14 13 4 10 15 8 9 5 11 12 6 7 1 2 16. Adsorbent HFO (NaOH, pH 9) HWP ( Pocket Sun) HWP ( Warmergotchi) Hand warmer powder () B2 Processed HWP (dil. HCl + 4 hr + heat) HWP () Vermiculite + activated carbon A2 Processed HWP (dil. HCl + 4 hr) Iron filings C2 Processed HWP (conc. HCl + 4 hr) HWP ()
Iron(III) oxide powder (*suspension observed)

Mean Titre (cm3) 14.20 16.90 18.00 18.35 18.50 18.67 19.00 19.02 19.12 19.37 19.67 19.93 19.97 20.20 20.60 19.70

% Change in Mean Titre (#) -27.9% -14.2% -8.6% -6.9% -6.1% -5.2% -3.6% -3.5% -2.9% -1.7% -0.15% +1.2% +1.4% +2.5% +4.6% / x 100%

Activated carbon HFO (NaOH, pH 5) HFO (NaOH, pH 7) Control

mean titre of calcium solution after treatment mean titre of control mean titre of control

P. 75

Mean Titre of Calcium Solutions after Treatment of HFOs

Mean Titre (cm3) 25 20 15 10 5 0
HFO (NaOH, HFO (NaOH, HFO (NaOH, pH 5) pH 7) pH9) Control

Adsorbents

Certain data obtained were found to be unusual, i.e. the mean titre obtained was even higher than that of the control, which should not be the case because the concentration of calcium ions should not be higher than that of the original solution it started with. To explain this result, we hypothesized that some of the iron present in HFO may have somehow dissolved into the calcium solution to form iron ions. Since EDTA reacts with iron ions, the volume of EDTA solution used would be greater than that of calcium ions alone. Another possible explanation is due to experimental errors. Effectiveness of Mg2+ adsorption: Rank 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. (#) = No. 9 10 1 8 11 2 6 3 7 12. Adsorbent A2 Processed HWP (dil. HCl + 4 hr) B2 Processed HWP (dil. HCl + 4 hr + heat) HFO (NaOH, pH 5) Vermiculite + activated carbon C2 Processed HWP (conc. HCl + 4 hr) HFO (NaOH, pH 7) Iron(III) oxide powder HFO (NaOH, pH 9) Activated carbon Control Mean Titre (cm3) 22.08 22.08 23.33 23.60 23.93 24.15 24.20 24.90 34.90 25.13 % Change in Mean Titre (#) -12.13% -12.13% -7.16% -6.09% -4.78% -3.90% -3.70% -0.92% +38.88% / x 100%

mean titre of magnesium solution after treatment mean titre of control mean titre of control

P. 76

Mean Titre of Magnesium Solutions after Treatment 40 35 Mean Titre (cm3) 30

25
20 15 10 5 0
HFO HFO (NaOH, pH (NaOH, pH 5) 7) HFO (NaOH, pH9) Iron(III) oxide powder Activated Vermiculite A2 B2 C2 carbon + activated Processed Processed Processed carbon HWP (dil. HWP (dil. HWP (conc. HCl + 4 hr) HCl + 4 hr + HCl + 4 hr) heat) Adsorbents Control

From the above graph, we can see that processed hand warmer powder (dil. HCl + 4 hr) and processed hand warmer powder (dil. HCl + 4 hr + heat) had the best two effects in adsorbing Mg2+ ions among all adsorbents. However, a complete comparison among all adsorbents was not possible since upon adding buffer solution of pH 10 to magnesium solution treated by untreated used hand warmer powder, brown precipitate was observed. Upon adding indicator, colour of solution turns brownish red instead of the usual wine red, and upon adding EDTA solution, the solution turned light brown, the end point cannot be easily detected. Thus, the Mg2+ adsorption ability of used hand warmer powder was unable to be investigated. Although experimental results were not able to be obtained, we are still able to deduce the Mg2+ adsorption ability based on available data. With the exception of activated carbon (in which the results were unusual for both calcium and magnesium), all other data attained in the magnesium experiment showed positive adsorption results. After comparison with the adsorption results of the same adsorbents in the calcium experiment, it can be deduced that used hand warmer powder can adsorb magnesium ions as well, because all the hand warmer powder were effective in adsorbing calcium ions.

P. 77

Effectiveness of hardness adsorption from mineral water:

To confirm our conclusion drawn from experiment A which used laboratory reagents, mineral water was also adsorbed. Results show that all brands of used hand warmer powder investigated have positive adsorption results. Pocket Sun has the best adsorption effect, which is consistent with experiment A. Since EDTA solution reacts with both calcium and magnesium ions, the mean titre obtained is a reflection of the overall sum of calcium and magnesium ions that have been adsorbed. Thus, it is not possible to determine the actual decrease in concentration of the respective two metal ions. Nonetheless, it can be concluded that there is a reduction in the amount of calcium and magnesium ions after adsorption by used hand warmer powder. Thus, used hand warmer powder is effective in removing hardness of water.

P. 78

Part IVA
Objective:

Investigating the effectiveness of filtration device and the regeneration of HFO in the device

To determine the effectiveness of toxic ions removal by hand warmer powder-packed column.

Principles:
To find out the effectiveness of toxic ions removal by hand warmer powder-packed column, a known volume of phosphate, dichromate, copper(II), zinc, lead(II) and nickel(II) ion solutions are allowed to pass through the Warmergotchi-packed columns. After washing the columns several times by deionized water, the amount of the remaining anions / metal cations in the resulting solutions can be determined by gravimetric measurement. For phosphate and dichromate, an excess of aqueous lead(II) nitrate is added to the solutions in order to precipitate out any remained phosphate and chromate ions as insoluble lead(II) phosphate and lead(II) chromate. Pb2+ (aq) + PO43- (aq) Pb3(PO4)2 (s) Pb2+ (aq) + CrO42-(aq) PbCrO4 (s) For metal cations, an excess of aqueous sodium carbonate is added to precipitate out any remained metal ions as insoluble metal carbonates. M2+(aq) + CO32- (aq) MCO3 (s) The precipitates are washed, dried and weighed. The mass of the precipitates is proportional to the number of moles of phosphate or dichromate or metal ions unadsorbed, if the ions have been successfully adsorbed by the Warmergotchi-packed column, the mass of the precipitates would be lower than that of the control.

The reaction for the adsorption of cations by hydrous ferric oxide is as follows: >FeOH + M2+(aq) FeOM+ + H+(aq)

In order to regenerate hydrous ferric oxide, dilute sulphuric acid should be added to the adsorbents to reverse the reaction.

P. 79

Chemicals used:
0.01M PbNO3 (aq), NiSO4 (aq), ZnSO4 (aq), K2Cr2O7 (aq), CuSO4 (aq), Na3PO4 (aq)

Hand warmer powder (Warmergotchi) 1M Na2CO3 (aq) 0.5M Pb(NO3)2 (aq)

Apparatus used:
Electronic balance Glass wear

Procedures:
1. 15g of untreated used Warmergotchi hand warmer powder was packed in each of six burettes as shown.

2. 25 cm3 of each ion solution was pipetted and allowed to run through the packed hand warmer powder column for adsorption.

P. 80

Metal ions solution

Phosphate solution

Dichromate solution

3. The columns were washed for three times with 25 cm3 of deionised water each time. 4. The filtrate collected was treated with 0.5M Pb(NO3)2(aq) and 1M Na2CO3(aq) respectively. The precipitates obtained were filtered under suction, washed and dried in an oven. 5. The mass of the precipitate was weighed and compared with that generated from the control solution.
Precipitates Precipitates Precipitates formed by formed by formed by phosphate control copper(II) control nickel(II) control Precipitates formed by zinc control Precipitates formed by lead(II) control Precipitates formed by dichromate control

Precipitates formed Precipitates formed Precipitates Precipitates by treated by treated formed by treated formed by treated phosphate solution copper(II) solution nickel(II) solution zinc solution

Precipitates Precipitates formed formed by treated by treated lead(II) solution dichromate solution

P. 81

Results:
Mass of precipitates formed by control solution 1.89g 0.34g 0.30g 0.70g 0.29g 2.09g Mass of precipitates formed by solution treated by Warmergotchi 1.44g 0g 0.22g 0g 0.02g 1.20g

Lead(II) phosphate Copper(II) carbonate Zinc carbonate Lead(II) carbonate Nickel(II) carbonate Lead(II) chromate

Discussion:

From the above table and graph, it can be shown that the Warmergotchi-packed column is extremely effective in adsorbing different ions. Despite the success of adsorbing different ions from solutions, it took a long time for some solutions, phosphate solution in particular, to pass through the Warmergotchi-packed column, resulting in the formation of iron ions precipitates which came from iron ions washed down from the Warmergotchi column for treated phosphate, zinc and lead(II) ions solution.

P. 82

However, some solutions, such as copper(II) solution and nickel(II) solution took a relatively shorter time to pass through the Warmergotchi-packed column. Nickel (II) and copper(II) solution were therefore used for the second part of the experiment. Separate nickel(II) solution was treated by the same Warmergotchi-packed column for three times, the resulting mass of nickel(II) carbonate formed by reacting the filtrate with sodium carbonate solution is as follows.

Mass of nickel(II) carbonate after different rounds of treatment 0.35 0.3 0.25 Mass 0.2 0.15 0.1 0.05 0 1st round 2nd round 3rd round Control

Mass

1st round 0.02g

2nd round 0.18g

3rd round 0.21g

Control 0.29g

P. 83

Separate copper(II) solution was treated by another Warmergotchi-packed column for three times, the resulting mass of copper(II) carbonate formed by reacting the filtrate with sodium carbonate solution is as follows.

Mass of copper(II) carbonate after different rounds of treatment 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

Mass

1st round

2nd round
1st round

3rd round
3rd round 0.23g

Control
Control 0.34g

2nd round 0.2g

Mass

0g

The results for both copper(II) and nickel(II) solutions show an increasing mass of precipitates formed with increasing number of treatment using the same Warmergotchi-packed column. This shows that the Warmergotchi-packed column becomes less effective with increasing number of treatments.

1st round
1st round 2nd round

2nd round

3rd round

Ni2
+

3rd round

Cu2+

P. 84

Cu2+ solution treated by regenerated column

Control

Our group tried to regenerate the Warmergotchi-packed column by adding dilute sulphuric acid to it. Copper(II) solution was then added to the column. The resulting solution showed a lighter blue colour than that of the control solution, indicating that the regeneration was successful.

Lighter

P. 85

Part IVB
Objectives:

Comparing the effectiveness of burette columns and compartmentalized container as filtration device

To compare the effectiveness of toxic ions removal by hand warmer powder-packed column with that of a compartmentalized filtration device.

Principles:
To compare the effectiveness of ions adsorption by hand warmer powder packed in a column or a compartmentalized filtration device, a known volume of a mixture of cations solutions are allowed to pass through the Warmergotchi placed in the two devices. After washing the columns several times by deionized water, the amount of the remaining metal cations in the resulting solutions can be determined by gravimetric measurement. An excess of aqueous sodium carbonate is added to precipitate out any remained metal ions as insoluble metal carbonates. M2+(aq) + CO32- (aq) MCO3 (s) The precipitates are washed, dried and weighed. The mass of the precipitates formed after passing through the burette and the device are compared to see which is more effective.

Chemicals used:
0.05M NiNO3(aq), ZnNO3(aq), CuNO3(aq) Hand warmer powder (Warmergotchi) 1M Na2CO3(aq)

NiNO3

ZnNO3

CuNO3

Apparatus used: Electronic balance Glasswear

P. 86

Procedures:
1. 50g of untreated used Warmergotchi hand warmer powder was packed into a burette and filtration device. 2. 50cm3 of the cations mixture was allowed to run through the packed hand warmer powder, another 100cm3 of it was allowed to run through the filtration device. 3. The column and the device was washed for three times with 25cm3 of deionized water each time. 4. The filtrate collected was treated with 1M Na2CO3 (aq), the precipitates obtained were filtered under suction, washed and dried in an oven. 5. The mass of the precipitate was weighed and compared with that generated from the control solution. 6. The percentage change in mass for the burette and the filtration device was compared.

Results:
Device used Mass of precipitates formed by control solution 0.86 2.76 Mass of precipitates Percentage formed by treated change in mass solution 0.04 -95.3% 2.58 -6%

Burette column Filtration device

Precipitates formed by Precipitates formed by cations cations mixture control mixture treated by burette column

Precipitates formed by cations mixture control

Precipitates formed by cations mixture treated by compartmentalized filtration device

P. 87

Discussion:
In view of the long time taken for most solutions to run through the entire burette, another device was used for adsorbing pollutants. Warmergotchi hand warmer powder was placed in the device, and a mixture of cations solution was poured into the device. The cations solution contains nickel(II) nitrate solution, copper(II) nitrate solution and zinc nitrate solution. This is to test the Warmergotchi-packed devices ability to remove heavy metal ions. However, lead(II) ions is not included in the solution because upon adding lead(II) nitrate solution to the mixture, white precipitates are formed. This may be due to impurities like SO42 or Cl present in nickel(II) nitrate, copper(II) nitrate or zinc nitrate which form precipitate with the lead(II) ion.

Control

Cations mixture solution treated by Warmergotchi column for the 1st round

Cations mixture solution treated by the same Warmergotchi column for the 2nd round

The same cation solution was added to another burette packed with the same mass of Warmergotchi as the one in the device mentioned above. Separate cations solution was treated by the same Warmergotchi-packed column to see the whether the column is still effective after being used once.

The results show that the burette column is much more effective than the filtration device. Despite the long time required for solution to pass through the burette column, the increased contact time of pollutants with the adsorbents prove to be very effective in removing the pollutants. Hence the burette column is a much better device for treating water.

P. 88

Comparisons between different adsorbents

Adsorbents HFO (NaOH, pH 5) HFO (NaOH, pH 7) HFO (NaOH, pH 9) (original) Iron filings Iron(III) oxide powder Activated carbon Vermiculite + Activated carbon Processed hand warmer powder (dil. HCl + 4 hr) Processed hand warmer powder (dil. HCl + 4 hr + heat) Processed hand warmer powder (conc. HCl + 4 hr) HWP (original, ) HWP (original, Warmergotchi) HWP (original, Pocket Sun) HWP (original, ) PO43

Cr2O7

Zn2+

Cu2+

Ni2+

Pb2+
/

Ca2+
/ / / /

Mg2+
/ / /

Overall score 2.5 3.38 3.63 2.38 2 1.63 1.75 2.63

2.38

2.25

2.13

/ / / /

2.38 3.13 2.63 2.75

Key: : Lowest absorbance/ smallest mass of precipitates formed/ smallest titre (Lowest concentration of an adsorbate) : Highest absorbance/ smallest mass of precipitates formed/ smallest titre (Highest concentration of an adsorbate) /: Poor results (i.e. absorbance close to or higher than that of control; titre close to or greater than that of control; mass of precipitates close to or greater than that of control)

P. 89

From the table above, it can be seen that HFO (NaOH, pH 9) is the most effective adsorbent, while HFO (NaOH, pH 7) is the second most effective adsorbent. , Pocket Sun and mixture of vermiculite and activated carbon are also effective adsorbents. The worst adsorbent is iron(III) oxide powder, followed by activated carbon. Iron filings, processed hand warmer powder (conc. HCl + 4 hr) and processed hand warmer powder (dil. HCl + 4 hr + heat) also perform poorly. Although hand warmer powders do not perform as well as HFO, considering the fact that used hand warmer powder shows good adsorption ability for phosphate ions, and also ranks quite high among all the adsorbents used, with at 3rd place and Pocket Sun at 4th place, it is still useful to use used hand warmer powder to adsorb pollutants from wastewater. This is particularly true because HFO, the most effective adsorbent, is very time consuming to produce, whereas hand warmer powder is a domestic waste that can be obtained easily. Moreover, hand warmer powder can be used to adsorb pollutants directly since generally speaking, treated hand warmer powders do not perform better than untreated ones.

P. 90

Sources of Error
Part IA: Preparation of hydrous ferric oxide (HFO) 1. The adjustment of pH value during the preparation of HFO may not be accurate due to discrepancies in determining the colour of pH paper. 2. The addition of hydrochloric acid to adjust the pH of the supernatant liquid may interfere with the formation of hydrous ferrous oxide. 3. There is mass loss during the transfer of hydrous ferrous oxide from filter papers onto watch glasses for drying in the oven. 4. There is mass loss during the transfer of dried, grinded ferrous oxide from mortar to watch glass for weighing. Part IB: Preparation of Processed Hand Warmer Powder (HWP) 1. Although the hand warmer powder used in all four treatments is of the same brand, the composition in different packets may be different, resulting in an unfair test. 2. There is mass loss during the transfer of processed hand warmer powder from filter papers onto watch glasses for drying in the oven. 3. It is difficult to judge the proportion of iron and iron(III) ions present in the mixture by just looking at the colour of the solution, so our deductions about the composition in the various processed hand warmer powder may not be true. 4. There may be other substances present in the used hand warmer powder, apart from those that we deduced, which may or may not affect the overall adsorption ability of processed hand warmer powder. Parts II: Investigating the effectiveness of anion adsorption on various adsorbents 1. The markings of the colorimeter were not fine enough that discrepancies among the readings could not be observed or determined accurately. 2. Suspension was observed in some adsorbent samples and thus some colorimeter readings were affected and could not reflect the actual situation.
3. The samples with phosphate or dichromate solution were allowed to stand for 9

hours without intermittent or continuous stirring. This may affect the adsorption performance.

P. 91

Part III:

Investigating the effectiveness of cation adsorption on various adsorbents

1. The end point of titration in Part IIIA was difficult to detect and different people might have different sensitivity to the end point. 2. In part IIIB, suspension was formed so the reading from the colorimeter might not be accurate. 3. In Part IIIC, ions other than Pb2+ might be precipitated out which contribute to the mass of precipitate. 4. In Part IIID, the treated mineral water and the EDTA solution were both diluted 5 times before titration, any small amount of addition or loss of mineral water or solution during handling of chemicals would lead to a relatively high percentage of experimental error. 5. There may be impurities present in the solution which maybe react with EDTA solution, resulting in an inaccurate determination of results in Part IIID. Part IV: Investigating the effectiveness of filtration device and the regeneration of HFO in the device 1. PO43-, Cr2O72- and metal ions solution took a long time to pass through the burette columns, allowing iron compounds from the burette column to be dissolved in the ions solution, resulting in the formation of brown precipitates after treatment of the solution by the Warmergotchi column. PO43-, Cr2O72- and metal ions cannot be completely washed out of the Warmergotchi powder by 3 rounds of deionized water, particularly for the compartmentalized device since deionized water used to wash the powder would pass through the Warmergotchi powder much quicker than in the burette columns, this result in an increase of the mass of the precipitates formed at the end of the experiments.

2.

P. 92

Suggestions for Improvements

Part IA: Preparation of hydrous ferric oxide (HFO) 1. Measure the pH of the supernatant using a pH meter. 2. Add sodium hydroxide solution slowly and gradually to prevent overshooting of pH value of the supernatant liquid. 3. Instead of transferring the hydrous ferrous oxide from filter papers to watch glasses, place the filter papers which hold wet hydrous ferrous oxide after filtration into the oven for drying directly. The mass of dried hydrous ferric oxide can be determined by the subtraction of the mass of the piece of filter paper which has been initially weighed from the total mass of the filter paper and its contents after drying. 4. After drying in the oven, obtain the mass of the dried hydrous ferrous oxide before grinding by subtracting the mass of the watch glass from the total mass of watch glass and its contents. Part IB: Preparation of Processed Hand Warmer Powder (HWP) 1. Mix all the packets of the used hand warmer powder of the same brand together and take out samples for treatments from this large batch, so as to ensure more similar compositions for each sample. 2. Instead of transferring the processed hand warmer powder from filter papers to watch glasses, place the filter papers which hold powder after filtration into the oven for drying directly. The mass of dried powder can be determined by the subtraction of the mass of the piece of filter paper which has been initially weighed from the total mass of the filter paper and its contents after drying. 3. More conditions for treatments can be conducted on the used hand warmer powder, such as using acid concentrations in between 2M and 11M or adopting time lengths in between 2, 4 and 6 hours. Comparisons can be made easier and more reliable to obtain more accurate deductions about the compositions of the processed hand warmer powder. Parts II: Investigating the effectiveness of anion adsorption on various adsorbents 1. Use a colorimeter with finer markings. 2. Use filter paper with finer pores when filtering the adsorbents. 3. Stir the mixtures at intervals evenly throughout the standing process.

P. 93

Part III:

Investigating the effectiveness of cation adsorption on various adsorbents

1. Assign one person to carry out all titrations in order to reduce the errors caused by human factors.
2. Instead of doing gravimetric analysis through precipitation in Part IIIC, use

another determination method to cross check the results. 3. A higher concentration of EDTA could be used to reduce the percentage error. Another improvement is to perform the titrations for a larger number of times such that a more reliable result can be obtained. Part IV: Investigating the effectiveness of filtration device and the regeneration of HFO in the device

1. Insert cotton wool intermittently between Warmergotchi powder in a burette column to relieve the pressure from the lower part of the burette column, resulting in a quicker flow of the ions solution, reducing the formation of brown precipitates due to presence of iron ions. 2. Increase the number of washings to be carried out after each round.

P. 94

Conclusion
Part I: Preparation of various adsorbents To create the adsorbents necessary to remove pollutants from water, our group has chosen to synthesize hydrous ferric oxide from chemicals available in the laboratory since according to other research, HFO is a successful adsorbent for many pollutants and may also resemble the composition of hand warmer powder. Our group has also chosen a second approach towards creating an adsorbent: To use used hand warmer powder to adsorb pollutants, such that these materials can be recycled and used for water treatment.
pH 5 (NaOH) pH 11 (NaOH) pH 7 (NH3)

pH 5 (NaOH)

pH 7 (NaOH)

pH 9 (NaOH)

In synthesizing HFO, it was noted that a supernatant liquid of pH 7 creates the most amount of precipitates. A supernatant liquid of pH 5 creates precipitates that are too small, though the surface area of the precipitates must be significantly greater, it is difficult to collect. It was also noted that sodium hydroxide is a better solution to use than ammonia solution since using sodium hydroxide solution would produce more precipitates. Hand warmer powder was also used to adsorb pollutants. By using different treatments, we were able to deduce roughly the composition of the hand warmer powder, and we could use the treated hand warmer powder to carry out further experiments to test which treatment produces the best adsorbents. Although the hand warmer powder may exhibit weaker adsorption abilities, hand warmer powder is a domestic waste, and by putting the used powder into good use, the powder will not be wasted and this is environmentally friendly. Part II: Investigating the effectiveness of PO43 and Cr2O72 adsorption on various adsorbents 3 For PO4 adsorption, HFO (NH3, pH 7) is the most effective while iron filings is the least effective. Generally speaking, HFO formed are most effective in adsorbing PO43 ions, and while the adsorption ability of processed hand warmer powder and unprocessed hand warmer powder varied, they are still comparable to that of HFO. Among the HFO samples, HFO produced in an alkaline medium shows better adsorption effects of phosphate ions than that in acidic or neutral medium. However, the general adsorption performance of HFO samples is still very satisfactory.

P. 95

Among the processed hand warmer powder samples, those treated with dilute HCl was found to be very effective in adsorbing PO43 ions, with the PO43 concentration reduced by more that 90%. It was also found that iron(III) oxide is more effective than iron in the removal of phosphate ions. Among all hand warmer powder brands, WarmerGotChi hand warmer powder was found to be the most effective phosphate adsorbent while the lowest effectiveness was observed for Pocket Sun hand warmer powder. For Cr2O72 ions, HFO produced in a neutral medium was found to be the most effective in the removal of dichromate while iron filings were shown to be the least effective adsorbents. It was also found that vermiculite is not effective or even hinders the removal of dichromate. For HFO, the average adsorption power was the highest among all absorbents. Moreover, HFO produced in neutral and alkaline mediums were found to have better adsorption effects than that produced in an acidic medium. For hand warmer powder, it was found out that the original hand warmer powder is more effective than all treated samples. For optimized adsorption effects, untreated hand warmer powder should be used. Among all the brands, hand warmer powder of brand was shown to be the most effective dichromate adsorbent while the lowest effectiveness was observed for Pocket Sun hand warmer powder. Although the average dichromate adsorption power of HFO is the highest, some used hand warmer powder samples are also very effective in the removal of dichromate.

P. 96

Part III: Investigating the effectiveness of metal ions adsorption on various adsorbents HFO produced in a neutral or alkaline medium adsorbs Zn2+, Cu2+ and Ni2+ ions better than that of HFO produced in an acidic medium. For Pb2+ ions, HFO produced in acidic and alkaline medium perform better than that in neutral medium. It was found that among the three types of HFOs, HFO(NaOH, pH 9) is the most suitable in adsorbing Zn2+ and Cu2+ ions while HFO(NaOH, pH 7) is found to be the most suitable in adsorbing Ni2+ ions. As for the adsorption of Pb2+ ions, taking into consideration of the fact that the amount of yield of HFO(NaOH, pH 9) during production was greater than that of HFO(NaOH, pH 5), and the production of HFO (NaOH, pH 9) was much was easier than that of HFO (NaOH, pH 5), HFO (NaOH, pH 9) was taken to be the most effective HFO in adsorbing Pb2+ ions. As for used hand warmer powder, they are shown to be just as effective in adsorbing metal ions as HFOs. It was also found that with the exception of Ni2+, untreated hand warmer powders were more effective in adsorbing metal ions than untreated ones, For Zn2+ ions, the most effective adsorbent is Pocket Sun. For Cu2+, it is HFO synthesized at pH 9, followed by Pocket Sun. For Ni2+, it is Warmergotchi. For Pb2+ ions, iron filings were the best adsorbent, followed by the hand warmer powder . The adsorption effect of the hand warmer powder, with the exception of Pocket Sun and , were even better than that of the HFOs and it was found that untreated hand warmer powders adsorbed Pb2+ ions better than the treated ones. Considering the adsorption effects of all the ions tested, HFO (NaOH, pH 9) is the best adsorbent, followed closely by HFO (NaOH, pH 7). The weakest adsorbent is iron(III) oxide, followed by activated carbon and iron filings. Although the used hand warmer powders are not among the best adsorbents, they were proved to be quite effective, in particular Warmergotchi and , of negligible cost and are easily available. They could be potential adsorbents to treat industrial wastewater.

HFO (NaOH, pH9)

HFO (NaOH, pH7)

P. 97

Experiments on Ca2+ and Mg2+ were also carried out to test the effectiveness of hardness removal of different adsorbents. For Ca2+, HFO synthesized at pH 9 was most effective, followed by untreated Pocket Sun. For Mg2+, hand warmer powders processed by dilute HCl performed the best, followed by HFO synthesized at pH 5.

Part IV:

Investigating the effectiveness of filtration devices and the regeneration of HFO in the device

A filtration device was made by packing Warmergotchi powder into a burette column. It was found that such device is extremely effective in removing pollutants since it allows a large contact area and long contact time for the adsorption of different ions, PO43 solution, Cr2O72 solution and all the other metal ions solution passed through the column all showed a significant decrease in the mass of precipitates formed upon adding lead(II) nitrate solution and sodium carbonate solution compared with that of the control.

Cu2+ 1st round

Cu 2nd round

2+

Cu2+ 3rd round

Though the effectiveness of the Warmergotchi-packed column decreases with the number of times a solution has run through it, regeneration of its adsorption ability was found to be possible by passing the used column with dilute sulphuric acid. In view of the solutions taking a long time to pass through the burette columns, a compartmentalized device was used to see if this could replace the very effective burette columns. It was found that the reduction in heavy metal ions after being treated in the new device is significantly lower than that of the burette columns, indicating that such device is not as effective as the burette column. Despite the long time it takes for the solution to pass through the burette column, it is still better to use the burette column to ensure a greater removal of pollutants from effluents.

P. 98

References
Dwyer, Robert F.; Birdsall, Clair M. (1964) Process for the preparation of hydrous ferric oxide. Union Carbide Corp. Goswami, Saswati; Bhat, Subhas Chandra; Ghosh, Uday Chand. (2006) Crystalline Hydrous Ferric Oxide: An Adsorbent for Chromium(VI)-Contaminated Industrial Wastewater Treatment. Water Environment Research. Department of Chemistry, Presidency College, West Bengal, Kolkata, India. De Jager, Pieter Christiaan. (2002) A phosphate sorption and desorption study on an acid sandy clay soil. Plant Production and Soil Science, University of Pretoria. Kersten, Michael; Kulik, Dmitrii A. (2005) Competitive Scavenging of Trace Metals by HFO and HMO during redox-driven Early Diagenesis of Ferromanganese Nodules. Journal of Soils and Sediments. Geoscience Institute, Gutenberg-University, D-55099 Mainz, Germany; Waste Management Laboratory, Paul-Scherrer-Institute, CH-5232 Villigen-PSI, Switzerland. Elimelech M;Borkovec M.; Hering J.. (1999) Interfacial and Colloidal Phenomena in Aquatic Environments - Chemical Processes at the Solid-Water Interface. Preprints of Extended Abstracts. Division of Environmental Chemistry, American Chemical Society Lund, Tracy J; Koretsky, Carla M; Landry, Christopher J; Schaller, Melinda S; Das, Soumya. 2008. Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite. Geochemical Transactions Journals. BioMed Central Ltd. http://chemlab.truman.edu/CHEM222manual/pdf/edta.pdf http://en.wikipedia.org/wiki/Complexometric_titration