AIMS :

To estimate the carbonate and bicarbonate species in the water solution with the help
of colour indicators and pH titration method . To estimate the behaviour of buffer mechanism of the aquatic bodies and thus estimating the possible biological impacts on aquatic life in the event of toxic pollution To estimate the effectiveness of the indicator method and pH titration method in estimating the equivalence points of carbonic acid species. Introduction : The dissolution of carbon dioxide in aquatic environment is one of the most important processes making it a focal point of study for the aquatic chemists and environmentalists. Many pathways can be described in the carbon cycle for explanation of dissolution of CO 2 in aquatic environment. The inorganic form of dissolved CO2 mainly enter the aquatic environment through air-water surface and through the weathering of calcareous rocks. During the photosynthesis , oxidation and respiration processes triggered by the activities of micro organisms present in the water , a significant amount of CO 2 is reduced or increased in the water depending upon the process. Algal growth is one of the most significant example , as algae photosynthesise during which the CO2 is reduced while the same is increased due to respiration of algae during night. Thus a great fluctuation of pH is exerted on the water bodies during these processes. The aquatic life in water bodies is pH dependent and a fluctuation in pH may cause severe damage to the life. It is the ability of the carbonate species to resist the pH change in the event of toxic pollution and thus prevent the damage to aquatic life . Thus the enumeration of these carbonate species is fundamental to aquatic geochemistry . Carbonic Species in Water : Dissolved CO2 is present mainly in aqueous form in the water but it also forms a weak diprotic carbonic acid (H2CO3) in water and CO2 is presented by this weak acid only. CO2(aq) + H2O

H2CO3* -------------------- (1)

As this carbonic acid is diprotic its dissociation can be described with two equations. Carbonic acid is in equilibrium with bicarbonate ion and hydrogen ion and bicarbonate ion is in equilibrium with carbonate ion . The dissociation equations and dissociation coefficients can be described as following equations . H2CO3 H+ + HCO3- , K1 = [ H+] [ HCO3-] [H2CO3*] -----(2)

HCO3-

-------(3) [HCO3-] These carbonate species ( HCO3- , CO3-2 , OH- , H2CO3) act as proton acceptor and donor and thus plays a significant role during acid-base and exchange reactions occurring in the aquatic systems. The pH regulation and overall composition of natural waters are highly influenced by the these activities of these carbonic species. pH as a master variable : Water is in equilibrium with hydrogen and hydroxyl ion with a dissociation coefficient having a value of Kw=10-14 H2O

H+ + CO32- , K2 = [ H+] [ CO3-2]

H+ + OH- , Kw=[ H+] [ OH-]

[H2O]

=10-14 ------ (4)

However the ionized concentration of water is such a low that the concentration of [H 2O] can be considered as 1. Therefore from equation(4) , the concentration of hydrogen ion can be calculated as :

[H+] [OH-] = Kw = 10-14 -----------------(5) From equation (5) the amount of hydrogen ion activity can be estimated for water.In 1909 Soverson suggested to represent hydrogen ion activity on logarithmic scale rather than in terms of molar concentration and this quantity is represented as pH . Therefore , pH = - log [H+] ------------------- ( 6) and pOH = 14 log [H+] Thus for example a pH of 7 represents the hydrogen ion concentration of 10-7 moles in water. From equation (1) to (3) a mass balance equation for carbonate species can be written as follows : Ct = [H2CO3] + [HCO3-] + [CO3-2] ---------------- (7) The concentration of each species can calculated from the equations given below : CH2CO3 = [ H2CO3] / Ct CHCO3- = [ HCO3-] /Ct CCO3-2 = [ CO3-2] /Ct ------------(8) -------------(9) -------------(10)

Computing the values of dissociation co-efficient K1 and K2 , the concentration of carbonic species can be expressed in terms of H+ ion and thus the concentration equation of species can be written as follows : CH2CO3 = CHCO3- = C CO3-2 = [H+]2 [ H ] + K1[ H+] + K1K2
+ 2

-----------(11) -----------(12) -----------(13)

K1 [H+] [ H ] + K1[ H+] + K1K2

+ 2

K1 K2 [ H+]2 + K1[ H+] + K1K2

From the above equations for a known value of pH (i.e molar concentration of H +) the concentration of carbonate species in the water can be estimated and the plot of Log of species against pH can be drawn as flows :

Graph 1 : Log Concentration of Carbonate species Against pH. From the graph 1 and equation (1) to (3) it is evident that the estimation of carbonic species can be made establishing three equivalence points.It is the distinct property of diprotic acid like carbonic acid that their species distribution can be explained with the help of three equivalence points. The three equivalence points for carbonic acid are as follows : 1) H2CO3 equivalence point (point A on the Graph 1) : For ph close to 6 , HCO3- and H2CO3 are present in comparable form but for a pH below 6 all dissolved carbon species are in the form of H2CO3 only. Thus for this region [H2CO3] >> [HCO3-] >> [CO3-2] . 2) HCO3- equivalence point (point B on the Graph 1) Between pH 7 to 9 , all carbonic species are present in the form of [HCO3-] and thus [HCO3-] >> [Co3-2] or [H2CO3-2] . 3) CO3-2 equivalence point (point C on the Graph 1). At pH 10.33 and above , the activity of [HCO3-] is reduces and all species are present in the form of [CO3-2] only. Thus in this region , [ CO3-2] >> [HCO3-] .If any two of the equivalence points are established using titration then the total concentration of carbonic species can be estimated from equation (7) . Buffer and buffer Capacity : Classically buffers are defined as the substances present in the solution which resist the change of pH on addition of acid or base. Thus the buffer capacity is defined as the ability of the substance to resist the pH change upon addition of acid or base. Carbonic species present in the natural waters act as significant buffers and resist the pH changes of water in the case of acute pollution events caused due to toxic acid or base pollutants. The Acid Neutralising Capacity (ANC) of a solution is defined as the ability of the solution to accept protons while Base Neutralising Capacity (BNC) is defined as the ability of the solution to behave as proton donor . The carbonic species (CO3-2 , HCO3- , OH- , ) behave as proton acceptor and act as buffer against acid addition to the solution. To enumerate the carbonic species their ability to act as a buffer against acid cane be utilised and with the help of suitable indicators the equivalence

points at each species can be traced out in the titration process. This is the basic principle of the experiment conducted for the measurement of the species. Approximation of Equivalence points (End points) : During acidimetric titration of the carbonic acid bicarbonate and carbonic acid equivalence points can be estimated using phenolphthalein and methyl orange as indicators. However it is to be noted here that the equivalence points determined in the concentration v/s pH curve are theoretical values while in practice with indicators We are trying to estimate these points and they are called end points . In acidimetric titration a strong acid is added to the solution and the approximation of the carbonic acid and bicarbonate equivalence points is made getting the end points of the reaction of carbonate and bicarbonate species with the acid . The carbonate equivalence point is not used in practice as it is difficult to estimate the end point of the reaction which is due to the masking effect of the buffering capacity of water . (1) Phenolphthalein End point : As strong acid is added to the solution, carbonate species present in the solution act as buffer and resist the pH change. But as the titration proceeds carbonate is converted to bicarbonate. CO3-2 + H+ HCO3- ----- (14) Theoretically the equivalence point when all carbonate ions are converted to bicarbonate ion is at the pH of 8.3 and at this pH range phenolphthalein changes its colour form pink to colour less and thus the end point of the reaction can be established. The mass balance equation can be written as : [CO3-2] + [OH-] - [H+] = 0 ----- (15) (2) Methyl Orange End point : For pH range of 7-9 , the bicarbonate is the dominant species and act as a buffer upon addition of acid. The equivalence point (point A) is at pH 4.5 . When the pH is lowered slightly below this point , methyl orange changes its colour and thus the end point can be established. At this point all bicarbonate ion are converted to carbonic acid which in turn converts to carbon dioxide and water . The reaction equation and mass balance equation can be written as follows : HCO3- + H + CO2 ------ (16) 2[CO3-2] + [HCO3-] + [OH-] [H+] = 0 . ------ (17) ALKALINITY :Alkalinity is defined as the existence of a net strong base associated with equivalent carbonic species in the solution .It is the ability of the carbonic species to neutralise the acids acting as proton acceptor on addition upon a strong acid in the solution. It measures the resistance of water bodies to acidification process in the events of addition of strong toxic acid substances to it. To measure the alkalinity strong acid is added to solution until the pH is equal to any two equivalence points getting the end points of the reaction of indicators. As the bicarbonate and carbonic acid points are established using phenolphthalein and methyl orange , the alkalinity at these points are termed as phenolphthalein and methyl orange alkalinity respectively. The phenolphthalein alkalinity is due to carbonate ion present in the solution while the methyl orange alkalinity represents the total alkalinity as all carbonic species are titrated at this point . Thus from the mass balance equation given above , We can write Phenolphthalein alkalinity (P-Alkalinity ) = [CO3-2] + [OH-] ------- (18) Total Alkalinity = 2[CO3-2] + [HCO3-] + [OH-] . ------(19)

Estimation of Carbonate and Bicarbonate : Why Half Carbonate? The hydroxyl ion in the water acts as proton acceptor and neutralise [H+] ion during the titration process. Its reaction can be described as OH- + H+ H20 -------- (20) If we consider that the alkalinity is due to carbonate ion and hydroxyl ion only , when we reach to phenolphthalein titration point (i.e pH = 8.3) We can say that the reactions described by equation (14) and (20) are completed. And by reaching the Methyl orange point (pH =4.3) the reaction given in (16) is completed. As , for each mole of carbonate ion one mole of hydrogen is consumed when it is titrated to phenolphthalein end point and the other is consumed for methyl orange point . If the volume of acid required to reach pH=8.3 end point(Vp) is equal to the volume of acid required to reach the pH from 8.3 to 4.3 (Vmo). We can estimate that the alkalinity is solely due to carbonate ion only. If the upon addition if phenolphthalein becomes colourless immediately and We require to add acid to reach to a pH of 4.3 , the alkalinity is solely due to bicarbonate ion only. The same way if We require to add acid to reach to pH=8.3 but no acid to reach pH of 4.3 , We can say that the alkalinity is due to hydroxyl ion only. Similarly if the volume of acid Vmo > Vp then We can say that the alkalinity is solely due to carbonate ion and bicarbonate ion only. Thus for this condition We can write the alkalinity equations (18) and (19) as follows : Phenolphthalein alkalinity (P-Alkalinity ) = [CO3-2] ------- (21) Total Alkalinity = 2[CO3-2] + [HCO3-] . ------(22) From equation (21) and (22) , We can estimate the amount of carbonate and bicarbonate species present in the solution . The complete titration of the one atom of carbonate species will consume two atoms of hydrogen (proton) . However , at the phenolphthalein end point all carbonate are converted to bicarbonate and thus the acid used to reach this point represents half the amount of hydrogen ions require to neutralise carbonate ions. Thus phenolphthalein end point is called half carbonate point .To calculate the carbonate alkalinity , the phenolphthalein alkalinity is multiplied with a fraction of two. The bicarbonate is calculated by subtracting the carbonate from the total alkalinity. Methodology : In the practical titration with pH indicator and pH titration methods were utilised. Using phenolphthalein and methyl orange as pH indicators the end point pH for carbonate and the total alkalinity were obtained for a sample of 25 ml solution.The volume of acid used for both the titration were recorded. In pH titration method 250 ml of distilled water was added to a sample of 25 ml of solution . The amount of the distilled water was adjusted to make complete coverage of the electrode. The pH of the solution was measured adding a unit amount Hcl to the sample As the end points were already determined with the help of indicator method , measurements were made at a frequent interval of 0.5 ml to 0.1 ml as the end points were approached . The graph of pH against volume of Hcl used was plotted. After carrying out necessary calculations the graph of DpH/DV volume was plotted for the correct estimation of the end points.

Results : Results for amount of HCL added for pH indicators method as well as the pH and corresponding volume of HCL added for pH titration are summarised in the following tables. A ) pH Indicator method : 1) TABLE 1 : AMOUNT OF HCL ADDED AT END POINTS Group Volume of HCL added at End points(ml) Phenolphthalein (X) 1. 2. 3. 4. 5. 5.8 5.8 4.3 4.0 3.8 3.85 4.5 4.5 6.0 5.9 Methyl Orange (Y) 21.0 21.1 14.8 14.8 14.7 14.7 14.7 14.6 21.2 21.0

Calculations : a) carbonate species : from the equilibrium equation of carbonate species and hydrochloric acid, CO3-2 + 2HCl = H2O + CO2 + Hcl , Therefore , 1 mole of carbonate = 2 moles of Hcl . So , 1 ml of 0.1 M Hcl = 1 X 10-4 mole HCL = X 10-4 mole CO3-2. = X 10-4 X 60,000 = 3 mg of CO3-2 ( Relative molecular mass of carbonate = 60 ,000 mg/mole) Considering the reading of phenolphthalein titration for group 1 , the acid added = 5.8 ml. Thus the carbonate ion = 5.8 X 3 = 17.4 mg which is half of the actual carbonate in the solution . Therefore , Total Carbonate = 2 X 17.4 = 34.8 mg / 25 ml . Calculating , the amount per litre = 34.8 X 1000 / 25 Total amount of carbonate per litre of solution = 1392 mg b) bicarbonate species : The equilibrium equation for bicarbonate is , HCO3- + HCL = H2O + CO2 + Clthus 1 mole bicarbonate = 1 mole of Hcl

1 ml of 0.1 M Hcl = 1X10-4 X 61,000 = 6.1 mg of bicarbonate . Now, The amount HCL required to titrate bicarbonate ions =Y 2X = 21.0 (2 x 5.8) = 9.4 mg Therefore bicarbonate = 9.4 X 6.1 = 57.34 mg /25 ml Thus bicarbonate per litre = 57.34 X1000 / 25 = 2293.6 mg . . B) pH Titration method : The readings of pH and amount of Hcl added along with the necessary calculation for the plotting of derivative curve are summarised as below. The buffer index (dV/dpH) represents the amount of acid requires to cause a unit change in the pH of the solution . As the titration is approached to the end point the buffer capacity of the solution is reduced and thus at the end point the buffer index will be minimum and the reciprocal of the index (dpH/dV) will be maximum. Thus by calculating the dpH/dV for each point of the titration and plotting these values against total volume acid added , at maximum points of the graph We can obtain the amount of acid used to titrate the relevant end points analogous to phenolphthalein and methyl orange inidcators. For , group 1 , from the derivative curve the total amount of Hcl added upon reaching the end points are 5.9 ml and 21.1 ml. The results of the class for derivative curve readings are summarised in the table 3. TABLE 2 : AMOUNT OF HCL ADDED AND PH . Volume of HCL added (b) 0 1 1 1 0.5 0.5 0.5 0.5 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 10.14 9.98 9.8 9.6 9.48 9.33 9.16 8.9 8.78 8.55 8.44 8.35 8.26 8.16 8.04 7.98 7.92 7.85 7.78 PH 0 0.16 0.18 0.20 0.12 0.15 0.17 0.26 0.12 0.23 0.11 0.090 0.09 0.1 0.12 0.06 0.06 0.07 0.07 DpH (a) Total Hcl used 0 1 2 3 3.5 4 4.5 5 5.2 5.4 5.5. 5.6 5.7 5.8 5.9 6.0 6.1 6.2 6.3 0 0.16 0.18 0.20 0.20 0.24 0.30 0.34 0.52 0.6 1.15 1.1 0.9 0.9 1 1.2 0.6 0.7 0.7 DpH/DV (a/b)

Volume of HCL added (b) 0.1 0.6 1 1 1 1 1 1 1 1 1 1 1 1 0.2 0.2 0.3 0.1 0.2 0.2 0.2 0.2 0.2 0.3 0.1 0.2 0.2 0.5 1 1 1 7.72 7.43 7.42 6.94 6.79 6.64 6.53 6.42 6.30 6.17 6.07 5.93 5.77 5.55 5.51 5.46 5.39 5.35 5.29 5.19 5.05 4.89 4.52 4.08 3.8 3.59 3.34 3.13 2.86 2.70 2.60

PH

DpH (a) 0.06 0.29 0.01 0.48 0.15 0.15 0.11 0.11 0.12 0.13 0.1 0.14 0.16 0.22 0.04 0.05 0.07 0.04 0.06 0.1 0.14 0.16 0.37 0.44 0.28 0.21 0.25 0.21 0.27 0.16 0.1

Total Hcl used 6.4 7 8 9 10 11 12 13 14 15 16 17 18 19 19.2 19.4 19.7 19.8 20 20.2 20.4 20.6 20.8 21 21.1 21.3 21.5 22 23 24 25

DpH/DV (a/b) 0.6 0.48 0.01 0.48 0.15 0.15 0.11 0.11 0.12 0.13 0.1 0.14 0.16 0.22 0.2 0.25 0.233 0.4 0.3 0.5 0.7 0.8 1.85 1.46 2.8 1.05 1.25 0.42 0.27 0.16 0.1

TABLE 3 : AMOUNT OF HCL CALCULATED FOR END POINTS FROM DERIVATIVE CURVE

Group 1 2 3 4 5

Bicarbonate End point 5.9 4.3 3.8 4.5 5.5

Carbonate End point 21.1 14.8 14.7 14.7 21.5

From the above table the amount of carbonate and bicarbonate can be calculated using the same calculations explained in indicator titration method. The amount of carbonate and bicarbonate obtained using both methods is summarised in the table given below: TABLE 3 : AMOUNT OF CARBONATE BICARBONATE SPECIES Group Carbonate (mg/lit) 1. 2 3. 4. 5. 1392 998.4 912 1080 1440 Indicators Bicarbonate (mg/lit) 2293.6 2596.16 2659.6 1390.8 2244.8 Carbonate (mg/lit) 1416 1032 912 1080 1320 PH-titration Bicarbonate (mg/lit) 2269.2 1488 1732.4 1390.8 2562

STATISTICS : The descriptive statistics for both the test and box plots of carbonate and bicarbonate species are given as below :
Variable Carbonate Bicarbonate Test I pH I pH N 5 5 5 5 Mean 1164 1152.0 2237 1888 SE Mean 106 93.6 227 227 StDev 238 209.2 507 508 Minimum 912 912.0 1391 1391 Median 1080 1080.0 2294 1732 Maximum 1440 1416.0 2660 2562 IQR 461 396.0 810 976

Note : The subscript I = Results for test using Indicators pH = Results for test using pH titration

Box plot of carbonate-bicarbonate values

I 1500 1400 1300 1200 1100 1000 900 I pH Test Carbonate 2750 2500 2250 2000 1750 1500 Bicarbonate pH
Test I pH

Results are very significant for both the tests. Looking at the box plot of carbonate species for both the tests , it is evident that the values for both the test have similar spread as the size of the interquartile boxes are almost same and even the mean symbol are located nearly at the centre of the boxes in both the test. This can be confirmed from the descriptive statistics of the tests as the mean for for indicators and pH tests are 1164 and 1152 respectively and their medians are same having a value of 1080. The similarity of the spread of data is further confirmed by the Standard deviations for both the tests which have quite similar values . Looking at the box plots for bicarbonate species , it is evident that the mean and median are quite higher for test using indicators for finding end points than the pH titration method.This may be the effect of outliers .The minimum , maximum and Interquartile range for both the test show similar results . The standard deviations for both the test indicates similar spread of values for both the tests. The difference in mean and median indicates that the values are higher in the indicators tests than the pH titration test. The probability plot given below indicates one very much significant result for the test. The probability of carbonate and bicarbonate species for pH titration test is higher than the indicators test which indicates the precision of the test .

Probability Plot of Carbonate, Bicarbonate

Normal
99 Variable Carbonate Carbonate Bicarbonate Bicarbonate Mean 1164 1152 2237 1888 StDev 237.8 209.2 506.7 507.7 N 5 5 5 5 Test I pH I pH P 0.294 0.536 0.144 0.443

95 90 80

Percent

70 60 50 40 30 20 10 5

AD 0.354 0.257 0.455 0.292

500

1000

1500

2000 Data

2500

3000

3500

The results of two sample T-test for both the species are summarised as follows :

Two-Sample T-Test and CI: Carbonate, Test

Two-sample T for Carbonate Test I pH N 5 5 Mean 1164 1152 StDev 238 209 SE Mean 106 94

Difference = mu (I) - mu (pH) Estimate for difference: 12.4800 95% CI for difference: (-314.1459, 339.1059) T-Test of difference = 0 (vs not =): T-Value = 0.09 Both use Pooled StDev = 223.9549

P-Value = 0.932

DF = 8

Two-Sample T-Test and CI: Bicarbonate, Test

Two-sample T for Bicarbonate Test I pH N 5 5 Mean 2237 1888 StDev 507 508 SE Mean 227 227

Difference = mu (I) - mu (pH) Estimate for difference: 348.512 95% CI for difference: (-391.193, 1088.217) T-Test of difference = 0 (vs not =): T-Value = 1.09 Both use Pooled StDev = 507.1875

P-Value = 0.309

DF = 8

The probability values for both the test are quite significant favouring the null hypothesis and thus confirming that the difference between the values of species obtained through both the tests are negligible.

DISCUSSION : For group 1 the values of carbonate for indicator test are 1392 mg/lit and for ph test are 1416 mg/lit . The values of the bicarbonate are 2293.6 mg/lit and 2269.2 mg/lit for indicator and ph titration test respectively. The mean of carbonate for indicator method is 1164 mg/lit with standard deviation of 238 and the mean for ph titration method are 1152 mg/lit with standard deviation of 209.2 The bicarbonate species for both the test are 2237 mg/lit with standard deviation of 507 for indicator method and a mean of 1888 mg/lit with a standard deviation of 508 for ph titration method. The statistical analysis of the data for both the tests reveals the possible errors that may cause deviations in results for the test. As the normality test suggest higher values of probability for pH titration method compare to indicators method ,it indicates that the pH titration test has more reproducibility of results than the indicator method. The possible cause of error in indicator method may be the identification of methyl orange end point visually. We can confirm it from the statistics. As the spread of data is very much similar in carbonate readings for both the tests while the data is slightly twisted with the effect of outliers when we compare both the tests for bicarbonate values . The bicarbonate values for indicator method shows higher mean and median compare to ph titration method pointing out the over estimation of the methyl orange end point. Methyl orange changes its colour for a pH range of 3.1 to 4.4 . Lowenthal et al (1976) stated that though the effect of CO2 on methyl orange end point is minimal , that can be overcome by applying magnetic stirring of the solution. The reproducibility of pH titration test also may be due to the same reason as magnetic stirring of the solution was employed while the stirring was manual in the indicator method. The two sample t- test for both the species show a probability values of 0.932 for carbonate species and 0.309 for bicarbonate species. It shows that any difference between the readings of both the test can be considered negligible and both the test cane utilised with precision for the measurement of the carbonate-bicarbonate species of the water. The higher values for carbonate species again points out the ease of end point identification for phenolphthalein end point and difficulty associate with methyl orange end point as the probability for bicarbonate two sample t- test is 0.309. CONCLUSION :

The values of carbonate-bicarbonate species for the solution can be estimated from
the following readings of 1 sample t- test.
Variable Carbonate Bicarbonate N 10 10 Mean 1158.24 2062.74 StDev 211.25 512.25 SE Mean 66.80 161.99 95% CI (1007.12, 1309.36) (1696.30, 2429.17)

The reproducibility of the pH titration test is higher compared to indicator method. But
both the test can be applied simultaneously . First with the help of indicator method the end points can be estimated and thus this end point estimation can be applied in the pH titration method to get the exact titration of the solution near the end points with more precise intervals of acid addition. With the application of magnetic stirring and careful examination of methyl orange end point the precision of the indicator method can be improved .

REFERENCES :

1) Colin Baird , 1998 , Environmental Chemistry , Second edition , W H Freeman &

Company .

2) James I Drever , 1982 , The geochemistry of Natural Waters , Prentice Hall Inc. 3) R E Lowenthal and G V R Marais , 1976 Carbonate Chemistry of Aquatic
Systems : Theory and Application , Ann Arbor Science Inc.

4) Samuel D. Faust and Osman M Aly , 1981 , Chemistry of Natural Waters , Ann
Arbor Science Publishers Inc

5) Vernon L Snoeyink and David Jenkins , 1980 , Water Chemistry , John Wiely &
Sons Inc.

6) Werner Stumm and James J Morgan , 1970 , Aquatic Chemistry : An introduction

emphasizing Chemical Equilibria in Natural Waters , John Wiley & Sons Inc.

MODULE CODE : GES 4031 MODULE TITLE : PHYSICO CHEMISTRY AND WATER QUALITY MODELLING MODULE LEADER : DR. HUW JONES MODULE TUTOR : MR. PAUL KERSHAW LABORATORY : MEASUREMENT OF PHOSPHORUS IN RIVER , LAKE AND UNKNOWN WATER SAMPLES SUING COLORIMETRIC METHODS STUDENT NAME : AMIT CHRISTIAN STUDENT ID : M00082846 SUBMISSION DATE : 12/12/2006 SUBMISSION DEADLINE : 15/12/2006