n 2 Factorial Experiment 4 Factor used to Remove Chemical Oxygen demand from Distillery Spent Wash R.K. Prasad and S.N. Srivastava (2009). “Electrochemical degradation of distillery spent wash using catalytic anode: Factorial design of experiments,” Chemical Engineering Journal, Vol. 146, pp. 22-29. Data Description • Response: Y = % Chemical Oxygen Demand Removed from Distillery Spent wash • Factors and Levels: A: Current Density (mA/cm2) – 14.285, 42.857 B: Dilution (%) – 10, 30 C: Time (hrs) – 2, 5 D: pH – 4, 9 • Experimental Runs: 16 – All 24 Combinations of levels of A,B,C,D Data – Normal Order Run 10 9 4 15 3 5 8 6 12 1 7 14 2 11 16 13 CurrDens Dilution 14.285 10 42.857 10 14.285 30 42.857 30 14.285 10 42.857 10 14.285 30 42.857 30 14.285 10 42.857 10 14.285 30 42.857 30 14.285 10 42.857 10 14.285 30 42.857 30 Time 2 2 2 2 5 5 5 5 2 2 2 2 5 5 5 5 pH 4 4 4 4 4 4 4 4 9 9 9 9 9 9 9 9 Label (1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd y 28.265 32.520 32.230 36.210 28.265 38.560 34.562 40.230 65.230 56.680 62.135 64.430 71.210 68.720 72.270 68.260 For the Label, any factor at its high level appears in lower case form. (1) Corresponds to the case when all factors are at their low levels. Table of Contrasts - I • Create a Column for the intercept (I), one for each Main Effect and each Interaction (A,…,D, AB,…,CD, ABC,…,BCD, ABCD), and one for the response (y). If there were multiple replicates per treatment, replace y with the mean of those r replicates • Create a row for each experimental run (treatment), using the Labels from the previous slide. • For the Intercept Column, put +1 in each row • For all Main Effects, Put +1 if that factor was at its high level, -1 if at its low level (Note: Books use +/-) Table of Contrasts - II Trt (1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 A -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 B -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 C -1 -1 -1 -1 1 1 1 1 -1 -1 -1 -1 1 1 1 1 D -1 -1 -1 -1 -1 -1 -1 -1 1 1 1 1 1 1 1 1 AB AC AD BC BD CD ABC ABD ACD BCD ABCD y 28.265 32.520 32.230 36.210 28.265 38.560 34.562 40.230 65.230 56.680 62.135 64.430 71.210 68.720 72.270 68.260 For Interactions, multiply the coefficients in each row for the Main Effects that make up that Interaction. For Row 1 and Column AB: A has coefficient -1, B has -1, so AB has (-1)(-1) = +1 For Row 1 and Column ABC: (-1)(-1)(-1) = -1 For Row 1 and Column ABCD: (-1)(-1)(-1)(-1) = +1 An Interaction will have a coefficient of +1 if it has an even number of its Main Effects at their low levels, -1 if an odd number. Table of Contrasts - III Trt (1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 A -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 B -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 C -1 -1 -1 -1 1 1 1 1 -1 -1 -1 -1 1 1 1 1 D -1 -1 -1 -1 -1 -1 -1 -1 1 1 1 1 1 1 1 1 AB 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 AC 1 -1 1 -1 -1 1 -1 1 1 -1 1 -1 -1 1 -1 1 AD 1 -1 1 -1 1 -1 1 -1 -1 1 -1 1 -1 1 -1 1 BC 1 1 -1 -1 -1 -1 1 1 1 1 -1 -1 -1 -1 1 1 BD 1 1 -1 -1 1 1 -1 -1 -1 -1 1 1 -1 -1 1 1 CD 1 1 1 1 -1 -1 -1 -1 -1 -1 -1 -1 1 1 1 1 ABC -1 1 1 -1 1 -1 -1 1 -1 1 1 -1 1 -1 -1 1 ABD -1 1 1 -1 -1 1 1 -1 1 -1 -1 1 1 -1 -1 1 ACD -1 1 -1 1 1 -1 1 -1 1 -1 1 -1 -1 1 -1 1 BCD -1 -1 1 1 1 1 -1 -1 1 1 -1 -1 -1 -1 1 1 ABCD 1 -1 -1 1 -1 1 1 -1 -1 1 1 -1 1 -1 -1 1 y 28.265 32.52 32.23 36.21 28.265 38.56 34.562 40.23 65.23 56.68 62.135 64.43 71.21 68.72 72.27 68.26 Create 4 Rows below this “matrix”: Contrast, Divisor, Effect, Sum of Squares 2n Contrast ki y i i 1 ki 1 In EXCEL, you can take the SUMPRODUCT of each Column with y 2n for the Intercept (I) Column Divisor n 1 2 for all other columns Contrast Effect Divisor r 2 Sum of Squares SS n Contrast Sum of Squares is not typically computed for Intercept 2 Table of Contrasts - IV Trt (1) a b ab c ac bc abc d ad bd abd cd acd bcd abcd Divisor Contrast Effect SumSq I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 16 799.777 49.986 A -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1 1 B -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 8 11.443 1.430 8.184 8 20.877 2.610 27.241 C -1 -1 -1 -1 1 1 1 1 -1 -1 -1 -1 1 1 1 1 D -1 -1 -1 -1 -1 -1 -1 -1 1 1 1 1 1 1 1 1 8 8 44.377 258.093 5.547 32.262 123.082 4163.250 AB 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 1 -1 -1 1 8 4.423 0.553 1.223 AC 1 -1 1 -1 -1 1 -1 1 1 -1 1 -1 -1 1 -1 1 8 7.483 0.935 3.500 AD 1 -1 1 -1 1 -1 1 -1 -1 1 -1 1 -1 1 -1 1 8 -36.953 -4.619 85.345 BC 1 1 -1 -1 -1 -1 1 1 1 1 -1 -1 -1 -1 1 1 8 -3.743 -0.468 0.876 BD 1 1 -1 -1 1 1 -1 -1 -1 -1 1 1 -1 -1 1 1 8 -10.367 -1.296 6.717 CD 1 1 1 1 -1 -1 -1 -1 -1 -1 -1 -1 1 1 1 1 ABC -1 1 1 -1 1 -1 -1 1 -1 1 1 -1 1 -1 -1 1 ABD -1 1 1 -1 -1 1 1 -1 1 -1 -1 1 1 -1 -1 1 8 19.593 2.449 23.993 8 -16.717 -2.090 17.466 8 14.227 1.778 12.650 ACD -1 1 -1 1 1 -1 1 -1 1 -1 1 -1 -1 1 -1 1 8 -7.973 -0.997 3.973 BCD -1 -1 1 1 1 1 -1 -1 1 1 -1 -1 -1 -1 1 1 8 -4.367 -0.546 1.192 ABCD 1 -1 -1 1 -1 1 1 -1 -1 1 1 -1 1 -1 -1 1 y 28.265 32.52 32.23 36.21 28.265 38.56 34.562 40.23 65.23 56.68 62.135 64.43 71.21 68.72 72.27 68.26 8 -8.013 -1.002 4.013 Effect A: y A,High y A,Low 32.52 36.21 38.56 40.23 56.68 64.43 68.72 68.26 28.265 32.23 28.265 34.562 65.23 62.135 71.21 72.27 405.61 394.167 1.430 8 8 8 Effect AB: y AB,High y AB,Low 28.265 36.21 28.265 40.23 65.23 64.43 71.21 68.26 32.52 32.23 38.56 34.562 56.68 62.135 68.72 72.27 402.1 397.677 0.553 8 8 8 Alternative Approach: 36.21 40.23 64.43 68.26 32.23 34.562 62.135 72.27 209.13 201.197 Effect A @ B 1: 1.98325 4 4 4 32.52 38.56 56.68 68.72 28.265 28.265 65.23 71.21 196.48 192.97 Effect A @ B 1: 0.8775 4 4 4 1 Effect AB: 1.98325 0.8775 0.553 2 Analysis of Variance SSA r 2 r 2 n 1 r 2n 2 2 n 1 22 n 1 y A,Low y y y A,Low 2 A,High Contrast A • • Source A B C D AB AC AD BC BD CD ABC ABD ACD BCD ABCD df SS 1 8.184 1 27.241 1 123.082 1 4163.250 1 1.223 1 3.500 1 85.345 1 0.876 1 6.717 1 23.993 1 17.466 1 12.650 1 3.973 1 1.192 1 4.013 • 2 y y A,High n 1 y A,High y r 2 y A,Low A,Low 2 2 2 2 y A,High y A,Low 2 2 2 y A,Low y A,High y A,High 2 2 2 r 2n 1 (2) r 2n 1 2 Contrast A Effect A 4 4 2n 1 r 1 2 2 Contrast A 11.43 8.184 n 2 16 SSA r 2 Contrast A n 2 Notes: Factor D (pH) has by far the largest effect on the outcome. With all mean effects and interactions, there are no error degrees of freedom, and no tests can be conducted Consider dropping interactions with small sums of squares to obtain an error term (Authors dropped: AB, AC, BC, and BCD) Source A B C D AD BD CD ABC ABD ACD ABCD Error df SS 1 8.184 1 27.241 1 123.082 1 4163.250 1 85.345 1 6.717 1 23.993 1 17.466 1 12.650 1 3.973 1 4.013 4 6.790 MS F_obs F(.05) P-value 8.184 4.821 7.709 0.093 27.241 16.048 7.709 0.016 123.082 72.509 7.709 0.001 4163.250 2452.601 7.709 0.000 85.345 50.278 7.709 0.002 6.717 3.957 7.709 0.118 23.993 14.134 7.709 0.020 17.466 10.289 7.709 0.033 12.650 7.452 7.709 0.052 3.973 2.341 7.709 0.201 4.013 2.364 7.709 0.199 1.697 Regression Approach 1 if A is at High Level Let: X 1 Similarly defined X 2 ( B), X 3 (C ), X 4 ( D) 1 if A is at Low Level E Y 0 1 X 1 2 X 2 3 X 3 4 X 4 12 X 1 X 2 13 X 1 X 3 14 X 1 X 4 23 X 2 X 3 24 X 2 X 4 34 X 3 X 4 123 X 1 X 2 X 3 124 X 1 X 2 X 4 134 X 1 X 3 X 4 234 X 2 X 3 X 4 1234 X 1 X 2 X 3 X 4 ^ Note: 0 Effect I ^ 1 1 Effect A since Effect A y A,High y A,Low 2 1 2 ^ Full Model: ^ Y 49.986 0.715 X 1 1.305 X 2 2.774 X 3 16.131X 4 0.276 X 1 X 2 0.468 X 1 X 3 2.310 X 1 X 4 0.234 X 2 X 3 0.648 X 2 X 4 1.225 X 3 X 4 1.045 X 1 X 2 X 3 0.889 X 1 X 2 X 4 0.498 X 1 X 3 X 4 0.273 X 2 X 3 X 4 0.501X 1 X 2 X 3 X 4 Reduced Model (Coefficients do not change due to orthogonal design): ^ Y 49.986 0.715 X 1 1.305 X 2 2.774 X 3 16.131X 4 2.310 X 1 X 4 0.648 X 2 X 4 1.225 X 3 X 4 1.045 X 1 X 2 X 3 0.889 X 1 X 2 X 4 0.498 X 1 X 3 X 4 0.501X 1 X 2 X 3 X 4 and so on... Further Model Reduction (Simplification) • When testing the effects after removing the Interactions with the smallest effects, we find BD, ACD, and ABCD all have P-values that are > 0.10. Now we remove them for a simpler model. Source A B C D AD CD ABC ABD Error ^ df SS 1 8.184 1 27.241 1 123.082 1 4163.250 1 85.345 1 23.993 1 17.466 1 12.650 7 21.493 MS F_obs F(.05) P-value 8.184 2.665 5.591 0.147 27.241 8.872 5.591 0.021 123.082 40.086 5.591 0.000 4163.250 1355.908 5.591 0.000 85.345 27.796 5.591 0.001 23.993 7.814 5.591 0.027 17.466 5.688 5.591 0.049 12.650 4.120 5.591 0.082 3.070 This model has: 8.184 12.650 R2 0.9952 8.184 12.650 21.493 Y 49.986 0.715 X 1 1.305 X 2 2.774 X 3 16.131X 4 2.310 X 1 X 4 1.225 X 3 X 4 1.045 X 1 X 2 X 3 0.889 X 1 X 2 X 4 Normal Probability Plot of Factor & Interaction Effects Under hypothesis of no main effects or interactions, estimated effects should be approximately normally distributed with mean 0. Construct a normal probability plot of estimated effects Effect std.norm -4.619 -1.739 -2.090 -1.245 -1.296 -0.946 -1.002 -0.714 -0.997 -0.515 -0.546 -0.335 -0.468 -0.165 0.553 0.000 0.935 0.165 1.430 0.335 1.778 0.515 2.449 0.714 2.610 0.946 5.547 1.245 32.262 1.739 Normal Probability Plot of Estimated Factor Effects and Interactions 2.000 1.500 1.000 Std. Normal Quantiles Trt AD ABC BD ABCD ACD BCD BC AB AC A ABD CD B C D 0.500 0.000 -0.500 -1.000 -1.500 Clearly, several effects fall well away from central line -2.000 -10.000 -5.000 0.000 5.000 10.000 15.000 Effect 20.000 25.000 30.000 35.000 A Simple Test for Effects & Interactions • Method described by Lenth (1989): Obtain s0 = 1.5*median(|Effects|) Compute: pseudo standard error: PSE = median(|Effects|*Indicator(|Effect| < 2.5*s0)) Compute Simultaneous Margin of Error: SME = t(.05/(2*Cm),d)*PSE where m = # of Effects, Cm=m(m-1)/2, d=m/3 s0 Consider effect significant if |Effect| > SME Based on this criteria, only pH main effect is significant. When not making adjustment for multiple tests (ME), 3 effects are significant or very close 2.5xs0 PSE d t(.975;d) ME gamma SME 2.145563 5.363906 1.943813 5 2.570582 4.996729 0.998293 10.14408 Estimates of Contrasts Simultaneous Margin of Error = 10.14 35 30 25 20 15 10 5 0 A -5 -10 B C D AB AC AD BC BD CD ABC ABD ACD BCD ABCD