Philippine Associated Smelting and Refining Corporation LIDE, Isabel, Leyte

Correlation Between As/Pb Concentration Ratio, As, and Pb Concentration of the Copper Anodes to the Density of the Slimes Produced After Electrolysis

Ian Dominic F. Tabaag Bachelor of Science in Chemical Engineering (BS-ChE) University of San Carlos Technological Center In-Plant Trainee 2011

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Acknowledgement . Abstract...

i-ii iii

I.Introduction 1 II.Objectives of the Study.. III.Significance of the Study.. IV.Scope and Limitations.. V.Review of Related Literature Vi.Methodology.. VII.Results and Discussions. VIII.Conclusions. IX.Recommendations X.Bibliography. XI.Appendices. 2 2 2 3-7 8-10 11-12 13 13 14 15-22

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Acknowledgement

This study would not have been possible without the guidance and the help of several individuals who in one way or another contributed and extended their valuable assistance in the preparation and completion of this study. The researcher would like to thank the following: To Engr. Severo Andrew B. Lacaba, the main proponent of this study, who shared his ideas about this study and made the researcher experience the job of being an area manager; To Engr. Joseph B. Morao, who shared his resources and other literature readings related this study. Furthermore, he taught the researcher well on how to handle speaking engagements and for letting the researcher experience a great deal happiness from the small irrelevant things; To Ms. Jemmy Liz B. Pohino, who gave the permission for the utilization of the tray oven and the vacuum pump of the By-Products Plant and also for being the self-proclaimed acting mom of the researcher in the Tankhouse; To Mr. Anthony Mark F. Lusica, who enlightened the researcher in the overall idea of this study and also for being the self-proclaimed acting dad of the researcher; To Engr. Mark Jun A. Talaban, who gave the researcher an idea on how to conduct the sampling of the anode slimes; To Engr. Hercules M. Amson, who gave the permission for the utilization of the former process mini-lab as a working space for the researcher; To Kuya Roger, who helped the researcher in the cleaning of the mini-lab; To Engr. Blessyl Marie Navalatan, who gave the permission to use the laboratory apparatus and equipment of the process laboratory; To the tankhouse personnel, who shared good conversations to the researcher during his free time; To all the ODT staff, who gave the IPTs moral support, provided the researcher with supplies (such as a marker, sticky tape, etc.), provided the IPTs with free food every time the ODT department sponsors an activity; To Ms. Leizel Ponce, for being the acting mother of the researcher during his stay here in PASAR;

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Philippine Associated Smelting and Refining Corporation To the Teaspoon Crew, who served food for the IPTs during their stay in the Guesthouse; To the fellow IPT-mates of the researcher, Kahar (the self-proclaimed best buddy of the researcher), Mamie, Bhel, Wena, Phebby, Ron, Beth, Irish, Jen, and LAMPY (the best representative of our school!) for sharing the gift of friendship to the researcher; To the family of the researcher, for the love and support that they gave to him during his stay here in PASAR; To the PASAR Corp., for giving the researcher an opportunity to undergo the In-Plant Training Program of the company and all the benefits that the researcher experienced as a trainee; Lastly, to our Almighty God the Father, for giving us the privilege to enjoy life and it is through Him that all things are made possible.

Thank you very much!!!

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Abstract

Floating slimes deposition is one of the main problems in electrorefining that greatly affects the cathode quality. In the present time, the anodes being used in the electrorefining have high levels of Arsenic and Lead which can be classified a impurities in the electrorefining process. This primary objective of this study is to establish a relevant correlation between the As and Pb concentration in the copper anodes to the density of the slimes it produces after electrolysis. Data of the As and Pb concentration of the anodes were gathered and samples of slimes were collected, filtered, dried, and the determination of its density. The obtained data from the experimentation was analyzed and then using regression methods, a relevant correlation between the As/Pb concentration ratio to the density of slimes was obtained. The correlation obtained in this study can be used as a basis as to why the As/Pb concentration ratio can be used as a measure of determining anode slime characteristics. Based from this study, maintaining the As/Pb concentration ratio of the copper anode in the range of ~0.87-1.12 will lead to the formation of high density slimes.

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I. Introduction It is stated in the Quality Policy of PASAR Corp. that the company is committed to provide Grade A Copper cathode to the satisfaction of the London Metal Exchange (LME) and other non-ferrous metals market. In producing high quality copper cathodes, the impurity levels in the copper anodes to be used in the electrorefining process must be maintained at a minimum level and when not maintained at low levels, it will lead to cathode contamination. Based from the daily anode charging report by the commercial cells section, it can be observed that the anodes currently used in the electrorefining process have high levels of impurities such as As, and Pb. These undesirable elements in the copper cathodes come from slime occlusions, and co-deposition of dissolved impurities in the electrolyte. Also, it has been observed by random cathode inspection that most of the nodulations present in the copper cathodes are due to the entrapment of floating slimes. This study concerns on establishing a correlation between the impurities present in the copper anodes (especially As and Pb) to the density of slimes it produces after the electrorefining process. This study will also find a way to minimize the entrapment of floating slimesduring the electrolysis process thus, improving cathode quality.

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II. Objective of the Study This study aims to establish a significant correlation between the As and Pb content in the copper anodes to the density of slimes being produced by these anodes after the electrolysis. III. Significance of the Study Floating slimes deposition is one of the main problems during the electrorefining process since they decrease the quality of the copper cathodes being produced. Thus, determining the concentration of the As and Pb, or the optimum As/Pb ratio in the anode that could lead to the formation of high-density slimes could greatly help in the minimization of the nodulations caused by the entrapment of floating slimes or floating slimes deposition and ultimately enhance the cathode quality after electrolysis. IV. Scope and Limitations This study focuses mainly on establishing a correlation between and As and Pb content in the copper anodes to the density of slimes it produces after electrolysis, where the place of study is limited only to Tankhouse 1 of the Refinery since Tankhouse 1 utilizes the additive Sanfloc as a flocculant. Samples of slimes being collected depend on the 3rd crop harvesting schedule since during the 3 rd crop harvest, the electrolysis cells are being drained of the electrolyte solution and which is suitable for the gathering of slime samples. The researcher intends to gather as many samples as possible to utilize the amount of time given for the study to be conducted (April 19 to May 11, 2011). Using the available equipment in the laboratory for the experimentation part of this study, the researcher has seen to it that the uncertainties in measurement were minimized.

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V. Review of Related Literature Anode Slimes: Considerable amount of As, Bi, and Sb report in the anode residues as they form compounds with copper and other impurities in the anode (i.e. 2 3 , ). Also, it is believed that to some extent, As, Sb, and Bi combine to form arsenate precipitates that also report to the anode slimes (Biswas, and Davenport, 1980). The amount of these three elements in the anode slimes depends not only on their concentration in the anode but also on the composition of the electrolyte and the composition of other anode impurities. Origin of this anode slime components include: 1. Compounds existing in the anode and compounds in the anolyte region, or 2. Precipitates which form in the bulk electrolyte due to solubility effects Kennecott test data have shown that antimony arsenate and bismuth arsenate can contribute greatly to the presence of As, Sb, and Bi in cathodes, anode slimes and pipelines. Further tests have shown that an increase in antimony and bismuth content forces an increased amount of arsenic to report to anode slimes. There is then an increased slime fall that corresponds to arsenate composition. Float slimes were found to be amorphous and chemically undefined compounds that contain Sb(III), Sb(V), Bi(III), and As(V).When antimony concentrations are in excess of 0.5 g/L, float slime formation occurs. Slime fall is much greater when electrolyte composition is maintained in a saturated or supersaturated condition with respect to arsenate solubility than in an unsaturated electrolyte.

Effect of Arsenic in the Anode: Arsenic is present in the anode and the one hand as a mixed crystal on the other hand as an oxide. During electrolysis, both the metallic and the oxidic arsenic are for the most part dissolved in the electrolyte; arsenic goes into the solution in trivalent form and in the course of electrolysis is oxidized to the pentavalent state by the atmospheric oxygen dissolved in the electrolyte. A layer of slime forms on the surface of the anode as a function of oxygen content of the anode and remains loosely adhering through the anode throughout the entire test. At low arsenic contents, most of this layer consists of copper and copper oxide; at higher contents, copper arsenide forms on the anode surface from the elemental copper and from the solution containing As(III). The formation of a covering layer on the anode causes the cell voltage to increase. The resulting slime becomes more fine-grained, due to the grain refinement, as the

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arsenic content of the anode increases. Because of its strong affinity to oxygen, arsenic binds a large amount of arsenic present in the anode, and as a result, this significantly influences copper enrichment and acid decomposition during electrolysis. It is found that arsenic goes almost completely into solution regardless of its oxygen content. (Cornelius, et al., 1997)

Effect of Lead in the anode: The study of slimes behavior phenomenon that occurs in the electrorefining process is influenced by variables such as chemical composition of the anode (especially Pb) and the current density. A high specific weight in the anode slimes can assure a minimum of suspended solids during the electrorefining process. On the other hand, an increase in the current densities with anodes of high lead content (~1539ppm Pb based on this study with current densities of 240 290 / 2 ), produces a synergistic effect to minimize the quantity of suspended slimes in the cell. Furthermore, it has been estimated that the lead can be the cause for the precipitation of antimony through the formation of Bindhemite (2 2 7 ) compounds in the anode slimes. A specific weight of 4.71g/cm^3 of the anode slimes showed a minimum concentration of suspended solids. (Cifuentes et al., 1999)

Mean absolute deviation The mean absolute deviation (MAD) is the mean absolute deviation from the mean. A related quantity, the mean absolute error (MAE), is a common measure of forecast error in time series analysis, where this measures the average absolute deviation of observations from their forecasts. Although the term mean deviation is used as a synonym for mean absolute deviation, to be precise it is not the same; in its strict interpretation (namely, omitting the absolute value operation), the mean deviation of any data set from its mean is always zero.

Grubbs Test for Detection of Outliers: Grubbs' test for outliers (Grubbs 1969 and Stefansky 1972 ) checks normally distributed data for outliers. This implies that one has to check whether the data show a normal distribution before applying the Grubbs test. The Grubbs test always checks the value which shows the

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largest absolute deviation from the mean. If an outlier has been indentified and removed, the test must not be repeated without adapting the critical value. The application of the test is quite simple and straightforward: one searches the maximum of the absolute differences between the values xi and the mean . The result is

divided by the standard deviation of the sample. If the resulting test statistic g is greater than the critical value, the corresponding value can be regarded to be an outlier. An extract of the critical values is shown in the table shown in the appendix. The formula for getting the statistic g is:

In some other literature data, the test statistic g is sometimes referred to as the Z statistic. The Z statistic notation was utilized in this study. Regression or Curve fitting: Field data is often accompanied by noise. Even though all control parameters (independent variables) remain constant, the resultant outcomes (dependent variables) vary. A process of quantitatively estimating the trend of the outcomes, also known as regression or curve fitting, therefore becomes necessary. The curve fitting process fits equations of approximating curves to the raw field data. Nevertheless, for a given set of data, the fitting curves of a given type are generally NOT unique. Thus, a curve with a minimal deviation from all data points is desired. This best-fitting curve can be obtained by the method of least squares.

Method of Least Squares Regression: The method of least squares assumes that the best-fit curve of a given type is the curve that has the minimal sum of the deviations squared (least square error) from a given set of data. Suppose that the data points are variable and , , ..., where is the independent from

is the dependent variable. The fitting curve , , ...,

has the deviation (error)

each data point, i.e.,

. According to the

method of least squares, the best fitting curve has the property that:

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This states that the sum of the residuals must be kept at minimum. Polynomial Least Squares Fitting: When using an mth degree polynomial

to approximate the given set of data, fitting curve

, ...,

, where

, the best

has the least square error, i.e.,

Please note that

, ..., and

are unknown coefficients while all , ,

and

are given. must yield

To obtain the least square error, the unknown coefficients zero first derivatives.

, ..., and

Expanding the above equations, we have

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The unknown coefficients linear equations.

, ..., and

can hence be obtained by solving the above

In this study, an iterative method was used in solving the parameters of the equation with the aid of MS Excel Solver function in the carrying out of the iterative procedures.

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VI. Methodology 1.Data Gathering Basing from the April and May harvest schedule, blocks to be harvested during 3 rd crop were noted. From the 3rd crop blocks to be harvested, the anode lot numbers from different cells were determined from the daily anode charging report and these anode lot numbers were verified by visual inspection. Those cells with anodes of the same lot numbers were noted for sample gathering. 2.Experimentation 2.1.Materials and Apparatus: Materials: Sampling cups Distilled or deionized water Electrolyte Ashless Filter Paper

Apparatus: Oven (tray drying) Top-loading balance (0.01 g) Heater (hot plate) crucibles Graduated cylinder (15mL, 0.10 mL ) Thermometer (alcohol) Erlenmeyer flask (500mL with cork stopper) Dessicating Cabinet Vacuum pump

2.2.Procedure: 2.2.1.)Sampling From the harvested blocks, slimes from cells with anodes of the same lot number were collected by means of scraping them from the anodes (the locations of the anodes that were scraped with slime were: near the electrolyte feed, middle, and near the electrolyte outlet). The

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block, lot, and cell numbers of the samples taken were recorded. Also, the current densities were recorded since the current densities were increased during the scope of the sampling time.

2.2.2.)Washing and Filtration The samples being collected were washed with distilled water until the blue color is removed (all CuSO4 solution that accompany the slimes are removed to prevent its crystallization upon drying) and then filtered using an ashless filter paper in a funnel and with the aid of a vacuum pump, the filtration time was minimized.

2.2.3.)Drying of Slimes The slimes being collected were placed in crucibles with cover. The samples were dried in an oven for at least 3 hours at 103-105. After 3 hours of drying, the samples are being cooled inside a desiccating cabinet to prevent the moisture from the air from being entrained in the dried samples. The cycle of drying, cooling, and weighing was repeated until a constant weight was obtained or the weight is changed less than 4%.1-3 grams of each sample were taken and then set aside.

2.2.4.)Density Determination Electrolyte solution from the feed of the cell was collected and placed in an Erlenmeyer flask and then heated to 64-68 in a hot plate. The graduated cylinder was washed with the electrolyte solution beforehand then it was filled with ~10mL of the electrolyte solution.After the preparation of the electrolyte solution, the 1-3 grams of dry sample prepared was placed into the graduated cylinder with the electrolyte solution and the volume change in the graduated cylinder was then recorded. The density of the sample was then determined by dividing the mass of the dry slime sample to the volume of electrolyte solution being displaced. Five runs of density determination were done to account for the random and systematic errors. 3.Data Treatment Construction of the Density vs. As, Pb, and As/Pb concentration plots: After obtaining the density values from all samples, the As, and Pb content of the anodes were obtained from the daily anode charging report with respect to the anode lot numbers of the samples. After determining the As and Pb concentrations of the anodes being

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charged, the density of the slimes samples obtained are to be plotted correspondingly using a spreadsheet software (MS Excel) against the As, Pb, and As/Pb ratio where these samples were taken. The correlation between the As and Pb concentration of the copper anodes to the density of the slimes being produced after electrolysis was obtained by regression of data using MS Excel.

4.Statistical Method: Using the five runs for the density determination, the Mean Absolute Deviation (MAD) was obtained. The mean average deviation was used in this study due to the limited amount of samples being obtained. Also, the mean absolute deviation was utilized because the sample run size is less than 30 and to account for the random and systematic errors that were being encountered during the experimentation. Grubbs test was used to detect and remove outliers.

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VII. Results and Discussion:

6.00 5.50 Density (g/mL) 5.00 4.50 As 4.00 3.50 3.00 400 500 600 700 800 900 1000 1100 Pb

concentration (ppm)

Figure 1: Density vs As and Pb concentration plot Figure 1 shows the plot of As and Pb anode concentration of the anode to the density of slimes it produces after electrolysis. It is shown that when Pb concentrations are within the range of 680 to 800ppm Pb, high density slimes are being produced. On the other hand, As concentrations within the range of 700 to 900ppm As also produces high density slimes. This we can attribute to the ability of As and Pb to coprecipitate with other impurities such as Bi, Sb, and O.

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4 Density (g/mL)

3 Actual Data Regressed Data 2

0
0.3 0.5 0.7 0.9 As/Pb 1.1 1.3 1.5

Figure 2: Density vs As/Pb ratio Figures 2shows a relevant correlation between the As/Pb concentration ratio to the density of slimes being produced. It can be observed from the figure that as the concentration ratio between As and Pb approaches to 1, high density slimes are formed. But when the ratio is less than or greater than 1, the density of the slimes tend to decrease. From literature, as the lead concentration in the anode increases, the density of slimes being formed also increases due to the fact that Pb can cause the formation of heavy precipitates.However, based from the data obtained, when Pb concentration exceeds ~800 ppm, the slime density starts to decrease and conversely for As concentration effect. In the regression of data, the polynomial least squares fitting method was utilized with the aid of the MS Excel Solver.

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VIII. Conclusion: Based on the data gathered, there is a more likely quadratic or parabolic correlation (with the correlation coefficient R^2 value of 0.910113) between the As/Pb concentration ratio to the density of slimes it produces after electrolysis for which it can be made as a basis in characterizing anode slimes and thus helps in minimizing a problem in floating slimes deposition. As shown Figure 2, Cu anodes with As/Pb ratio of ~0.87-1.12 can result in the formation of high density slimes. Furthermore, there was no correlation that has been established between the As concentration to the density of slimes and conversely for Pb concentration to the density of slimes since both As and Pb vary with each other.

IX. Recommendations: In establishing a correlation between As concentration to the density of slimes , the Pb concentration in the anode must be kept constant or vice versa since it has been shown in this study that As and Pb vary with each other. Also, advanced mathematical modeling methods can be used to correlate As, Pb, and Density of slimes given that a sufficient period of time is being allotted in doing this study. There is a need to minimize further the uncertainty of measurement that was done in this study since the apparatus used in determining the masses of the slime samples was a toploading balance (~0.01 g) due to the unavailability of equipment. This can be achieved by using an analytical balance (~0.0001 g). Further experimentation must be done in order to quantify more on the effect of As and Pb to the formation of composites in slimes or component analysis of slimes. Also, there is a need in the determination of the standard densities of the slimes at which there is minimum concentration of suspended solids and relate it to the As and Pb concentration of the copper anode.

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X. Bibliography: Standard Methods for the Examination of Water and Wastewater, 21st ed., Franson et al., Port City Press, Baltimore, Maryland, USA, 2005 Anode Slime Characteristics and Behavoiur in Copper Refining, Cifuentes et al., Proceedings of Copper 99-Cobre 99 International Conference Vol. 3., 1999 Prevention of Floating Slimes Precipitation, Abe et al., The Electrorefining and Winning of Copper, Pensylvania, 1987 Extractive Metallurgy of Copper 2 nd ed., Pergamon Press, Oxford, 1980 Daily Anode Charging Report, PASAR Corp., revised as of April 29,2010 April and May Harvest Schedule, PASAR Corp. http://www.statistics4u.info/fundstat_eng/ee_grubbs_outliertest.html http://www.efunda.com/math/leastsquares/leastsquares.cfm

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XI. Appendices Table 1: Data from the Daily Anode Charging Report: Anode Lot No. 115 116 117 114 121 123 122 119 118 111 127 129 130 131 As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630

Note: Red values indicate the concentrations that are within the range of the set point values used by the company as a standard (600-1000ppm for As and 690-710ppm for Pb).

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Table 2: Density Determination:

Trial 1 Anode Lot No. 115 116 117 114 121 123 122 119 118 111 127 129 130 131 As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630 As/Pb 0.71 0.95 1.25 1.19 1.40 1.05 1.28 0.65 1.12 0.87 1.09 0.98 0.84 0.79 mass sample (g) 1.29 1.12 1.07 1.05 1.02 1.04 1.06 1.25 1.13 2.06 2.28 2.07 2.09 2.03 volume change (ml) 0.30 0.20 0.20 0.20 0.30 0.30 0.30 0.30 0.20 0.40 0.45 0.35 0.40 0.40 Density (g/ml) 4.30 5.60 5.35 5.25 3.40 3.47 3.53 4.17 5.65 5.15 5.07 5.91 5.23 5.08 mass sample (g) 1.06 1.39 1.02 0.99 1.29 1.07 1.08 1.07 1.08 3.18 3.05 3.05 3.06 3.01

Trial 2 volume change (ml) 0.30 0.30 0.20 0.20 0.40 0.20 0.30 0.30 0.20 0.65 0.55 0.60 0.55 0.60 Density (g/ml) 3.53 4.63 5.10 4.95 3.23 5.35 3.60 3.57 5.40 4.89 5.55 5.08 5.56 5.02

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Trial 3 Anode Lot No. 115 116 117 114 121 123 122 119 118 111 127 129 130 131 As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630 As/Pb mass sample (g) 1.01 1.18 1.05 1.15 1.18 1.11 1.10 1.10 1.10 3.00 3.18 3.09 3.15 3.07 volume change (ml) 0.25 0.25 0.20 0.20 0.30 0.20 0.30 0.25 0.30 0.60 0.55 0.55 0.60 0.60 Density (g/ml) 4.04 4.72 5.25 5.75 3.93 5.55 3.67 4.40 3.67 5.00 5.78 5.62 5.25 5.12 mass sample (g) 1.04 0.99 1.17 1.04 1.07 1.22 1.17 1.14 1.10 3.16 3.23 3.19 3.01 3.17

Trial 4 volume change (ml) 0.30 0.20 0.25 0.20 0.30 0.25 0.30 0.25 0.20 0.65 0.65 0.55 0.55 0.65 Density (g/ml) 3.47 4.95 4.68 5.20 3.57 4.88 3.90 4.56 5.50 4.86 4.97 5.80 5.47 4.88 mass sample (g) 1.07 1.01 1.16 1.26 1.09 1.01 1.12 1.22 1.20 3.01 3.07 3.07 3.17 3.12

Trial 5 volume change (ml) 0.25 0.20 0.25 0.25 0.30 0.20 0.30 0.30 0.25 0.60 0.55 0.55 0.60 0.65 Density (g/ml) 4.28 5.05 4.64 5.04 3.63 5.05 3.73 4.07 4.80 5.02 5.58 5.58 5.28 4.80

0.71 0.95 1.25 1.19 1.40 1.05 1.28 0.65 1.12 0.87 1.09 0.98 0.84 0.79

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Table 3: Statistical Treatment of Data Table 3.1: Detection and Elimination of Outliers (Grubbs Test): Density (g/mL) As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630 As/Pb 0.71 0.95 1.25 1.19 1.40 1.05 1.28 0.65 1.12 0.87 1.09 0.98 0.84 0.79 Trial 1 4.30 5.60 5.35 5.25 3.40 5.20 3.53 4.17 5.65 5.15 5.07 5.91 5.23 5.08 Trial 2 3.53 4.63 5.10 4.95 3.23 5.35 3.60 3.57 5.40 4.89 5.08 5.56 5.13 5.02 Trial 3 4.04 4.72 5.25 5.75 3.93 5.55 3.67 4.40 5.50 5.00 5.78 5.62 5.25 5.12 Trial 4 3.47 4.95 4.68 5.20 3.56 4.88 3.90 4.56 5.50 4.86 4.97 5.80 5.47 4.87 Trial 5 4.28 5.05 4.64 5.04 3.63 5.05 3.73 4.07 4.80 5.00 5.44 5.58 5.28 4.80 D ave 3.92 4.99 5.00 5.24 3.55 5.21 3.69 4.15 5.51 4.98 5.23 5.69 5.27 4.98 D (SD) 0.40 0.38 0.33 0.31 0.26 0.26 0.14 0.38 0.33 0.11 0.34 0.15 0.12 0.14 D(eff) 3.52 4.61 4.68 4.93 3.29 4.95 3.54 3.78 5.18 4.87 4.89 5.54 5.15 4.84 Zcrit= Z1 0.94 1.60 1.06 0.04 0.57 0.02 1.11 0.04 0.42 1.49 0.46 1.41 0.34 0.74 1.71 Z2 0.98 0.95 0.29 0.93 1.22 0.55 0.61 1.54 0.34 0.79 0.43 0.87 1.14 0.31 Detection of Outliers Z3 0.29 0.71 0.75 1.65 1.45 1.32 0.11 0.65 0.04 0.18 1.65 0.48 0.18 1.03 Z4 1.13 0.11 0.99 0.12 0.04 1.26 1.52 1.07 0.04 1.05 0.76 0.69 1.59 0.79 Z5 0.89 0.16 1.11 0.64 0.30 0.60 0.31 0.22 2.15 0.18 0.64 0.74 0.06 1.29

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The red value for in the Z5 column is detected as an outlier since its Z is greater than the Zcrit. The highlighted cell was detected as an outlier since its resulting test statistic Z is greater than the Zcrit for 5% level of error. The green value represents a calculated mean with the outlier being neglected.

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Table 3.2: Mean Average Deviation: Mean Average Deviation As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630 As/Pb 0.71 0.95 1.25 1.19 1.40 1.05 1.28 0.65 1.12 0.87 1.09 0.98 0.84 0.79 D ave 3.92 4.99 5.00 5.24 3.55 5.21 3.69 4.15 5.51 4.98 5.23 5.69 5.27 4.98 T1 0.38 0.61 0.35 0.01 0.15 0.01 0.16 0.02 0.14 0.17 0.15 0.22 0.04 0.10 T2 0.39 0.36 0.10 0.29 0.32 0.14 0.09 0.58 0.11 0.09 0.15 0.13 0.14 0.04 T3 0.12 0.27 0.25 0.51 0.38 0.34 0.02 0.25 0.01 0.02 0.56 0.07 0.02 0.14 T4 0.45 0.04 0.32 0.04 0.01 0.33 0.21 0.41 0.01 0.12 0.26 0.11 0.20 0.11 T5 0.36 0.06 0.36 0.20 0.08 0.16 0.04 0.08 0.71 0.02 0.22 0.11 0.01 0.18 DEV AVE 0.34 0.27 0.28 0.21 0.19 0.20 0.10 0.27 0.07 0.08 0.27 0.13 0.08 0.11

In the calculation of the mean average deviation, the highlighted red value was not included in the calculation of the average deviation since this the value for this trial was designated as an outlier

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Table 4: Non-Linear Least Squares Regression: 4th order polynomial n= 3.3625 a= b= c= As (ppm) 672 694 670 816 1042 905 765 483 779 577 776 712 534 496 Pb (ppm) 941 730 537 687 742 862 600 742 695 660 709 729 639 630 As/Pb 0.71 0.95 1.25 1.19 1.4 1.05 1.28 0.65 1.12 0.87 1.09 0.98 0.84 0.79 D ave 3.92 4.99 5 5.24 3.55 5.21 3.69 4.15 5.51 4.98 5.23 5.69 5.27 4.98 DEV AVE D app Sr 0.1619 -0.4608 -1.5846 St 0.378551 0.430046 0.150634 0.07021 2.713572 0.770249 0.589724 0.828432 0.539589 0.073746 0.693805 0.58082 0.011269 0.031311 7.861957 d= e= 4.5969 2.9178 0

0.4 4.199736 0.0782523 0.38 5.47078 0.2311491 0.33 4.426885 0.3284603 0.31 5.079972 0.025609 0.26 3.167709 0.1461468 0.26 5.692639 0.2329406 0.14 4.047066 0.1274961 0.38 3.904818 0.0601141 0.33 5.549568 0.0015656 0.11 5.086563 0.0113557 0.34 5.64795 0.1746825 0.15 5.577117 0.0127427 0.12 4.921158 0.1216907 0.14 4.638052 0.1169286 AVE= 4.815001 SUM= 0.7066912

R^2 0.910113 From the results of the least squares method of iteration, the resulting polynomial equation is: = 0.1619 3.3625 4 0.4608 3.3625 3 1.5846 3.3625 2 + 4.5969 3.3625 + 2.9178

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Philippine Associated Smelting and Refining Corporation

With the R^2 value of 0.910113 Note: The green value (sum of residuals) was being minimized using the solver function of excel by changing the parameters a, b, c, d, e, and n. Table 5: Critical G or Z Values for the Determination of Outliers

gcrit =0.05

gcrit =0.01 1.1547 1.4962 1.7637 1.9728 2.1391 2.2744 2.3868 2.4821 2.5641 2.6357 2.6990 2.7554

gcrit =0.05

gcrit =0.01 2.8061 2.8521 2.8940 2.9325 2.9680 3.0008 3.1353 3.2361 3.3807 3.4825 3.5599 3.6217

gcrit =0.05

gcrit =0.01 3.6729 3.7163 3.7540 3.8167 3.8673 3.9097 3.9460 3.9777 4.0935 4.1707 4.2283 4.2740

3 4 5 6 7 8 9 10 11 12 13 14

1.1543 1.4812 1.7150 1.8871 2.0200 2.1266 2.2150 2.2900 2.3547 2.4116 2.4620 2.5073

15 16 17 18 19 20 25 30 40 50 60 70

2.5483 2.5857 2.6200 2.6516 2.6809 2.7082 2.8217 2.9085 3.0361 3.1282 3.1997 3.2576

80 90 100 120 140 160 180 200 300 400 500 600

3.3061 3.3477 3.3841 3.4451 3.4951 3.5373 3.5736 3.6055 3.7236 3.8032 3.8631 3.9109

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Philippine Associated Smelting and Refining Corporation

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